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Sample records for ion trap mass

  1. Mini ion trap mass spectrometer

    DOEpatents

    Dietrich, D.D.; Keville, R.F.

    1995-09-19

    An ion trap is described which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10{sup 9} and commercial mass spectrometers requiring 10{sup 4} ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products. 10 figs.

  2. Mini ion trap mass spectrometer

    DOEpatents

    Dietrich, Daniel D.; Keville, Robert F.

    1995-01-01

    An ion trap which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10.sup.9 and commercial mass spectrometers requiring 10.sup.4 ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products.

  3. Halo ion trap mass spectrometer.

    PubMed

    Austin, Daniel E; Wang, Miao; Tolley, Samuel E; Maas, Jeffrey D; Hawkins, Aaron R; Rockwood, Alan L; Tolley, H Dennis; Lee, Edgar D; Lee, Milton L

    2007-04-01

    We describe a novel radio frequency ion trap mass analyzer based on toroidal trapping geometry and microfabrication technology. The device, called the halo ion trap, consists of two parallel ceramic plates, the facing surfaces of which are imprinted with sets of concentric ring electrodes. Radii of the imprinted rings range from 5 to 12 mm, and the spacing between the plates is 4 mm. Unlike conventional ion traps, in which hyperbolic metal electrodes establish equipotential boundary conditions, electric fields in the halo ion trap are established by applying different radio frequency potentials to each ring. The potential on each ring can be independently optimized to provide the best trapping field. The halo ion trap features an open structure, allowing easy access for in situ ionization. The toroidal geometry provides a large trapping and analyzing volume, increasing the number of ions that can be stored and reducing the effects of space-charge on mass analysis. Preliminary mass spectra show resolution (m/Deltam) of 60-75 when the trap is operated at 1.9 MHz and 500 Vp-p. PMID:17335180

  4. Microscale ion trap mass spectrometer

    DOEpatents

    Ramsey, J. Michael; Witten, William B.; Kornienko, Oleg

    2002-01-01

    An ion trap for mass spectrometric chemical analysis of ions is delineated. The ion trap includes a central electrode having an aperture; a pair of insulators, each having an aperture; a pair of end cap electrodes, each having an aperture; a first electronic signal source coupled to the central electrode; a second electronic signal source coupled to the end cap electrodes. The central electrode, insulators, and end cap electrodes are united in a sandwich construction where their respective apertures are coaxially aligned and symmetric about an axis to form a partially enclosed cavity having an effective radius r.sub.0 and an effective length 2z.sub.0, wherein r.sub.0 and/or z.sub.0 are less than 1.0 mm, and a ratio z.sub.0 /r.sub.0 is greater than 0.83.

  5. Non-destructive ion trap mass spectrometer and method

    DOEpatents

    Frankevich, Vladimir E.; Soni, Manish H.; Nappi, Mario; Santini, Robert E.; Amy, Jonathan W.; Cooks, Robert G.

    1997-01-01

    The invention relates to an ion trap mass spectrometer of the type having an ion trapping volume defined by spaced end caps and a ring electrode. The ion trap includes a small sensing electrode which senses characteristic motion of ions trapped in said trapping volume and provides an image current. Ions are excited into characteristic motion by application of an excitation pulse to the trapped ions. The invention also relates to a method of operating such an ion trap.

  6. Universal collisional activation ion trap mass spectrometry

    DOEpatents

    McLuckey, S.A.; Goeringer, D.E.; Glish, G.L.

    1993-04-27

    A universal collisional activation ion trap comprises an ion trapping means containing a bath gas and having connected thereto a noise signal generator. A method of operating a universal collisional activation ion trap comprises the steps of: providing an ion trapping means; introducing into the ion trapping means a bath gas; and, generating a noise signal within the ion trapping means; introducing into the ion trapping means a substance that, when acted upon by the noise signal, undergoes collisional activation to form product ions.

  7. Universal collisional activation ion trap mass spectrometry

    DOEpatents

    McLuckey, Scott A.; Goeringer, Douglas E.; Glish, Gary L.

    1993-01-01

    A universal collisional activation ion trap comprises an ion trapping means containing a bath gas and having connected thereto a noise signal generator. A method of operating a universal collisional activation ion trap comprises the steps of: providing an ion trapping means; introducing into the ion trapping means a bath gas; and, generating a noise signal within the ion trapping means; introducing into the ion trapping means a substance that, when acted upon by the noise signal, undergoes collisional activation to form product ions.

  8. Miniaturized Linear Wire Ion Trap Mass Analyzer.

    PubMed

    Wu, Qinghao; Li, Ailin; Tian, Yuan; Zare, Richard N; Austin, Daniel E

    2016-08-01

    We report a linear ion trap (LIT) in which the electric field is formed by fine wires held under tension and accurately positioned using holes drilled in two end plates made of plastic. The coordinates of the hole positions were optimized in simulation. The stability diagram and mass spectra using boundary ejection were compared between simulation and experiment and good agreement was found. The mass spectra from experiments show peak widths (fwhm) in units of mass-to-charge of around 0.38 Th using a scan rate of 3830 Th/s. The limits of detection are 137 ppbv and 401 ppbv for benzene and toluene, respectively. Different sizes of the wire ion trap can be easily fabricated by drilling holes in scaled positions. Other distinguishing features, such as high ion and photon transmission, low capacitance, high tolerance to mechanical and assembly error, and low weight, are discussed. PMID:27373557

  9. Product ion scanning using a Q-q-Q linear ion trap (Q TRAP) mass spectrometer.

    PubMed

    Hager, James W; Yves Le Blanc, J C

    2003-01-01

    The use of a Q-q-Q(linear ion trap) instrument to obtain product ion spectra is described. The instrument is based on the ion path of a triple quadrupole mass spectrometer with Q3 operable as either a conventional RF/DC quadrupole mass filter or a linear ion trap mass spectrometer with axial ion ejection. This unique ion optical arrangement allows de-coupling of precursor ion isolation and fragmentation from the ion trap itself. The result is a high sensitivity tandem mass spectrometer with triple quadrupole fragmentation patterns and no inherent low mass cut-off. The use of the entrance RF-only section of the instrument as accumulation ion trap while the linear ion trap mass spectrometer is scanning enhances duty cycles and results in increased sensitivities by as much as a factor of 20. The instrument is also capable of all of the triple quadrupole scans including multiple-reaction monitoring (MRM) as well as precursor and constant neutral loss scanning. The high product ion scanning sensitivity allows the recording of useful product ion spectra near the MRM limit of quantitation.

  10. Microfabricated quadrupole ion trap for mass spectrometer applications.

    PubMed

    Pau, S; Pai, C S; Low, Y L; Moxom, J; Reilly, P T A; Whitten, W B; Ramsey, J M

    2006-03-31

    An array of miniaturized cylindrical quadrupole ion traps, with a radius of 20 microm, is fabricated using silicon micromachining using phosphorus doped polysilicon and silicon dioxide for the purpose of creating a mass spectrometer on a chip. We have operated the array for mass-selective ion ejection and mass analysis using Xe ions at a pressure of 10(-4). The scaling rules for the ion trap in relation to operating pressure, voltage, and frequency are examined. PMID:16605890

  11. Electron source for a mini ion trap mass spectrometer

    DOEpatents

    Dietrich, D.D.; Keville, R.F.

    1995-12-19

    An ion trap is described which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10{sup 9} and commercial mass spectrometers requiring 10{sup 4} ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products. 10 figs.

  12. Electron source for a mini ion trap mass spectrometer

    DOEpatents

    Dietrich, Daniel D.; Keville, Robert F.

    1995-01-01

    An ion trap which operates in the regime between research ion traps which can detect ions with a mass resolution of better than 1:10.sup.9 and commercial mass spectrometers requiring 10.sup.4 ions with resolutions of a few hundred. The power consumption is kept to a minimum by the use of permanent magnets and a novel electron gun design. By Fourier analyzing the ion cyclotron resonance signals induced in the trap electrodes, a complete mass spectra in a single combined structure can be detected. An attribute of the ion trap mass spectrometer is that overall system size is drastically reduced due to combining a unique electron source and mass analyzer/detector in a single device. This enables portable low power mass spectrometers for the detection of environmental pollutants or illicit substances, as well as sensors for on board diagnostics to monitor engine performance or for active feedback in any process involving exhausting waste products.

  13. Ion trap array mass analyzer: structure and performance.

    PubMed

    Li, Xiaoxu; Jiang, Gongyu; Luo, Chan; Xu, Fuxing; Wang, Yuanyuan; Ding, Li; Ding, Chuan-Fan

    2009-06-15

    An ion trap array (ITA) mass analyzer--a novel ion trap mass analyzer with multiple ion trapping and analyzing channels--was designed and constructed. Its property and performance were investigated and reported in this paper. The ITA was built with several planar electrodes including two parallel printed circuit board (PCB) plates. Each PCB plate was fabricated to several identical rectangular electric strips based on normal PCB fabrication technology and was placed symmetrically to those on the opposite plate. There is no electrode between any two adjacent strips. Every strip was supplied with an rf voltage while the polarity of the voltage applied to the adjacent two strips was opposite. So the electric potential at the central plane between two adjacent strips is zero. Multiple identical electric field regions that contain the dominant quadrupole plus some other high-order fields were produced between the two PCB plates. The multiple identical electric field regions will have the property of ion trapping, ion storage, and mass analysis functions. So an ITA could work as multiple ion trap mass analyzers. It could perform multiple sample ion storage, mass-selected ion isolation, ion ejection, and mass analysis simultaneously. The ITA was operated at both "digital ion trap mode" and "conventional rf mode" experimentally. A preliminary mass spectrum has been carried out in one of the ion trap channels, and it shows a mass resolution of over 1000. Additional functions such as mass-selected ion isolation and mass-selected ion ejection have also been tested. Furthermore, the ITA has a small size and very low cost. An ITA with four channels is less than 30 cm(3) in total volume, and it shows a great promise for the miniaturization of the whole mass spectrometer instrument and high-throughput mass analysis. PMID:19441854

  14. Fundamental studies of ion injection and trapping of electrosprayed ions on a quadrupole ion trap mass spectrometer

    NASA Astrophysics Data System (ADS)

    Quarmby, Scott Thomas

    The quadrupole ion trap is a highly versatile and sensitive analytical mass spectrometer. Because of the advantages offered by the ion trap, there has been intense interest in coupling it to ionization techniques such as electrospray which form ions externally to the ion trap. In this work, experiments and computer simulations were employed to study the injection of electrosprayed ions into the ion trap of a Finnigan MAT LCQ LC/MS n mass spectrometer. The kinetic energy distribution of the ion beam was characterized and found to be relatively wide, a result of the high pressures from the atmospheric pressure source. One of the most important experimental parameters which affects ion injection efficiency is the RF voltage applied to the ring electrode. A theoretical model was fit to experimental data allowing the optimum RF voltage for trapping a given m/z ion to be predicted. Computer simulations of ion motion were performed to study the effect of various instrumental parameters on trapping efficiency. A commercially available ion optics program, SIMION v6.0, was chosen because it allowed the actual ion trap electrode geometry including endcap holes to be simulated. In contrast to previous computer simulations, SIMION provided the ability to start ions outside the ion trap and to simulate more accurately the injection of externally formed ions. The endcap holes were found to allow the RF field to penetrate out of the ion trap and affect ions as they approached the ion trap. From these simulations, a model for the process by which injected ions are trapped was developed. Using these computer simulations, techniques of improving trapping efficiency were investigated. Most previous techniques perturb ions which are already in the ion trap and therefore cannot be used to accumulate ions; the ability to accumulate ions is a necessity with ionization sources such as electrospray which form ions continuously. One such novel technique for improving trapping efficiency

  15. Differentially pumped dual linear quadrupole ion trap mass spectrometer

    SciTech Connect

    Owen, Benjamin C.; Kenttamaa, Hilkka I.

    2015-10-20

    The present disclosure provides a new tandem mass spectrometer and methods of using the same for analyzing charged particles. The differentially pumped dual linear quadrupole ion trap mass spectrometer of the present disclose includes a combination of two linear quadrupole (LQIT) mass spectrometers with differentially pumped vacuum chambers.

  16. Laser desorption in an ion trap mass spectrometer

    SciTech Connect

    Eiden, G.C.; Cisper, M.E.; Alexander, M.L.; Hemberger, P.H.; Nogar, N.S.

    1993-02-01

    Laser desorption in a ion-trap mass spectrometer shows significant promise for both qualitative and trace analysis. Several aspects of this methodology are discussed in this work. We previously demonstrated the generation of both negative and positive ions by laser desorption directly within a quadrupole ion trap. In the present work, we explore various combinations of d.c., r.f., and time-varying fields in order to optimize laser generated signals. In addition, we report on the application of this method to analyze samples containing compounds such as amines, metal complexes, carbon clusters, and polynuclear aromatic hydrocarbons. In some cases the ability to rapidly switch between positive and negative ion modes provides sufficient specificity to distinguish different compounds of a mixture with a single stage of mass spectrometry. In other experiments, we combined intensity variation studies with tandem mass spectrometry experiments and positive and negative ion detection to further enhance specificity.

  17. Collisional activation with random noise in ion trap mass spectrometry

    SciTech Connect

    McLuckey, S.A.; Goeringer, D.E.; Glish, G.L.

    1992-07-01

    Random noise applied to the end caps of a quadrupole ion trap is shown to be an effective means for the collisional activation of trapped ions independent of mass/charge ratio and number of ions. This technique is compared and contrasted with conventional single-frequency collisional activation for the molecular ion of N,N-dimethylaniline, protonated cocaine, the molecular anion of 2,4,6-trinitrotoluene, and doubly protonated neuromedin U-8. Collisional activation with noise tends to produce more extensive fragmentation than the conventional approach due to the fact that product ions are also kinetically excited in the noise experiment. The efficiency of the noise experiment in producing detectable product ions relative to the conventional approach ranges from being equivalent to being a factor of 3 less efficient. Furthermore, discrimination against low mass/charge product ions is apparent in the data from multiply charged biomolecules. Nevertheless, collisional activation with random noise provides a very simple means for overcoming problems associated with the dependence of single-frequency collisional activation on mass/charge ratio and the number of ions in the ion trap. 45 refs., 7 figs.

  18. Recent developments in ion detection techniques for Penning trap mass spectrometry at TRIGA-TRAP

    NASA Astrophysics Data System (ADS)

    Ketelaer, J.; Blaum, K.; Block, M.; Eberhardt, K.; Eibach, M.; Ferrer, R.; George, S.; Herfurth, F.; Ketter, J.; Nagy, Sz.; Repp, J.; Schweikhard, L.; Smorra, C.; Sturm, S.; Ulmer, S.

    2009-12-01

    The highest precision in the determination of nuclear and atomic masses can be achieved by Penning trap mass spectrometry. The mass value is obtained through a measurement of the cyclotron frequency of the stored charged particle. Two different approaches are used at the Penning trap mass spectrometer TRIGA-TRAP for the mass determination: the destructive Time-Of-Flight Ion Cyclotron Resonance (TOF-ICR) technique and the non-destructive Fourier Transform Ion Cyclotron Resonance (FT-ICR) method. New developments for both techniques are described, which will improve the detection efficiency and the suppression of contaminations in the case of TOF-ICR. The FT-ICR detection systems will allow for the investigation of an incoming ion bunch from a radioactive-beam facility on the one hand, and for the detection of a single singly charged ion in the Penning trap on the other hand.

  19. "Fast excitation" CID in a quadrupole ion trap mass spectrometer.

    PubMed

    Murrell, J; Despeyroux, D; Lammert, S A; Stephenson, J L; Goeringer, D E

    2003-07-01

    Collision-induced dissociation (CID) in a quadrupole ion trap mass spectrometer is usually performed by applying a small amplitude excitation voltage at the same secular frequency as the ion of interest. Here we disclose studies examining the use of large amplitude voltage excitations (applied for short periods of time) to cause fragmentation of the ions of interest. This process has been examined using leucine enkephalin as the model compound and the motion of the ions within the ion trap simulated using ITSIM. The resulting fragmentation information obtained is identical with that observed by conventional resonance excitation CID. "Fast excitation" CID deposits (as determined by the intensity ratio of the a(4)/b(4) ion of leucine enkephalin) approximately the same amount of internal energy into an ion as conventional resonance excitation CID where the excitation signal is applied for much longer periods of time. The major difference between the two excitation techniques is the higher rate of excitation (gain in kinetic energy) between successive collisions with helium atoms with "fast excitation" CID as opposed to the conventional resonance excitation CID. With conventional resonance excitation CID ions fragment while the excitation voltage is still being applied whereas for "fast excitation" CID a higher proportion of the ions fragment in the ion cooling time following the excitation pulse. The fragmentation of the (M + 17H)(17+) of horse heart myoglobin is also shown to illustrate the application of "fast excitation" CID to proteins.

  20. "Fast Excitation" CID in Quadrupole Ion Trap Mass Spectrometer

    SciTech Connect

    Murrell, J.; Despeyroux, D.; Lammert, Stephen {Steve} A; Stephenson Jr, James {Jim} L; Goeringer, Doug

    2003-01-01

    Collision-induced dissociation (CID) in a quadrupole ion trap mass spectrometer is usually performed by applying a small amplitude excitation voltage at the same secular frequency as the ion of interest. Here we disclose studies examining the use of large amplitude voltage excitations (applied for short periods of time) to cause fragmentation of the ions of interest. This process has been examined using leucine enkephalin as the model compound and the motion of the ions within the ion trap simulated using ITSIM. The resulting fragmentation information obtained is identical with that observed by conventional resonance excitation CID. ''Fast excitation'' CID deposits (as determined by the intensity ratio of the a{sub 4}/b{sub 4} ion of leucine enkephalin) approximately the same amount of internal energy into an ion as conventional resonance excitation CID where the excitation signal is applied for much longer periods of time. The major difference between the two excitation techniques is the higher rate of excitation (gain in kinetic energy) between successive collisions with helium atoms with ''fast excitation'' CID as opposed to the conventional resonance excitation CID. With conventional resonance excitation CID ions fragment while the excitation voltage is still being applied whereas for ''fast excitation'' CID a higher proportion of the ions fragment in the ion cooling time following the excitation pulse. The fragmentation of the (M + 17H){sup 17+} of horse heart myoglobin is also shown to illustrate the application of ''fast excitation'' CID to proteins.

  1. 10 K Ring Electrode Trap - Tandem Mass Spectrometer for Infrared Spectroscopy of Mass Selected Ions

    SciTech Connect

    Goebbert, Daniel J.; Meijer, Gerard; Asmis, Knut R.

    2009-03-17

    A novel instrumental setup for measuring infrared photodissociation spectra of buffer gas cooled, mass-selected ions is described and tested. It combines a cryogenically cooled, linear radio frequency ion trap with a tandem mass spectrometer, optimally coupling continuous ion sources to pulsed laser experiments. The use of six independently adjustable DC potentials superimposed over the trapping radio frequency field provides control over the ion distribution within, as well as the kinetic energy distribution of the ions extracted from the ion trap. The scheme allows focusing the ions in space and time, such that they can be optimally irradiated by a pulsed, widely tunable infrared photodissociation laser. Ion intensities are monitored with a time-of-flight mass spectrometer mounted orthogonally to the ion trap axis.

  2. Octupole Excitation of Trapped Ion Motion for Precision Mass Measurements

    NASA Astrophysics Data System (ADS)

    Bollen, G.; Ringle, R.; Schury, P.; Schwarz, S.; Sun, T.

    2005-04-01

    National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI, USA An azimuthal octupole radiofrequency field has been used to excite the ion motion of ^40Ar^+ ions stored in a Penning trap. A resonant response was observed at twice the ions' true cyclotron frequency φc=q/m.B. The experiment has been performed with the 9.4-T Penning trap system of the recently commissioned LEBIT facility at the NSCL at MSU [1]. Similar to the excitation with an azimuthal quadrupole field at φc [2,3], octupole excitation at 2φc gives rise to a periodic beating of the ion motion between magnetron and reduced cyclotron motion. Differences are observed in the dependence of the excited ion motion on initial amplitudes and phases of the radial eigen motions. The observed behavior of the ions is found to be in good agreement with the results of numerical simulations. The technique still requires further testing but the first results indicate that 2φc excitation may provide benefits that are similar to doubling the magnetic field strength B. In particular precision mass measurements of short-lived rare isotopes may benefit from this technique by being able to reach a given precision with shorter ion storage and observation times. [1] S. Schwarz et al, Nucl. Instr. Meth. B204 (2004) 507 [2] G. Bollen et al., J. Appl. Phys. 68 (1990) 4355 [3] M. König et al., Int. J. Mass Spec. Ion. Proc. 142 (1995) 95

  3. Laser desorption lamp ionization source for ion trap mass spectrometry.

    PubMed

    Wu, Qinghao; Zare, Richard N

    2015-01-01

    A two-step laser desorption lamp ionization source coupled to an ion trap mass spectrometer (LDLI-ITMS) has been constructed and characterized. The pulsed infrared (IR) output of an Nd:YAG laser (1064 nm) is directed to a target inside a chamber evacuated to ~15 Pa causing desorption of molecules from the target's surface. The desorbed molecules are ionized by a vacuum ultraviolet (VUV) lamp (filled with xenon, major wavelength at 148 nm). The resulting ions are stored and detected in a three-dimensional quadrupole ion trap modified from a Finnigan Mat LCQ mass spectrometer operated at a pressure of ≥ 0.004 Pa. The limit of detection for desorbed coronene molecules is 1.5 pmol, which is about two orders of magnitude more sensitive than laser desorption laser ionization mass spectrometry using a fluorine excimer laser (157 nm) as the ionization source. The mass spectrum of four standard aromatic compounds (pyrene, coronene, rubrene and 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (OPC)) shows that parent ions dominate. By increasing the infrared laser power, this instrument is capable of detecting inorganic compounds. PMID:25601688

  4. Absorption mode Fourier transform electrostatic linear ion trap mass spectrometry.

    PubMed

    Hilger, Ryan T; Wyss, Phillip J; Santini, Robert E; McLuckey, Scott A

    2013-09-01

    In Fourier transform mass spectrometry, it is well-known that plotting the spectrum in absorption mode rather than magnitude mode has several advantages. However, magnitude spectra remain commonplace due to difficulties associated with determining the phase of each frequency at the onset of data acquisition, which is required for generating absorption spectra. The phasing problem for electrostatic traps is much simpler than for Fourier transform ion cyclotron resonance (FTICR) instruments, which greatly simplifies the generation of absorption spectra. Here, we present a simple method for generating absorption spectra from a Fourier transform electrostatic linear ion trap mass spectrometer. The method involves time shifting the data prior to Fourier transformation in order to synchronize the onset of data acquisition with the moment of ion acceleration into the electrostatic trap. Under these conditions, the initial phase of each frequency at the onset of data acquisition is zero. We demonstrate that absorption mode provides a 1.7-fold increase in resolution (full width at half maximum, fwhm) as well as reduced peak tailing. We also discuss methodology that may be applied to unsynchronized data in order to determine the time shift required to generate an absorption spectrum.

  5. Characterization of protonated phospholipids as fragile ions in quadrupole ion trap mass spectrometry

    PubMed Central

    Garrett, Timothy J.; Merves, Matthew; Yost, Richard A.

    2011-01-01

    Some ions exhibit “ion fragility” in quadrupole ion trap mass spectrometry (QIT-MS) during mass analysis with resonance ejection. In many cases, different ions generated from the same compound exhibit different degrees of ion fragility, with some ions (e.g., the [M+H]+ ion) stable and other ions (e.g., the [M+Na]+ ion) fragile. The ion fragility for quadrupole ion trap (QIT) mass spectrometry (MS) for protonated and sodiated ions of three phospholipids, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, PC (16:0/16:0), 1,2-dipalmitoyl-sn-glycero-3-phophoethanolamine, PE (16:0/16:0), and N-palmitoyl-D-erythro-sphingosylphosphorylcholine, SM (d18:1/16:0), was determined using three previously developed experiments: 1) the peak width using a slow scan speed, 2) the width of the isolation window for efficient isolation, and 3) the energy required for collision-induced dissociation. In addition, ion fragility studies were designed and performed to explore a correlation between ion fragility in QIT mass analysis and ion fragility during transport between the ion source and the ion trap. These experiments were: 1) evaluating the amount of thermal-induced dissociation as a function of heated capillary temperature, and 2) determining the extent of fragmentation occurring with increasing tube lens voltage. All phospholipid species studied exhibited greater ion fragility as protonated species in ion trap mass analysis than as sodiated species. In addition, the protonated species of both SM (d18:0/16:0) and PC (16:0/16:0) exhibited greater tendencies to fragment at higher heated capillary temperatures and high tube lens voltages, whereas the PE (16:0/16:0) ions did not appear to exhibit fragility during ion transport. PMID:22247650

  6. Ion sponge: a 3-dimentional array of quadrupole ion traps for trapping and mass-selectively processing ions in gas phase.

    PubMed

    Xu, Wei; Li, Linfan; Zhou, Xiaoyu; Ouyang, Zheng

    2014-05-01

    In this study, the concept of ion sponge has been explored for developing 3D arrays of large numbers of ion traps but with simple configurations. An ion sponge device with 484 trapping units in a volume of 10 × 10 × 3.2 cm has been constructed by simply stacking 9 meshes together. A single rf was used for trapping ions and mass-selective ion processing. The ion sponge provides a large trapping capacity and is highly transparent for transfer of ions, neutrals, and photons for gas phase ion processing. Multiple layers of quadrupole ion traps, with 121 trapping units in each layer, can operate as a single device for MS or MS/MS analysis, or as a series of mass-selective trapping devices with interlayer ion transfers facilitated by AC and DC voltages. Automatic sorting of ions to different trapping layers based on their mass-to-charge (m/z) ratios was achieved with traps of different sizes. Tandem-in-space MS/MS has also been demonstrated with precursor ions and fragment ions trapped in separate locations.

  7. Ion Sponge: A 3-Dimentional Array of Quadrupole Ion Traps for Trapping and Mass-Selectively Processing Ions in Gas Phase

    PubMed Central

    2015-01-01

    In this study, the concept of ion sponge has been explored for developing 3D arrays of large numbers of ion traps but with simple configurations. An ion sponge device with 484 trapping units in a volume of 10 × 10 × 3.2 cm has been constructed by simply stacking 9 meshes together. A single rf was used for trapping ions and mass-selective ion processing. The ion sponge provides a large trapping capacity and is highly transparent for transfer of ions, neutrals, and photons for gas phase ion processing. Multiple layers of quadrupole ion traps, with 121 trapping units in each layer, can operate as a single device for MS or MS/MS analysis, or as a series of mass-selective trapping devices with interlayer ion transfers facilitated by AC and DC voltages. Automatic sorting of ions to different trapping layers based on their mass-to-charge (m/z) ratios was achieved with traps of different sizes. Tandem-in-space MS/MS has also been demonstrated with precursor ions and fragment ions trapped in separate locations. PMID:24758328

  8. Monitoring Trace Contaminants in Air Via Ion Trap Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Palmer, Peter T.; Karr, Dane; Pearson, Richard; Valero, Gustavo; Wong, Carla

    1995-01-01

    Recent passage of the Clean Air Act with its stricter regulation of toxic gas emissions, and the ever-growing number of applications which require faster turnaround times between sampling and analysis are two major factors which are helping to drive the development of new instrument technologies for in-situ, on-line, real-time monitoring. The ion trap, with its small size, excellent sensitivity, and tandem mass spectrometry capability is a rapidly evolving technology which is well-suited for these applications. In this paper, we describe the use of a commercial ion trap instrument for monitoring trace levels of chlorofluorocarbons (CFCs) and volatile organic compounds (VOCs) in air. A number of sample introduction devices including a direct transfer line interface, short column GC, and a cryotrapping interface are employed to achieve increasing levels of sensitivity. MS, MS/MS, and MS/MS/MS methods are compared to illustrate trade-offs between sensitivity and selectivity. Filtered Noise Field (FNF) technology is found to be an excellent means for achieving lower detection limits through selective storage of the ion(s) of interest during ionization. Figures of merit including typical sample sizes, detection limits, and response times are provided. The results indicate the potential of these techniques for atmospheric assessments, the High Speed Research Program, and advanced life support monitoring applications for NASA.

  9. Fluorescence Imaging for Visualization of the Ion Cloud in a Quadrupole Ion Trap Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Talbot, Francis O.; Sciuto, Stephen V.; Jockusch, Rebecca A.

    2013-12-01

    Laser-induced fluorescence is used to visualize populations of gaseous ions stored in a quadrupole ion trap (QIT) mass spectrometer. Presented images include the first fluorescence image of molecular ions collected under conditions typically used in mass spectrometry experiments. Under these "normal" mass spectrometry conditions, the radial ( r) and axial ( z) full-width at half maxima (FWHM) of the detected ion cloud are 615 and 214 μm, respectively, corresponding to ~6 % of r 0 and ~3 % of z 0 for the QIT used. The effects on the shape and size of the ion cloud caused by varying the pressure of helium bath gas, the number of trapped ions, and the Mathieu parameter q z are visualized and discussed. When a "tickle voltage" is applied to the exit end-cap electrode, as is done in collisionally activated dissociation, a significant elongation in the axial, but not the radial, dimension of the ion cloud is apparent. Finally, using spectroscopically distinguishable fluorophores of two different m/ z values, images are presented that illustrate stratification of the ion cloud; ions of lower m/ z (higher q z ) are located in the center of the trapping region, effectively excluding higher m/ z (lower q z ) ions, which form a surrounding layer. Fluorescence images such as those presented here provide a useful reference for better understanding the collective behavior of ions in radio frequency (rf) trapping devices and how phenomena such as collisions and space-charge affect ion distribution.

  10. Multiple mass analysis using an ion trap array (ITA) mass analyzer.

    PubMed

    Yu, Xiao; Chu, Yanqiu; Ling, Xing; Ding, Zhengzhi; Xu, Chongsheng; Ding, Li; Ding, Chuan-Fan

    2013-09-01

    A novel ion trap array (ITA) mass analyzer with six ion trapping and analyzing channels was investigated. It is capable of analyzing multiple samples simultaneously. The ITA was built with several planar electrodes made of stainless steel and 12 identical parallel zirconia ceramic substrates plated with conductive metal layers. Each two of the opposing ceramic electrode plates formed a boundary of an ion trap channel and six identical ion trapping and analyzing channels were placed in parallel without physical electrode between any two adjacent channels. The electric field distribution inside each channel was studied with simulation. The new design took the advantage of high precision machining attributable to the rigidity of ceramic, and the convenience of surface patterning technique. The ITA system was tested by using a two-channel electrospray ionization source, a multichannel simultaneous quadruple ion guide, and two detectors. The simultaneous analysis of two different samples with two adjacent ITA channels was achieved and independent mass spectra were obtained. For each channel, the mass resolution was tested. Additional ion trap functions such as mass-selected ion isolation and collision-induced dissociation (CID) were also tested. The results show that one ITA is well suited for multiple simultaneous mass analyses. PMID:23797864

  11. Multiple Mass Analysis Using an Ion Trap Array (ITA) Mass Analyzer

    NASA Astrophysics Data System (ADS)

    Xiao, Yu; Chu, Yanqiu; Ling, Xing; Ding, Zhengzhi; Xu, Chongsheng; Ding, Li; Ding, Chuan-Fan

    2013-09-01

    A novel ion trap array (ITA) mass analyzer with six ion trapping and analyzing channels was investigated. It is capable of analyzing multiple samples simultaneously. The ITA was built with several planar electrodes made of stainless steel and 12 identical parallel zirconia ceramic substrates plated with conductive metal layers. Each two of the opposing ceramic electrode plates formed a boundary of an ion trap channel and six identical ion trapping and analyzing channels were placed in parallel without physical electrode between any two adjacent channels. The electric field distribution inside each channel was studied with simulation. The new design took the advantage of high precision machining attributable to the rigidity of ceramic, and the convenience of surface patterning technique. The ITA system was tested by using a two-channel electrospray ionization source, a multichannel simultaneous quadruple ion guide, and two detectors. The simultaneous analysis of two different samples with two adjacent ITA channels was achieved and independent mass spectra were obtained. For each channel, the mass resolution was tested. Additional ion trap functions such as mass-selected ion isolation and collision-induced dissociation (CID) were also tested. The results show that one ITA is well suited for multiple simultaneous mass analyses.

  12. A hand-portable digital linear ion trap mass spectrometer.

    PubMed

    Xue, Bing; Sun, Lulu; Huang, Zhengxu; Gao, Wei; Fan, Rongrong; Cheng, Ping; Ding, Li; Ma, Li; Zhou, Zhen

    2016-10-01

    A hand-portable digital linear ion trap mass spectrometer (DLIT-MS) has been developed for VOC analysis. It has a weight of 18 kg with dimensions of 49 cm × 39 cm × 16 cm, and consumes an average power of ca. 60 W. As a result of the introduction of a digital waveform, the DLIT-MS can be driven at a lower voltage (±100 V) to cover a mass range of 30-300 Th with a unit resolution. Compact electronics has been designed to control the DLIT-MS and record mass spectra. The mass drift was reduced after the improvement in electronics to stabilize the digital waveform voltage during the mass scan. Tandem mass spectrometry (MS) has been achieved by using digital asymmetric waveform isolation (DAWI), forward and reverse scan, and collision induced dissociation (CID). The isolation and CID efficiency for methyl salicylate were 83.9% and 81.3%, respectively. A novel buffer gas inlet system was designed to enhance the sensitivity and allow easy and safe use of the instrument. Limits of detection below 1 ppbv were obtained for several mixed gaseous samples. PMID:27396834

  13. A hand-portable digital linear ion trap mass spectrometer.

    PubMed

    Xue, Bing; Sun, Lulu; Huang, Zhengxu; Gao, Wei; Fan, Rongrong; Cheng, Ping; Ding, Li; Ma, Li; Zhou, Zhen

    2016-10-01

    A hand-portable digital linear ion trap mass spectrometer (DLIT-MS) has been developed for VOC analysis. It has a weight of 18 kg with dimensions of 49 cm × 39 cm × 16 cm, and consumes an average power of ca. 60 W. As a result of the introduction of a digital waveform, the DLIT-MS can be driven at a lower voltage (±100 V) to cover a mass range of 30-300 Th with a unit resolution. Compact electronics has been designed to control the DLIT-MS and record mass spectra. The mass drift was reduced after the improvement in electronics to stabilize the digital waveform voltage during the mass scan. Tandem mass spectrometry (MS) has been achieved by using digital asymmetric waveform isolation (DAWI), forward and reverse scan, and collision induced dissociation (CID). The isolation and CID efficiency for methyl salicylate were 83.9% and 81.3%, respectively. A novel buffer gas inlet system was designed to enhance the sensitivity and allow easy and safe use of the instrument. Limits of detection below 1 ppbv were obtained for several mixed gaseous samples.

  14. The effective temperature of ions stored in a linear quadrupole ion trap mass spectrometer.

    PubMed

    Donald, William A; Khairallah, George N; O'Hair, Richard A J

    2013-06-01

    The extent of internal energy deposition into ions upon storage, radial ejection, and detection using a linear quadrupole ion trap mass spectrometer is investigated as a function of ion size (m/z 59 to 810) using seven ion-molecule thermometer reactions that have well characterized reaction entropies and enthalpies. The average effective temperatures of the reactants and products of the ion-molecule reactions, which were obtained from ion-molecule equilibrium measurements, range from 295 to 350 K and do not depend significantly on the number of trapped ions, m/z value, ion trap q z value, reaction enthalpy/entropy, or the number of vibrational degrees of freedom for the seven reactions investigated. The average of the effective temperature values obtained for all seven thermometer reactions is 318 ± 23 K, which indicates that linear quadrupole ion trap mass spectrometers can be used to study the structure(s) and reactivity of ions at near ambient temperature.

  15. A mass- and velocity-broadband ion deflector for off-axis ion injection into a cyclotron resonance ion trap

    NASA Astrophysics Data System (ADS)

    Guan, Shenheng; Marshall, Alan G.

    1996-02-01

    Off-axis ion injection into an FT-ICR ion trap is desirable for capturing ions from a continuously generated beam (e.g., electrospray). A conventional E×B (Wien) filter focuses ions of a single velocity (independent of mass). Here we show that by segmenting opposed flat electrodes into small sections, the electric field may be tailored to produce well-focused ion trajectories over a wide range of ion velocity and mass-to-charge ratio, m/z. In the limit of infinitely extended deflector electrodes, small m/z, and/or high B, ion trajectories vary as powers or roots of distance.

  16. Development and Evaluation of a Variable-Temperature Quadrupole Ion Trap Mass Spectrometer.

    PubMed

    Derkits, David; Wiseman, Alex; Snead, Russell F; Dows, Martina; Harge, Jasmine; Lamp, Jared A; Gronert, Scott

    2016-02-01

    A new, variable-temperature mass spectrometer system is described. By applying polyimide heating tape to the end-cap electrodes of a Bruker (Bremen, Germany) Esquire ion trap, it is possible to vary the effective temperature of the system between 40 and 100°C. The modification does not impact the operation of the ion trap and the heater can be used for extended periods without degradation of the system. The accuracy of the ion trap temperatures was assessed by examining two gas-phase equilibrium processes with known thermochemistry. In each case, the variable-temperature ion trap provided data that were in good accord with literature data, indicating the effective temperature in the ion trap environment was being successfully modulated by the changes in the set-point temperatures on the end-cap electrodes. The new design offers a convenient and effective way to convert commercial ion trap mass spectrometers into variable-temperature instruments. PMID:26483183

  17. Augmenting Ion Trap Mass Spectrometers Using a Frequency Modulated Drift Tube Ion Mobility Spectrometer.

    PubMed

    Morrison, Kelsey A; Siems, William F; Clowers, Brian H

    2016-03-15

    Historically, high pressure ion mobility drift tubes have suffered from low ion duty cycles and this problem is magnified when such instrumentation is coupled with ion trap mass spectrometers. To significantly alleviate these issues, we outline the result from coupling an atmospheric pressure, dual-gate drift tube ion mobility spectrometer (IMS) to a linear ion trap mass spectrometer (LIT-MS) via modulation of the ion beam with a linear frequency chirp. The time-domain ion current, once Fourier transformed, reveals a standard ion mobility drift spectrum that corresponds to the standard mode of mobility analysis. By multiplexing the ion beam, it is possible to successfully obtain drift time spectra for an assortment of simple peptide and protein mixtures using an LIT-MS while showing improved signal intensity versus the more common signal averaging technique. Explored here are the effects of maximum injection time, solution concentration, total experiment time, and frequency swept on signal-to-noise ratios (SNRs) and resolving power. Increased inject time, concentration, and experiment time all generally led to an improvement in SNR, while a greater frequency swept increases the resolving power at the expense of SNR. Overall, chirp multiplexing of a dual-gate IMS system coupled to an LIT-MS improves ion transmission, lowers analyte detection limits, and improves spectral quality. PMID:26854901

  18. Electron Flood Charge Compensation Device for Ion Trap Secondary Ion Mass Spectrometry

    SciTech Connect

    Appelhans, Anthony David; Ward, Michael Blair; Olson, John Eric

    2002-11-01

    During secondary ion mass spectrometry (SIMS) analyses of organophosphorous compounds adsorbed onto soils, the measured anion signals were lower than expected and it was hypothesized that the low signals could be due to sample charging. An electron flood gun was designed, constructed and used to investigate sample charging of these and other sample types. The flood gun was integrated into one end cap of an ion trap secondary ion mass spectrometer and the design maintained the geometry of the self-stabilizing extraction optics used in this instrument. The SIMION ion optics program was used to design the flood gun, and experimental results agreed with the predicted performance. Results showed the low anion signals from the soils were not due to sample charging. Other insulating and conducting samples were tested using both a ReO4- and a Cs+ primary ion beam. The proximity of the sample and electron source to the ion trap aperture resulted in generation of background ions in the ion trap via electron impact (EI) ionization during the period the electron gun was flooding the sample region. When using the electron gun with the ReO4- primary beam, the required electron current was low enough that the EI background was negligible; however, the high electron flood current required with the Cs+ beam produced background EI ions that degraded the quality of the mass spectra. The consequences of the EI produced cations will have to be evaluated on a sample-by-sample basis when using electron flood. It was shown that the electron flood gun could be intentionally operated to produce EI spectra in this instrument. This offers the opportunity to measure, nearly simultaneously, species evaporating from a sample, via EI, and species bound to the surface, via SIMS.

  19. UV photodissociation of trapped ions following ion mobility separation in a Q-ToF mass spectrometer.

    PubMed

    Bellina, Bruno; Brown, Jeffery M; Ujma, Jakub; Murray, Paul; Giles, Kevin; Morris, Michael; Compagnon, Isabelle; Barran, Perdita E

    2014-12-21

    An ion mobility mass spectrometer has been modified to allow optical interrogation of ions with different mass-to-charge (m/z) ratios and/or mobilities (K). An ion gating and trapping procedure has been developed which allows us to store ions for several seconds enabling UV photodissociation (UVPD).

  20. Microfabricated ion trap array

    DOEpatents

    Blain, Matthew G.; Fleming, James G.

    2006-12-26

    A microfabricated ion trap array, comprising a plurality of ion traps having an inner radius of order one micron, can be fabricated using surface micromachining techniques and materials known to the integrated circuits manufacturing and microelectromechanical systems industries. Micromachining methods enable batch fabrication, reduced manufacturing costs, dimensional and positional precision, and monolithic integration of massive arrays of ion traps with microscale ion generation and detection devices. Massive arraying enables the microscale ion traps to retain the resolution, sensitivity, and mass range advantages necessary for high chemical selectivity. The reduced electrode voltage enables integration of the microfabricated ion trap array with on-chip circuit-based rf operation and detection electronics (i.e., cell phone electronics). Therefore, the full performance advantages of the microfabricated ion trap array can be realized in truly field portable, handheld microanalysis systems.

  1. Advances in ion trap mass spectrometry: Photodissociation as a tool for structural elucidation

    SciTech Connect

    Stephenson, J.L. Jr.; Booth, M.M.; Eyler, J.R.; Yost, R.A.

    1995-12-01

    Photo-induced dissociation (PID) is the next most frequently used method (after collisional activation) for activation of Polyatomic ions in tandem mass spectrometry. The range of internal energies present after the photon absorption process are much narrower than those obtained with collisional energy transfer. Therefore, the usefulness of PID for the study of ion structures is greatly enhanced. The long storage times and instrumental configuration of the ion trap mass spectrometer are ideally suited for photodissociation experiments. This presentation will focus on both the fundamental and analytical applications of CO{sub 2} lasers in conjunction with ion trap mass spectrometry. The first portion of this talk will examine the fundamental issues of wavelength dependence, chemical kinetics, photoabsorption cross section, and collisional effects on photodissociation efficiency. The second half of this presentation will look at novel instrumentation for electrospray/ion trap mass spectrometry, with the concurrent development of photodissociation as a tool for structural elucidation of organic compounds and antibiotics.

  2. Secondary Ion Mass Spectrometry of Zeolite Materials: Observation of Abundant Aluminosilicate Oligomers Using an Ion Trap

    SciTech Connect

    Groenewold, Gary Steven; Kessinger, Glen Frank; Scott, Jill Rennee; Gianotto, Anita Kay; Appelhans, Anthony David; Delmore, James Edward

    2000-12-01

    Oligomeric oxyanions were observed in the secondary ion mass spectra (SIMS) of zeolite materials. The oxyanions have the general composition AlmSinO2(m+n)H(m-1)- (m + n = 2 to 8) and are termed dehydrates. For a given mass, multiple elemental compositions are possible because (Al + H) is an isovalent and isobaric substitute for Si. Using 18 keV Ga+ as a projectile, oligomer abundances are low relative to the monomers. Oligomer abundance can be increased by using the polyatomic projectile ReO4- (~5 keV). Oligomer abundance can be further increased using an ion trap (IT-) SIMS; in this instrument, long ion lifetimes (tens of ms) and relatively high He pressure result in significant collisional stabilization and increased high-mass abundance. The dehydrates rapidly react with adventitious H2O present in the IT-SIMS to form mono-, di-, and trihydrates. The rapidity of the reaction and comparison to aluminum oxyanion hydration suggest that H2O adds to the aluminosilicate oxyanions in a dissociative fashion, forming covalently bound product ions. In addition to these findings, it was noted that production of abundant oligomeric aluminosilicates could be significantly increased by substituting the countercation (NH4+) with the larger alkali ions Rb+ and Cs+. This constitutes a useful tactic for generating large aluminosilicate oligomers for surface characterization and ion-molecule reactivity studies.

  3. Experimental Characterization of Secular Frequency Scanning in Ion Trap Mass Spectrometers.

    PubMed

    Snyder, Dalton T; Pulliam, Christopher J; Wiley, Joshua S; Duncan, Jason; Cooks, R Graham

    2016-07-01

    Secular frequency scanning is implemented and characterized using both a benchtop linear ion trap and a miniature rectilinear ion trap mass spectrometer. Separation of tetraalkylammonium ions and those from a mass calibration mixture and from a pesticide mixture is demonstrated with peak widths approaching unit resolution for optimized conditions using the benchtop ion trap. The effects on the spectra of ion trap operating parameters, including waveform amplitude, scan direction, scan rate, and pressure are explored, and peaks at black holes corresponding to nonlinear (higher-order field) resonance points are investigated. Reverse frequency sweeps (increasing mass) on the Mini 12 are shown to result in significantly higher ion ejection efficiency and superior resolution than forward frequency sweeps that decrement mass. This result is accounted for by the asymmetry in ion energy absorption profiles as a function of AC frequency and the shift in ion secular frequency at higher amplitudes in the trap due to higher order fields. We also found that use of higher AC amplitudes in forward frequency sweeps biases ions toward ejection at points of higher order parametric resonance, despite using only dipolar excitation. Higher AC amplitudes also increase peak width and decrease sensitivity in both forward and reverse frequency sweeps. Higher sensitivity and resolution were obtained at higher trap pressures in the secular frequency scan, in contrast to conventional resonance ejection scans, which showed the opposite trend in resolution on the Mini 12. Mass range is shown to be naturally extended in secular frequency scanning when ejecting ions by sweeping the AC waveform through low frequencies, a method which is similar, but arguably superior, to the more usual method of mass range extension using low q resonance ejection. Graphical Abstract ᅟ. PMID:27032650

  4. Experimental Characterization of Secular Frequency Scanning in Ion Trap Mass Spectrometers

    NASA Astrophysics Data System (ADS)

    Snyder, Dalton T.; Pulliam, Christopher J.; Wiley, Joshua S.; Duncan, Jason; Cooks, R. Graham

    2016-07-01

    Secular frequency scanning is implemented and characterized using both a benchtop linear ion trap and a miniature rectilinear ion trap mass spectrometer. Separation of tetraalkylammonium ions and those from a mass calibration mixture and from a pesticide mixture is demonstrated with peak widths approaching unit resolution for optimized conditions using the benchtop ion trap. The effects on the spectra of ion trap operating parameters, including waveform amplitude, scan direction, scan rate, and pressure are explored, and peaks at black holes corresponding to nonlinear (higher-order field) resonance points are investigated. Reverse frequency sweeps (increasing mass) on the Mini 12 are shown to result in significantly higher ion ejection efficiency and superior resolution than forward frequency sweeps that decrement mass. This result is accounted for by the asymmetry in ion energy absorption profiles as a function of AC frequency and the shift in ion secular frequency at higher amplitudes in the trap due to higher order fields. We also found that use of higher AC amplitudes in forward frequency sweeps biases ions toward ejection at points of higher order parametric resonance, despite using only dipolar excitation. Higher AC amplitudes also increase peak width and decrease sensitivity in both forward and reverse frequency sweeps. Higher sensitivity and resolution were obtained at higher trap pressures in the secular frequency scan, in contrast to conventional resonance ejection scans, which showed the opposite trend in resolution on the Mini 12. Mass range is shown to be naturally extended in secular frequency scanning when ejecting ions by sweeping the AC waveform through low frequencies, a method which is similar, but arguably superior, to the more usual method of mass range extension using low q resonance ejection.

  5. Experimental Characterization of Secular Frequency Scanning in Ion Trap Mass Spectrometers.

    PubMed

    Snyder, Dalton T; Pulliam, Christopher J; Wiley, Joshua S; Duncan, Jason; Cooks, R Graham

    2016-07-01

    Secular frequency scanning is implemented and characterized using both a benchtop linear ion trap and a miniature rectilinear ion trap mass spectrometer. Separation of tetraalkylammonium ions and those from a mass calibration mixture and from a pesticide mixture is demonstrated with peak widths approaching unit resolution for optimized conditions using the benchtop ion trap. The effects on the spectra of ion trap operating parameters, including waveform amplitude, scan direction, scan rate, and pressure are explored, and peaks at black holes corresponding to nonlinear (higher-order field) resonance points are investigated. Reverse frequency sweeps (increasing mass) on the Mini 12 are shown to result in significantly higher ion ejection efficiency and superior resolution than forward frequency sweeps that decrement mass. This result is accounted for by the asymmetry in ion energy absorption profiles as a function of AC frequency and the shift in ion secular frequency at higher amplitudes in the trap due to higher order fields. We also found that use of higher AC amplitudes in forward frequency sweeps biases ions toward ejection at points of higher order parametric resonance, despite using only dipolar excitation. Higher AC amplitudes also increase peak width and decrease sensitivity in both forward and reverse frequency sweeps. Higher sensitivity and resolution were obtained at higher trap pressures in the secular frequency scan, in contrast to conventional resonance ejection scans, which showed the opposite trend in resolution on the Mini 12. Mass range is shown to be naturally extended in secular frequency scanning when ejecting ions by sweeping the AC waveform through low frequencies, a method which is similar, but arguably superior, to the more usual method of mass range extension using low q resonance ejection. Graphical Abstract ᅟ.

  6. Ion Funnel Trap Interface for Orthogonal Time-of-Flight Mass Spectrometry

    SciTech Connect

    Ibrahim, Yehia M.; Belov, Mikhail E.; Tolmachev, Aleksey V.; Prior, David C.; Smith, Richard D.

    2007-10-15

    A combined electrodynamic ion funnel and ion trap coupled to an orthogonal acceleration (oa)-time-of-flight mass spectrometer was developed and characterized. The ion trap was incorporated through the use of added terminal electrodynamic ion funnel electrodes enabling control over the axial dc gradient in the trap section. The ion trap operates efficiently at a pressure of ~1 Torr, and measurements indicate a maximum charge capacity of ~3 × 107 charges. An order of magnitude increase in sensitivity was observed in the analysis of low concentration peptides mixtures with orthogonal acceleration (oa)-time-of-flight mass spectrometry (oa-TOF MS) in the trapping mode as compared to the continuous regime. A signal increase in the trapping mode was accompanied by reduction in the chemical background, due to more efficient desolvation of, for example, solvent related clusters. Controlling the ion trap ejection time was found to result in efficient removal of singly charged species and improving signal-to-noise ratio (S/N) for the multiply charged analytes.

  7. Ion Trap with Narrow Aperture Detection Electrodes for Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Nagornov, Konstantin O.; Kozhinov, Anton N.; Tsybin, Oleg Y.; Tsybin, Yury O.

    2015-05-01

    The current paradigm in ion trap (cell) design for Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is the ion detection with wide aperture detection electrodes. Specifically, excitation and detection electrodes are typically 90° wide and positioned radially at a similar distance from the ICR cell axis. Here, we demonstrate that ion detection with narrow aperture detection electrodes (NADEL) positioned radially inward of the cell's axis is feasible and advantageous for FT-ICR MS. We describe design details and performance characteristics of a 10 T FT-ICR MS equipped with a NADEL ICR cell having a pair of narrow aperture (flat) detection electrodes and a pair of standard 90° excitation electrodes. Despite a smaller surface area of the detection electrodes, the sensitivity of the NADEL ICR cell is not reduced attributable to improved excite field distribution, reduced capacitance of the detection electrodes, and their closer positioning to the orbits of excited ions. The performance characteristics of the NADEL ICR cell are comparable with the state-of-the-art FT-ICR MS implementations for small molecule, peptide, protein, and petroleomics analyses. In addition, the NADEL ICR cell's design improves the flexibility of ICR cells and facilitates implementation of advanced capabilities (e.g., quadrupolar ion detection for improved mainstream applications). It also creates an intriguing opportunity for addressing the major bottleneck in FTMS—increasing its throughput via simultaneous acquisition of multiple transients or via generation of periodic non-sinusoidal transient signals.

  8. Infrared ion spectroscopy in a modified quadrupole ion trap mass spectrometer at the FELIX free electron laser laboratory

    NASA Astrophysics Data System (ADS)

    Martens, Jonathan; Berden, Giel; Gebhardt, Christoph R.; Oomens, Jos

    2016-10-01

    We report on modifications made to a Paul-type quadrupole ion trap mass spectrometer and discuss its application in infrared ion spectroscopy experiments. Main modifications involve optical access to the trapped ions and hardware and software coupling to a variety of infrared laser sources at the FELIX infrared free electron laser laboratory. In comparison to previously described infrared ion spectroscopy experiments at the FELIX laboratory, we find significant improvements in efficiency and sensitivity. Effects of the trapping conditions of the ions on the IR multiple photon dissociation spectra are explored. Enhanced photo-dissociation is found at lower pressures in the ion trap. Spectra obtained under reduced pressure conditions are found to more closely mimic those obtained in the high-vacuum conditions of an Fourier transform ion cyclotron resonance mass spectrometer. A gas-mixing system is described enabling the controlled addition of a secondary gas into helium buffer gas flowing into the trap and allows for ion/molecule reactions in the trap. The electron transfer dissociation (ETD) option of the mass spectrometer allows for IR structure characterization of ETD-generated peptide dissociation products.

  9. Infrared Multiphoton Dissociation of Peptide Cations in a Dual Pressure Linear Ion Trap Mass Spectrometer

    PubMed Central

    Gardner, Myles W.; Smith, Suncerae I.; Ledvina, Aaron R.; Madsen, James A.; Coon, Joshua J.; Schwartz, Jae C.; Stafford, George C.; Brodbelt, Jennifer S.

    2009-01-01

    A dual pressure linear ion trap mass spectrometer was modified to permit infrared multiphoton dissociation (IRMPD) in each of the two cells - the first a high pressure cell operated at nominally 5 × 10-3 Torr and the second a low pressure cell operated at nominally 3 × 10-4 Torr. When IRMPD was performed in the high pressure cell, most peptide ions did not undergo significant photodissociation; however, in the low pressure cell peptide cations were efficiently dissociated with less than 25 ms of IR irradiation regardless of charge state. IRMPD of peptide cations allowed the detection of low m/z product ions including the y1 fragments and immonium ions which are not typically observed by ion trap collision induced dissociation (CID). Photodissociation efficiencies of ~100% and MS/MS (tandem mass spectrometry) efficiencies of greater than 60% were observed for both multiply and singly protonated peptides. In general, higher sequence coverage of peptides was obtained using IRMPD over CID. Further, greater than 90% of the product ion current in the IRMPD mass spectra of doubly charged peptide ions was composed of singly charged product ions compared to the CID mass spectra in which the abundances of the multiply and singly charged product ions were equally divided. Highly charged primary product ions also underwent efficient photodissociation to yield singly charged secondary product ions, thus simplifying the IRMPD product ion mass spectra. PMID:19739654

  10. ANALYSIS OF POLYCYCLIC AROMATIC HYDROCARBONS BY ION TRAP TANDEM MASS SPECTROMETRY

    EPA Science Inventory

    An ion-trap mass spectrometer with a wave board and tandem mass spectrometry software was used to analyze gas chromatographically separated polycyclic aromatic hydrocarbons (PAHs) by using collision-induced dissociation (CID). The nonresonant (multiple collision) mode was used to...

  11. Final Report - Advanced Ion Trap Mass Spectrometry Program - Oak Ridge National Laboratory - Sandia National Laboratory

    SciTech Connect

    Whitten, W.B.

    2002-12-18

    This report covers the three main projects that collectively comprised the Advanced Ion Trap Mass Spectrometry Program. Chapter 1 describes the direct interrogation of individual particles by laser desorption within the ion trap mass spectrometer analyzer. The goals were (1) to develop an ''intelligent trigger'' capable of distinguishing particles of biological origin from those of nonbiological origin in the background and interferent particles and (2) to explore the capability for individual particle identification. Direct interrogation of particles by laser ablation and ion trap mass spectrometry was shown to have good promise for discriminating between particles of biological origin and those of nonbiological origin, although detailed protocols and operating conditions were not worked out. A library of more than 20,000 spectra of various types of biological particles has been assembled. Methods based on multivariate analysis and on neural networks were used to discriminate between particles of biological origin and those of nonbiological origin. It was possible to discriminate between at least some species of bacteria if mass spectra of several hundred similar particles were obtained. Chapter 2 addresses the development of a new ion trap mass analyzer geometry that offers the potential for a significant increase in ion storage capacity for a given set of analyzer operating conditions. This geometry may lead to the development of smaller, lower-power field-portable ion trap mass spectrometers while retaining laboratory-scale analytical performance. A novel ion trap mass spectrometer based on toroidal ion storage geometry has been developed. The analyzer geometry is based on the edge rotation of a quadrupolar ion trap cross section into the shape of a torus. Initial performance of this device was poor, however, due to the significant contribution of nonlinear fields introduced by the rotation of the symmetric ion-trapping geometry. These nonlinear resonances

  12. Computer Modeling of an Ion Trap Mass Analyzer, Part I: Low Pressure Regime.

    PubMed

    Nikolić, Dragan; Madzunkov, Stojan M; Darrach, Murray R

    2015-12-01

    We present the multi-particle simulation program suite Computational Ion Trap Analyzer (CITA) designed to calculate the ion trajectories within a Paul quadrupole ion trap developed by the Jet Propulsion Laboratory (JPL). CITA uses an analytical expression of the electrodynamic field, employing up to six terms in multipole expansion and a modified velocity-Verlet method to numerically calculate ion trajectories. The computer code is multithreaded and designed to run on shared-memory architectures. CITA yields near real-time simulations with full propagation of 26 particles per second per core. As a consequence, a realistic numbers of trapped ions (100+ million) can be used and their trajectories modeled, yielding a representative prediction of mass spectrometer analysis of trace gas species. When the model is compared with experimental results conducted at low pressures using the conventional quadrupole and dipole excitation modes, there is an excellent agreement with the observed peak shapes. Owing to the program's efficiency, CITA has been used to explore regions of trapping stability that are of interest to experimental research. These results are expected to facilitate a fast and reliable modeling of ion dynamics in miniature quadrupole ion trap and improve the interpretation of observed mass spectra. Graphical Abstract ᅟ. PMID:26286456

  13. Computer Modeling of an Ion Trap Mass Analyzer, Part I: Low Pressure Regime

    NASA Astrophysics Data System (ADS)

    Nikolić, Dragan; Madzunkov, Stojan M.; Darrach, Murray R.

    2015-12-01

    We present the multi-particle simulation program suite Computational Ion Trap Analyzer (CITA) designed to calculate the ion trajectories within a Paul quadrupole ion trap developed by the Jet Propulsion Laboratory (JPL). CITA uses an analytical expression of the electrodynamic field, employing up to six terms in multipole expansion and a modified velocity-Verlet method to numerically calculate ion trajectories. The computer code is multithreaded and designed to run on shared-memory architectures. CITA yields near real-time simulations with full propagation of 26 particles per second per core. As a consequence, a realistic numbers of trapped ions (100+ million) can be used and their trajectories modeled, yielding a representative prediction of mass spectrometer analysis of trace gas species. When the model is compared with experimental results conducted at low pressures using the conventional quadrupole and dipole excitation modes, there is an excellent agreement with the observed peak shapes. Owing to the program's efficiency, CITA has been used to explore regions of trapping stability that are of interest to experimental research. These results are expected to facilitate a fast and reliable modeling of ion dynamics in miniature quadrupole ion trap and improve the interpretation of observed mass spectra.

  14. Microfabricated ion trap mass spectrometry for characterization of organics and potential biomarkers

    NASA Astrophysics Data System (ADS)

    Austin, Daniel

    Mass spectrometry is a powerful analytical technique with a strong history in planetary exploration, and is the method of choice for detection and identification of organic and biological molecules. MS instrumentation can also be combined with techniques such as gas chromatography, liquid chromatography, or chiral separation, which are particularly important for analysis of complex mixtures or possible homochirality. Ion traps have several inherent advantages, including speed of analysis (important for GC-MS), MS/MS capabilities (important to identification of unknown compounds), excellent sensitivity, and ease of coupling with ambient ionization techniques that are under development for biomolecule detection. We report on progress in using microfabrication techniques to produce radiofrequency quadrupole ion traps that are much smaller, lighter, and lower power than existing instruments. We produce ion traps using an assembly of two ceramic plates, the facing surfaces of which are lithographically patterned with electrodes. This approach allows great flexibility in the trap geometry, and we have demonstrated working mass spectrometers with quadrupole, linear, and toroidal trapping fields. The approach also allows correction of higher-order terms in the electric field. With this system, mass resolution of up to 1300 has been demonstrated, which is adequate for identification of a wide range of potential biomarkers. Capabilities such as tandem analysis have also been demonstrated. Of particular interest is an ion trap that contains both quadrupole and toroidal trapping regions simultaneously and coaxially. Ions can be trapped as a large reservoir in the toroidal region and introduced in small batches to the quadrupole region for mass analysis. This capability is particularly valuable where the sample of interest is very small, such as microfossil with trace organics, and where the organic inventory is both complex and unknown. Development and results of this device

  15. Operational Parameters, Considerations, and Design Decisions for Resource-Constrained Ion Trap Mass Spectrometers

    NASA Technical Reports Server (NTRS)

    Danell, Ryan M.; VanAmerom, Friso H. W.; Pinnick, Veronica; Cotter, Robert J.; Brickerhoff, William; Mahaffy, Paul

    2011-01-01

    Mass spectrometers are increasingly finding applications in new and unique areas, often in situations where key operational resources (i.e. power, weight and size) are limited. One such example is the Mars Organic Molecule Analyzer (MOMA). This instrument is a joint venture between NASA and the European Space Agency (ESA) to develop an ion trap mass spectrometer for chemical analysis on Mars. The constraints on such an instrument are significant as are the performance requirements. While the ideal operating parameters for an ion trap are generally well characterized, methods to maintain analytical performance with limited power and system weight need to be investigated and tested. Methods Experiments have been performed on two custom ion trap mass spectrometers developed as prototypes for the MOMA instrument. This hardware consists of quadrupole ion trap electrodes that are 70% the size of common commercial instrumentation. The trapping RF voltage is created with a custom tank circuit that can be tuned over a range of RF frequencies and is driven using laboratory supplies and amplifiers. The entire instrument is controlled with custom Lab VIEW software that allows a high degree of flexibility in the definition of the scan function defining the ion trap experiment. Ions are typically generated via an internal electron ionization source, however, a laser desorption source is also in development for analysis of larger intact molecules. Preliminary Data The main goals in this work have been to reduce the power required to generate the radio frequency trapping field used in an ion trap mass spectrometer. Generally minimizing the power will also reduce the volume and mass of the electronics to support the instrument. In order to achieve optimum performance, commercial instruments typically utilize RF frequencies in the 1 MHz range. Without much concern for power usage, they simply generate the voltage required to access the mass range of interest. In order to reduce the

  16. Trapping radioactive ions

    NASA Astrophysics Data System (ADS)

    Kluge, H.-J.; Blaum, K.

    2004-12-01

    Trapping devices for atomic and nuclear physics experiments with radioactive ions are becoming more and more important at accelerator facilities. While about ten years ago only one online Penning trap experiment existed, namely ISOLTRAP at ISOLDE/CERN, meanwhile almost every radioactive beam facility has installed or plans an ion trap setup. This article gives an overview on ion traps in the operation, construction or planing phase which will be used for fundamental studies with short-lived radioactive nuclides such as mass spectrometry, laser spectroscopy and nuclear decay spectroscopy. In addition, this article summarizes the use of gas cells and radiofrequency quadrupole (Paul) traps at different facilities as a versatile tool for ion beam manipulation like retardation, cooling, bunching, and cleaning.

  17. Characterization of environmental samples using ion trap-secondary ion mass spectrometry

    SciTech Connect

    Groenewold, G.S.; Appelhans, A.D.; Ingram, J.C.

    1998-02-01

    The detection of chemical warfare agent residues on environmental surfaces is an important analytical activity because of the potential for proliferation of these weapons, and for environmental monitoring in areas where they are stored. Historically, one of the most widely used agents has been bis(2-chloroethyl) sulfide, also known as mustard gas and HD. It was initially used in combat in 1917; by the end of the First World War, more than 16% of all casualties were due to chemicals, in most cases mustard. Manufacture of mustard is continuing to this day; consequently, there are ongoing opportunities for exposure. 2-Chloroethyl ethyl sulfide (CEES) is used as a simulant for mustard (HD) in a study to develop secondary ion mass spectrometry (SIMS) for rapid, semi-quantitative detection of mustard on soil. Using SIMS with single stage mass spectrometry, a signature for CEES can be unequivocally observed only at the highest concentrations (0.1 monolayer and above). Selectivity and sensitivity are markedly improved employing multiple-stage mass spectrometry using an ion trap. C{sub 2}H{sub 5}SC{sub 2}H{sub 4}{sup +} from CEES eliminates C{sub 2}H{sub 4} and H{sub 2}S, which are highly diagnostic. CEES was detected at 0.0012 monolayer on soil. A single analysis could be conducted in under 5 minutes.

  18. Airborne nanoparticle characterization with a digital ion trap-reflectron time of flight mass spectrometer

    NASA Astrophysics Data System (ADS)

    Wang, Shenyi; Johnston, Murray V.

    2006-12-01

    A digital ion trap-reflectron time of flight mass spectrometer is described for airborne nanoparticle characterization. Charged particles sampled into this nanoaerosol mass spectrometer (NAMS) are captured in the ion trap and ablated with a high fluence laser pulse to reach the "complete ionization limit". Atomic ions produced from the trapped particle(s) are mass analyzed by time of flight, and the elemental composition is determined from the relative signal intensities in the mass spectrum. The particle size range captured in the ion trap is selected by the frequency applied to the ring electrode. Size selection is based on the mass normalized particle diameter, defined as the diameter of a spherical particle with unit density that has the same mass as the particle being analyzed. For the current instrument configuration, ring electrode frequencies between 5 and 140 kHz allow selective trapping of particles with a mass normalized diameter between 7 and 25 nm with a geometric standard deviation of about 1.1. The particle detection efficiency, defined as the fraction of charged particles entering the mass spectrometer that are subsequently captured and analyzed, is between l x l0-4 and 3 x l0-4 over this size range. The effective particle density can be determined from simultaneous measurement of the mobility and mass normalized diameters. Test nanoparticles composed of sucrose, polyethylene glycol, polypropylene glycol, sodium chloride, ammonium sulfate and copper(II) chloride are investigated. In most cases, the measured elemental compositions match the expected elemental compositions within +/-5% or less and the measured compositions do not change with particle size. The one exception is copper chloride, which does not yield a well-developed plasma when it is irradiated by the laser pulse.

  19. Evaluation of ion trap mass spectrometry for the determination of ambient nicotine

    SciTech Connect

    Wise, M.B.; Higgins, C.E.; Ilgner, R.H.; Guerin, M.R.

    1989-01-01

    A thermal desorption unit has been interfaced directly with a Finnigan Ion Trap mass spectrometer (ITMS) for the identification and quantification of trace organics in air. No chromatographic separation of the desorbed constituents is performed prior to introduction into the mass spectrometer. Instead, positive identification of a compound is made based on its collision induced dissociation (CID) tandem (MS/MS) mass spectrum. Using this technique, as little as 50 pg of a constituent desorbed from resin trap can be characterized and quantified with a sample turnaround time of only 2--3 minutes. 3 refs.

  20. Microfabricated cylindrical ion trap

    DOEpatents

    Blain, Matthew G.

    2005-03-22

    A microscale cylindrical ion trap, having an inner radius of order one micron, can be fabricated using surface micromachining techniques and materials known to the integrated circuits manufacturing and microelectromechanical systems industries. Micromachining methods enable batch fabrication, reduced manufacturing costs, dimensional and positional precision, and monolithic integration of massive arrays of ion traps with microscale ion generation and detection devices. Massive arraying enables the microscale cylindrical ion trap to retain the resolution, sensitivity, and mass range advantages necessary for high chemical selectivity. The microscale CIT has a reduced ion mean free path, allowing operation at higher pressures with less expensive and less bulky vacuum pumping system, and with lower battery power than conventional- and miniature-sized ion traps. The reduced electrode voltage enables integration of the microscale cylindrical ion trap with on-chip integrated circuit-based rf operation and detection electronics (i.e., cell phone electronics). Therefore, the full performance advantages of microscale cylindrical ion traps can be realized in truly field portable, handheld microanalysis systems.

  1. Resonant laser ablation ion trap mass spectrometry -- Recent applications for chemical analysis

    SciTech Connect

    Gill, C.G.; Garrett, A.W.; Hemberger, P.H.; Nogar, N.S.

    1995-12-31

    Resonant Laser Ablation (RLA) is a useful ionization process for selectively producing gas phase ions from a solid sample. Recent use of RLA for mass spectrometry by this group and by others has produced a wealth of knowledge and useful analytical techniques. The method relies upon the focusing of modest intensity laser pulses ({le} 10{sup 7} W {center_dot} Cm{sup {minus}2}) upon a sample surface. A small quantity of material is vaporized, and atoms of desired analyte are subsequently ionized by (n + m) photon processes in the gas phase (where n = number of photons to a resonant transition and m = number of photons to exceed the ionization limit). The authors have been using (2 + 1) resonant ionization schemes for this work. Quadrupole ion trap mass spectrometry is realizing a very prominent role in current mass spectrometric research. Ion traps are versatile, powerful and extremely sensitive mass spectrometers, capable of a variety of ionization modes, MS{sup n} type experiments, high mass ranges and high resolution, all for a fraction of the cost of other instrumentation with similar capabilities. Quadrupole ion traps are ideally suited to pulsed ionization sources such as laser ionization methods, since their normal operational method (Mass Selective Instability) relies upon the storage of ions from a finite ionization period followed by ejection and detection of these ions based upon their mass to charge ratios. The paper describes selective ionization for trace atomic analysis, selective reagent ion source for ion chemistry investigations, and the analysis of ``difficult`` environmental contaminants, i.e., TBP.

  2. Ion trap mass spectrometry on a comet nucleus: the Ptolemy instrument and the Rosetta space mission.

    PubMed

    Todd, John F J; Barber, Simeon J; Wright, Ian P; Morgan, Geraint H; Morse, Andrew D; Sheridan, Simon; Leese, Mark R; Maynard, Jon; Evans, Suzanne T; Pillinger, Colin T; Drummond, Duncan L; Heys, Samantha C; Huq, S Ejaz; Kent, Barry J; Sawyer, Eric C; Whalley, Martin S; Waltham, Nicholas R

    2007-01-01

    In May 2014, the Rosetta spacecraft is scheduled to rendezvous with the comet Churyumov-Gerasimenko ('67P'). One of the instruments on board the 'Lander' which will descend on to the surface of the comet is a miniaturised GC/MS system that incorporates an ion trap mass spectrometer, specially developed for isotope ratio analysis. This article describes the development and optimisation of the ion trap for this unique application, and presents a summary of the range of pre-programmed experiments that will contribute to the characterisation of the solid and volatile cometary materials.

  3. Ion trap mass spectrometry on a comet nucleus: the Ptolemy instrument and the Rosetta space mission.

    PubMed

    Todd, John F J; Barber, Simeon J; Wright, Ian P; Morgan, Geraint H; Morse, Andrew D; Sheridan, Simon; Leese, Mark R; Maynard, Jon; Evans, Suzanne T; Pillinger, Colin T; Drummond, Duncan L; Heys, Samantha C; Huq, S Ejaz; Kent, Barry J; Sawyer, Eric C; Whalley, Martin S; Waltham, Nicholas R

    2007-01-01

    In May 2014, the Rosetta spacecraft is scheduled to rendezvous with the comet Churyumov-Gerasimenko ('67P'). One of the instruments on board the 'Lander' which will descend on to the surface of the comet is a miniaturised GC/MS system that incorporates an ion trap mass spectrometer, specially developed for isotope ratio analysis. This article describes the development and optimisation of the ion trap for this unique application, and presents a summary of the range of pre-programmed experiments that will contribute to the characterisation of the solid and volatile cometary materials. PMID:17154436

  4. An integrated ion trap and time-of-flight mass spectrometer for chemical and photo- reaction dynamics studies.

    PubMed

    Schowalter, Steven J; Chen, Kuang; Rellergert, Wade G; Sullivan, Scott T; Hudson, Eric R

    2012-04-01

    We demonstrate the integration of a linear quadrupole trap with a simple time-of-flight mass spectrometer with medium-mass resolution (m/Δm ∼ 50) geared towards the demands of atomic, molecular, and chemical physics experiments. By utilizing a novel radial ion extraction scheme from the linear quadrupole trap into the mass analyzer, a device with large trap capacity and high optical access is realized without sacrificing mass resolution. This provides the ability to address trapped ions with laser light and facilitates interactions with neutral background gases prior to analyzing the trapped ions. Here, we describe the construction and implementation of the device as well as present representative ToF spectra. We conclude by demonstrating the flexibility of the device with proof-of-principle experiments that include the observation of molecular-ion photodissociation and the measurement of trapped-ion chemical reaction rates.

  5. Stored waveform inverse Fourier transform (SWIFT) ion excitation in trapped-ion mass spectometry: Theory and applications

    NASA Astrophysics Data System (ADS)

    Guan, Shenheng; Marshall, Alan G.

    1996-12-01

    Stored waveform excitation produced by inverse Fourier transformation of a specified magnitude/phase excitation spectrum offers the most general and versatile means for broadband mass-selective excitation and ejection in Penning (FT-ICR) and Paul (quadrupole) ion trap mass spectrometry. Since the last comprehensive review of SWIFT excitation in 1987, the technique has been adopted, modified, and extended widely in both the ICR and quadrupole ion trap communities. Here, we review the principles, variations, algorithms, hardware implementation, and some applications of SWIFT for both ICR and quadrupole ion trap mass spectrometry. We show that the most desirable SWIFT waveform is that optimized to reduce both the time-domain SWIFT maximum amplitude and the amplitude near the start and end of the SWIFT waveform. We examine the "true" magnitude excitation spectrum, obtained by zero-filling and forward Fourier transforming the SWIFT time-domain waveform, in order to evaluate the trade-off between spectral magnitude uniformity and frequency (mass) selectivity. Apodization of the SWIFT waveform is optimally conducted by smoothing the excitation magnitude spectrum prior to generation of the SWIFT waveform by inverse FT. When (as for broadband ejection in a quadrupole ion trap) it is important that ions be excited near-simultaneously over a wide mass range, the phase spectrum (before inverse FT to generate the SWIFT waveform) may be overmodulated or randomly modulated ("filtered noise field"), with the recognition that very substantial non-uniformity in the "true" excitation magnitude spectrum will result.

  6. Evaluation of Pulse Counting for the Mars Organic Mass Analyzer (MOMA) Ion Trap Detection Scheme

    NASA Technical Reports Server (NTRS)

    Van Amerom, Friso H.; Short, Tim; Brinckerhoff, William; Mahaffy, Paul; Kleyner, Igor; Cotter, Robert J.; Pinnick, Veronica; Hoffman, Lars; Danell, Ryan M.; Lyness, Eric I.

    2011-01-01

    The Mars Organic Mass Analyzer is being developed at Goddard Space Flight Center to identify organics and possible biological compounds on Mars. In the process of characterizing mass spectrometer size, weight, and power consumption, the use of pulse counting was considered for ion detection. Pulse counting has advantages over analog-mode amplification of the electron multiplier signal. Some advantages are reduced size of electronic components, low power consumption, ability to remotely characterize detector performance, and avoidance of analog circuit noise. The use of pulse counting as a detection method with ion trap instruments is relatively rare. However, with the recent development of high performance electrical components, this detection method is quite suitable and can demonstrate significant advantages over analog methods. Methods A prototype quadrupole ion trap mass spectrometer with an internal electron ionization source was used as a test setup to develop and evaluate the pulse-counting method. The anode signal from the electron multiplier was preamplified. The an1plified signal was fed into a fast comparator for pulse-level discrimination. The output of the comparator was fed directly into a Xilinx FPGA development board. Verilog HDL software was written to bin the counts at user-selectable intervals. This system was able to count pulses at rates in the GHz range. The stored ion count nun1ber per bin was transferred to custom ion trap control software. Pulse-counting mass spectra were compared with mass spectra obtained using the standard analog-mode ion detection. Prelin1inary Data Preliminary mass spectra have been obtained for both analog mode and pulse-counting mode under several sets of instrument operating conditions. Comparison of the spectra revealed better peak shapes for pulse-counting mode. Noise levels are as good as, or better than, analog-mode detection noise levels. To artificially force ion pile-up conditions, the ion trap was overfilled

  7. Broad spectrum drug screening using liquid chromatography-hybrid triple quadrupole linear ion trap mass spectrometry.

    PubMed

    Stone, Judy

    2010-01-01

    Centrifuged urine, internal standard (promazine), and ammonium formate buffer are mixed in an autosampler vial to achieve a 10-fold dilution of the specimen. Without additional pretreatment, 10 microL of the sample is injected onto a C18 reverse phase column for gradient analysis with ammonium formate/acetonitrile mobile phases. Drugs in the column eluent become charged in the ion source using positive electrospray atmospheric pressure ionization. Pseudomolecular drug ions are analyzed by a hybrid triple quadrupole linear ion trap mass spectrometer operated with a 264-drug selected ion monitoring (SRM) acquisition method that includes an information-dependant acquisition (IDA) algorithm. PMID:20077072

  8. Advanced Automation for Ion Trap Mass Spectrometry-New Opportunities for Real-Time Autonomous Analysis

    NASA Technical Reports Server (NTRS)

    Palmer, Peter T.; Wong, C. M.; Salmonson, J. D.; Yost, R. A.; Griffin, T. P.; Yates, N. A.; Lawless, James G. (Technical Monitor)

    1994-01-01

    The utility of MS/MS for both target compound analysis and the structure elucidation of unknowns has been described in a number of references. A broader acceptance of this technique has not yet been realized as it requires large, complex, and costly instrumentation which has not been competitive with more conventional techniques. Recent advancements in ion trap mass spectrometry promise to change this situation. Although the ion trap's small size, sensitivity, and ability to perform multiple stages of mass spectrometry have made it eminently suitable for on-line, real-time monitoring applications, advance automation techniques are required to make these capabilities more accessible to non-experts. Towards this end we have developed custom software for the design and implementation of MS/MS experiments. This software allows the user to take full advantage of the ion trap's versatility with respect to ionization techniques, scan proxies, and ion accumulation/ejection methods. Additionally, expert system software has been developed for autonomous target compound analysis. This software has been linked to ion trap control software and a commercial data system to bring all of the steps in the analysis cycle under control of the expert system. These software development efforts and their utilization for a number of trace analysis applications will be described.

  9. Development and Deployment of Retrofit PolarisQ Ion Trap Mass Spectrometer for Isotope Ratio Measurements

    SciTech Connect

    Thompson, Cyril V.; Whitten, William B.

    2015-11-01

    This report describes Oak Ridge National Laboratory’s (ORNL) FY15 progress in support of National Nuclear Security Administration’s (NNSA) Portable Mass Spectrometer project. A retrofit PolarisQ ion trap mass spectrometer (RPMS) has been assembled from components of two PolarisQ ion trap mass spectrometers used in previous isotope ratio programs. The retrofit mass spectrometer includes a custom Hastelloy vacuum chamber which is about ¼ the size of the standard aluminum vacuum chamber and reduces the instrument weight from the original by nine pounds. In addition, the new vacuum chamber can be independently heated to reduce impurities such as water, which reacts with UF6 to produce HF in the vacuum chamber. The analyzer and all components requiring service are mounted on the chamber lid, facilitating quick and easy replacement of consumable components such as the filament and electron multiplier.

  10. Design and performance of an instrument for electron impact tandem mass spectrometry and action spectroscopy of mass/charge selected macromolecular ions stored in RF ion trap*

    NASA Astrophysics Data System (ADS)

    Ranković, Milos Lj.; Giuliani, Alexandre; Milosavljević, Aleksandar R.

    2016-06-01

    A new apparatus was designed, coupling an electron gun with a linear quadrupole ion trap mass spectrometer, to perform m/ z (mass over charge) selected ion activation by electron impact for tandem mass spectrometry and action spectroscopy. We present in detail electron tracing simulations of a 300 eV electron beam inside the ion trap, design of the mechanical parts, electron optics and electronic circuits used in the experiment. We also report examples of electron impact activation tandem mass spectra for Ubiquitin protein, Substance P and Melittin peptides, at incident electron energies in the range from 280 eV to 300 eV.

  11. Rapid environmental organic analysis by direct sampling Glow Discharge Mass Spectrometry and Ion Trap Mass Spectrometry: Summary of pilot studies

    SciTech Connect

    Wise, M.B.; Buchanan, M.V.; Guerin, M.R.

    1990-03-01

    Direct Sampling Mass Spectrometry (DSMS) techniques employing both Glow Discharge Mass Spectrometry and Ion Trap Mass Spectrometry are being developed to quantitatively determine preselected organics in water, soil, and air samples at part per billion levels in less than five minutes. Direct sampling requires little or no sample preparation and no prior chromatographic separation and is applicable to both volatile and semivolatile organics. 25 figs., 3 tabs.

  12. Hybrid quadrupole mass filter/quadrupole ion trap/time-of-flight-mass spectrometer for infrared multiple photon dissociation spectroscopy of mass-selected ions

    SciTech Connect

    Gulyuz, Kerim; Stedwell, Corey N.; Wang Da; Polfer, Nick C.

    2011-05-15

    We present a laboratory-constructed mass spectrometer optimized for recording infrared multiple photon dissociation (IRMPD) spectra of mass-selected ions using a benchtop tunable infrared optical parametric oscillator/amplifier (OPO/A). The instrument is equipped with two ionization sources, an electrospray ionization source, as well as an electron ionization source for troubleshooting. This hybrid mass spectrometer is composed of a quadrupole mass filter for mass selection, a reduced pressure ({approx}10{sup -5} Torr) quadrupole ion trap (QIT) for OPO irradiation, and a reflectron time-of-flight drift tube for detecting the remaining precursor and photofragment ions. A helium gas pulse is introduced into the QIT to temporarily increase the pressure and hence enhance the trapping efficiency of axially injected ions. After a brief pump-down delay, the compact ion cloud is subjected to the focused output from the continuous wave OPO. In a recent study, we implemented this setup in the study of protonated tryptophan, TrpH{sup +}, as well as collision-induced dissociation products of this protonated amino acid [W. K. Mino, Jr., K. Gulyuz, D. Wang, C. N. Stedwell, and N. C. Polfer, J. Phys. Chem. Lett. 2, 299 (2011)]. Here, we give a more detailed account on the figures of merit of such IRMPD experiments. The appreciable photodissociation yields in these measurements demonstrate that IRMPD spectroscopy of covalently bound ions can be routinely carried out using benchtop OPO setups.

  13. Mass determination of light ions in a Penning trap by time-of-flight detection of ion resonances

    NASA Astrophysics Data System (ADS)

    Kern, J.; Engel, T.; Hagena, D.; Werth, G.

    1992-12-01

    We describe an experimental setup to determine the cyclotron frequencies of ions confined in a Penning trap by resonant excitation of the ions eigenfrequencies and a time-of-flight detection of the resonances. Systematic shifts from trap- and B-field imperfections are discussed and methods to minimize those effects in our experiment are presented. Results on the mass ratio for 4He/D2 and 3He/H2 demonstrate the experimentally obtained precision in the ppb range, which might be further improved by modification of our apparatus.

  14. Comparison of functional group selective ion-molecule reactions of trimethyl borate in different ion trap mass spectrometers

    SciTech Connect

    Habicht, S C; Vinueza, Nelson R; Amundson, Lucas M; Kenttämaa, Hilkka I

    2011-02-01

    We report here a comparison of the use of diagnostic ion–molecule reactions for the identification of oxygen-containing functional groups in Fourier-transform ion cyclotron resonance (FTICR) and linear quadrupole ion trap (LQIT) mass spectrometers. The ultimate goal of this research is to be able to identify functionalities in previously unknown analytes by using many different types of mass spectrometers. Previous work has focused on the reactions of various boron reagents with protonated oxygen-containing analytes in FTICR mass spectrometers. By using a LQIT modified to allow the introduction of neutral reagents into the helium buffer gas, this methodology has been successfully implemented to this type of an ion trap instrument. The products obtained from the reactions of trimethyl borate (TMB) with various protonated analytes are compared for the two instruments. Finally, the ability to integrate these reactions into LC-MS experiments on the LQIT is demonstrated.

  15. Oligosaccharide sequences in Quillaja saponins by electrospray ionization ion trap multiple-stage mass spectrometry.

    PubMed

    Broberg, Susanna; Nord, Lars I; Kenne, Lennart

    2004-06-01

    Ten different samples with 13 previously identified saponin structures from Quillaja saponaria Molina were investigated by electrospray ionization ion trap multiple-stage mass spectrometry (ESI-ITMS(n)) in positive and negative ion modes. Both positive and negative ion mode MS(1)-MS(4) spectra were analyzed, showing that structural information on the two oligosaccharide parts in the saponin can be obtained from positive ion mode spectra whereas negative ion mode spectra mainly gave information on one of the oligosaccharide parts. Analysis of MS(1)-MS(4) spectra identified useful key fragment ions important for the structural elucidation of Quillaja saponins. A flowchart involving a stepwise procedure based on key fragments from MS(1)-MS(3) spectra was constructed for the identification of structural elements in the saponin. Peak intensity ratios in MS(3) spectra were found to be correlated with structural features of the investigated saponins and are therefore of value for the identification of terminal monosaccharide residues.

  16. An electrodynamic ion funnel interface for greater sensitivity and higher throughput with linear ion trap mass spectrometers

    NASA Astrophysics Data System (ADS)

    Page, Jason S.; Tang, Keqi; Smith, Richard D.

    2007-09-01

    An electrospray ionization interface incorporating an electrodynamic ion funnel has been designed and implemented on a linear ion trap mass spectrometer (Thermo Electron, LTQ). We found ion transmission to be greatly improved by replacing the standard capillary-skimmer interface with the capillary-ion funnel interface. An infusion study using a serial dilution of a reserpine solution showed that ion injection (accumulation) times to fill the ion trap at a given automatic gain control (AGC) target value were reduced by ~90% which resulted in an ~10-fold increase in peak intensities. In liquid chromatography tandem MS (LC-MS/MS) experiments performed using a global protein digest sample from the bacterium, Shewanella oneidensis, more peptides and proteins were identified when the ion funnel interface was used in place of the standard interface. This improvement was most pronounced at lower sample concentrations, where extended ion accumulation times are required, resulting in an ~2-fold increase in the number of protein identifications. Implementation of the ion funnel interface on a LTQ Fourier transform (FT) mass spectrometer showed a ~25-50% reduction in spectrum acquisition time. The duty cycle improvement in this case was due to the ion accumulation event contributing a larger portion to the total spectrum acquisition time.

  17. An electrodynamic ion funnel interface for greater sensitivity and higher throughput with linear ion trap mass spectrometers

    SciTech Connect

    Page, Jason S.; Tang, Keqi; Smith, Richard D.

    2007-09-01

    An electrospray ionization interface incorporating an electrodynamic ion funnel has been designed and implemented in conjunction with a linear ion trap mass spectrometer (Thermo Electron, LTQ). We found ion transmission to be greatly improved by replacing the standard capillary-skimmer interface with the capillary-ion funnel interface. An infusion study using a serial dilution of a reserpine solution showed that ion injection times to fill the ion trap were reduced by ~90% which resulted in an ~10-fold increase in reported peak intensities. In liquid chromatography (LC)-MS and LC tandem MS (MS/MS) experiments performed using a proteomic sample from the bacterium, Shewanella oneidensis, the ion funnel interface provided an ~7-fold reduction in ion injection (accumulation) times. In a series of LC-MS/MS experiments we found that more dilute S. oneidensis samples provided more peptide and protein identifications when the ion funnel interface was used in place of the standard interface. This improvement was most pronounced at lower sample concentrations, where extended ion accumulation times are required, resulting in an ~2-fold increase in the number of protein identifications. Implementation of the ion funnel interface with a LTQ Fourier transform (FT) MS requiring much greater ion populations resulted in spectrum acquisition times reduced by ~25 to 50%.

  18. Human Biomonitoring of DNA Adducts by Ion Trap Multistage Mass Spectrometry.

    PubMed

    Guo, Jingshu; Turesky, Robert J

    2016-01-01

    Humans are continuously exposed to hazardous chemicals in the environment. These chemicals or their electrophilic metabolites can form adducts with genomic DNA, which can lead to mutations and the initiation of cancer. The identification of DNA adducts is required for understanding exposure and the etiological role of a genotoxic chemical in cancer risk. The analytical chemist is confronted with a great challenge because the levels of DNA adducts generally occur at <1 adduct per 10(7) nucleotides, and the amount of tissue available for measurement is limited. Ion trap mass spectrometry has emerged as an important technique to screen for DNA adducts because of the high level sensitivity and selectivity, particularly when employing multi-stage scanning (MS(n) ). The product ion spectra provide rich structural information and corroborate the adduct identities even at trace levels in human tissues. Ion trap technology represents a significant advance in measuring DNA adducts in humans. © 2016 by John Wiley & Sons, Inc. PMID:27584705

  19. Developments of multiplexed and miniature two-dimensional quadrupole ion trap mass spectrometers

    NASA Astrophysics Data System (ADS)

    Smith, Scott A.

    Quadrupole ion trap mass spectrometry (QIT MS) is a powerful and commonly-employed method for the specific analysis of mass, composition, and structure of gas-phase ionic chemical species. Useful for a wide variety of tasks, applications of ion traps include environmental monitoring, surface analysis (including depth profiling and imaging), ion thermochemical property elucidation, protein and DNA sequencing, and high-resolution chemical separations (through ion soft-landing). Though the principles of QIT MS have been known for over half a century, innovations in instrumentation and applications continue. As new needs for specific and sensitive chemical analysis arise, so also do new and more efficient analytical devices and methods of analysis. Such a trend is exemplified through the construction of a dual-source QIT mass spectrometer (described herein) capable of multi-source chemical analyses for the purposes of enhanced proteomic sequence coverage and for the strictly-controlled comparison of the structural differences in ion populations generated by different ionization techniques. Furthermore, as mass spectrometry becomes increasingly commonplace outside the bounds of the analytical laboratory, demand for capable researcher equipment is also increasing. Advances in instrument performance, such as can be had through enhanced power efficiency and the enabling of chemical analysis of high mass-to-charge ratio (m/z) species (e.g., proteins), will open new doors to in situ chemical analysis hand-portable mass spectrometers. Hence, research into new mass analyzer designs and methods of fabrication using stereolithography apparatus (SLA) for the purpose of creating enhanced-performance mass spectrometers are accordingly described in the text of this dissertation.

  20. A new technique for unbiased external ion accumulation in a quadrupole two-dimensional ion trap for electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Belov, M E; Nikolaev, E N; Alving, K; Smith, R D

    2001-01-01

    External ion accumulation in a two-dimensional (2D) multipole trap has been shown to increase the sensitivity, dynamic range and duty cycle of a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. However, it is important that trapped ions be detected without significant bias at longer accumulation times in the external 2D multipole trap. With increasing ion accumulation time pronounced m/z discrimination was observed when trapping ions in an accumulation quadrupole. In this work we show that superimposing lower rf-amplitude dipolar excitation over the main rf-field in the accumulation quadrupole results in disruption of the m/z discrimination and can potentially be used to achieve unbiased external ion accumulation with FTICR.

  1. Determination of interfering triazine degradation products by gas chromatography-ion trap mass spectrometry.

    PubMed

    Magnuson, M L; Speth, T F; Kelty, C A

    2000-01-28

    Deethylatrazine (DEA), an atrazine degradation product, has been added to the US Environmental Protection Agency's Drinking Water Contaminant Candidate List (CCL). In its gas chromatographic analysis, DEA can coelute with deisopropylatrazine (DIA), another degradation product. The present work demonstrates that the coelution of DEA and DIA can induce a significant (up to approximately 50%) positive bias in the DEA determination, when using an ion-trap mass spectrometer as the detector. The DIA determination is unaffected by the coelution within experimental error. This may be explained in terms of gas-phase ion fragment populations. A correction factor to the observed DEA concentration may be developed based on the measured DIA concentration.

  2. A comb-sampling method for enhanced mass analysis in linear electrostatic ion traps

    SciTech Connect

    Greenwood, J. B.; Kelly, O.; Calvert, C. R.; Duffy, M. J.; King, R. B.; Belshaw, L.; Graham, L.; Alexander, J. D.; Williams, I. D.; Bryan, W. A.; Turcu, I. C. E.; Cacho, C. M.; Springate, E.

    2011-04-15

    In this paper an algorithm for extracting spectral information from signals containing a series of narrow periodic impulses is presented. Such signals can typically be acquired by pickup detectors from the image-charge of ion bunches oscillating in a linear electrostatic ion trap, where frequency analysis provides a scheme for high-resolution mass spectrometry. To provide an improved technique for such frequency analysis, we introduce the CHIMERA algorithm (Comb-sampling for High-resolution IMpulse-train frequency ExtRAaction). This algorithm utilizes a comb function to generate frequency coefficients, rather than using sinusoids via a Fourier transform, since the comb provides a superior match to the data. This new technique is developed theoretically, applied to synthetic data, and then used to perform high resolution mass spectrometry on real data from an ion trap. If the ions are generated at a localized point in time and space, and the data is simultaneously acquired with multiple pickup rings, the method is shown to be a significant improvement on Fourier analysis. The mass spectra generated typically have an order of magnitude higher resolution compared with that obtained from fundamental Fourier frequencies, and are absent of large contributions from harmonic frequency components.

  3. Characterization of phosphoantigens by high-performance anion-exchange chromatography-electrospray ionization ion trap mass spectrometry and nanoelectrospray ionization ion trap mass spectrometry.

    PubMed

    Pont, F; Luciani, B; Belmant, C; Fournié, J J

    2001-08-01

    New phosphorylated microbial metabolites referred to as phosphoantigens activate immune responses in humans. Although these molecules have leading applications in medical research, no direct method allows their rapid and unambiguous structural identification. Here, we interfaced online HPAEC (high performance anion-exchange chromatography) with ESI-ITMS (electrospray ionization ion trap mass spectrometry) to identify such pyrophosphorylated molecules. A self-regenerating anion suppressor located upstream of electrospray ionization enabled the simultaneous detection of pyrophosphoester by conductimetry, UV and MS. By HPAEC-ITMS and HPAEC-ITMS2, a single run permitted characterization of reference phosphoantigens and of related structures. Although all compounds were resolved by HPAEC, MS enabled their detection and identification by [M-H]- and fragment ions. Isobaric phosphoantigen analogues were also separated by HPAEC and distinguished by MS2. The relevance of this device was demonstrated for phosphoantigens analysis in human urine and plasma. Furthermore, identification of natural phosphoantigens by automatically generated 2D mass spectra from nano-ESI-ITMS is presented. This last technique permits the simultaneous performance of molecular screening of natural phosphoantigen extracts and their identification.

  4. Two Ions Simultaneously Trapped to Measure the Antiproton Charge-to-Mass Ratio

    NASA Astrophysics Data System (ADS)

    Khabbaz, A.; Hall, D. S.; Gabrielse, G.; Heimann, C.; Kalinowsky, H.; Jhe, W.

    1998-05-01

    The antiproton (barp) and proton (php) charge-to-mass ratios are improved by an order of magnitude(G. Gabrielse, D. Phillips, W. Quint, H. Kalinowsky, G. Rouleau, W. Jhe, Phys. Rev. Lett. 77), 3544 (1995).. A single php, dressed with two electrons to form the negative hydrogen ion (H^-), is simultaneously trapped with a single barp in a Penning Trap. With the barp excited into a large cyclotron orbit, the eigenfrequencies of the centered H^- are measured. Next, roles are reversed and the eigenfrequencies of the centered barp are measured. After including the well known proton-to-electron mass ratio and the H^- binding energy, the H^- and barp frequency comparison determines the ratio of (q/m) for the antiproton/proton. The biggest systematic of the previous measurement is eliminated since we compare particles of the same sign of charge, and the time between measurements is shorter. This measurement is among the most accurate mass spectroscopy measurements made, is the first precise measurement made with two ions trapped at the same time, and confirms most accurately that CPT holds for protons.

  5. Plasticizer contamination from vacuum system O-rings in a quadrupole ion trap mass spectrometer.

    PubMed

    Verge, Kent M; Agnes, George R

    2002-08-01

    The outgassing of plasticizers from Buna-N and Viton o-rings under vacuum lead to undesired ion-molecule chemistry in an Electrospray Quadrupole Ion Trap Mass Spectrometer. In experiments with the helium bath gas pressure >1.2 mTorr, or whenever analyte ions were stored for >100 ms, extensive loss of analyte ions by proton transfer or adduction with o-ring plasticizers bis(2-ethylhexyl) phthalate and bis(2-ethylhexyl) adipate occurred. A temporary solution to this contamination problem was found to be overnight refluxing in hexane of all the o-rings in the vacuum system. This procedure alleviated this plasticizer contamination for approximately 100 hours of operation. These results, and those that lead to identification of the contamination as plasticizers outgassing from o-rings are described. PMID:12216729

  6. Differentiation of microorganisms based on pyrolysis-ion trap mass spectrometry using chemical ionization.

    PubMed

    Barshick, S A; Wolf, D A; Vass, A A

    1999-02-01

    The ability to differentiate microorganisms using pyrolysision trap mass spectrometry was demonstrated for five Gram-negative disease-causing organisms: Brucella melitensis, Brucella suis, Vibrio cholera, Yersinia pestis, and Francisella tularensis. Bacterial profiles were generated for gamma-irradiated bacterial samples using pyrolytic methylation and compared for electron ionization and chemical ionization using several liquid reagents with increasing proton affinities. Electron ionization combined with pyrolysis caused extensive fragmentation, resulting in a high abundance of lower mass ions and diminishing the diagnostic value of the technique for compound identification and bacterial profiling. Chemical ionization reduced the amount of fragmentation due to ionization while enhancing the molecular ion region of the fatty acids. As the proton affinity of the reagent increased, the protonated molecular ions of the fatty acids became the predominant ions observed in the mass spectrum. As a result, chemical ionization was shown to be more effective than electron ionization in bacterial profiling. Whereas the bacteria could be distinguished at the Genera level using electron ionization, further differentiation to the subspecies level was possible using chemical ionization. The greatest separation among the five test organisms, in terms of Euclidean distances, was obtained using ethanol as the chemical ionization reagent and using pooled masses representing specific fatty acid biomarkers rather than total ion profiles. PMID:9989380

  7. Buffer-Gas Cooling of a Single Ion in a Multipole Radio Frequency Trap Beyond the Critical Mass Ratio

    NASA Astrophysics Data System (ADS)

    Höltkemeier, Bastian; Weckesser, Pascal; López-Carrera, Henry; Weidemüller, Matthias

    2016-06-01

    We theoretically investigate the dynamics of a trapped ion immersed in a spatially localized buffer gas. For a homogeneous buffer gas, the ion's energy distribution reaches a stable equilibrium only if the mass of the buffer gas atoms is below a critical value. This limitation can be overcome by using multipole traps in combination with a spatially confined buffer gas. Using a generalized model for elastic collisions of the ion with the buffer-gas atoms, the ion's energy distribution is numerically determined for arbitrary buffer-gas distributions and trap parameters. Three regimes characterized by the respective analytic form of the ion's equilibrium energy distribution are found. Final ion temperatures down to the millikelvin regime can be achieved by adiabatically decreasing the spatial extension of the buffer gas and the effective ion trap depth (forced sympathetic cooling).

  8. Development of a linear ion trap/orthogonal-time-of-flight mass spectrometer for time-dependent observation of product ions by ultraviolet photodissociation of peptide ions.

    PubMed

    Kim, Tae-Young; Schwartz, Jae C; Reilly, James P

    2009-11-01

    A hybrid linear ion trap/orthogonal time-of-flight (TOF) mass spectrometer has been developed to observe time-dependent vacuum ultraviolet photodissociation product ions. In this apparatus, a reflectron TOF mass analyzer is orthogonally interfaced to an LTQ using rf-only octopole and dc quadrupole ion guides. Precursor ions are generated by electrospray ionization and isolated in the ion trap. Subsequently they are directed to the TOF source where photodissociation occurs and product ions are extracted for mass analysis. To detect photodissociation product ions having axially divergent trajectories, a large rectangular detector is utilized. With variation of the time between photodissociation and orthogonal extraction in the TOF source, product ions formed over a range of times after photoexcitation can be sampled. Time-dependent observation of product ions following 157 nm photodissociation of a singly charged tryptic peptide ion (NWDAGFGR) showed that prompt photofragment ions (x- and v-type ions) dominate the tandem mass spectrum up to 1 micros after the laser shot, but the intensities of low energy thermal fragment ions (y-type ions) become comparable several microseconds later. Different proton mobilization time scales were observed for arginine- and lysine-terminated tryptic peptides.

  9. TITAN: An ion trap facility for on-line mass measurement experiments

    NASA Astrophysics Data System (ADS)

    Kwiatkowski, A. A.; Andreoiu, C.; Bale, J. C.; Brunner, T.; Chaudhuri, A.; Chowdhury, U.; Delheij, P.; Ettenauer, S.; Frekers, D.; Gallant, A. T.; Grossheim, A.; Gwinner, G.; Jang, F.; Lennarz, A.; Ma, T.; Mané, E.; Pearson, M. R.; Schultz, B. E.; Simon, M. C.; Simon, V. V.; Dilling, J.

    2014-01-01

    Precision determinations of ground state or even isomeric state masses reveal fingerprints of nuclear structure. In particular, at the limits of existence for very neutron-rich or -deficient isotopes, one can extract detailed information about nuclear structure from separation energies or binding energies. Mass measurements are important to uncover new phenomena, to test new theoretical predictions, or to refine model approaches. For example, the N = 28 shell has proven more stable than previously expected; however, the predicted new "magic" number at N = 34 in the K and Ca isotopes has yet to be confirmed experimentally. For these neutron-rich nuclei, the inclusion of three-body forces leads to significantly better predictions of the ground-state mass. Similarly, halo nuclei present an excellent application for ab-initio theory, where ground state properties, like masses and radii, test our understanding of nuclear structure. Precision mass determinations at TRIUMF are carried out with the TITAN (TRIUMF's Ion Traps for Atomic and Nuclear science) facility. It is an ion-trap setup coupled to the on-line facility ISAC. TITAN has measured masses of isotopes as short-lived as 9 ms (almost an order of magnitude shorter-lived than any other Penning trap system), and it is the only one with charge breeding capabilities, which allow us to boost the precision by almost 2 orders of magnitude. We recently made use of this feature by measuring short-lived, proton-rich Rb-isotopes, up to 74Rb while reaching the 12 + charge state, which together with other improvements led to an increase in precision by a factor 36.

  10. MEMS Fabrication of Micro Cylindrical Ion Trap Mass Spectrometer for CubeSats Application

    NASA Astrophysics Data System (ADS)

    Zheng, Y.

    2015-10-01

    Microelectromechanical Systems (MEMS) technology is used to fabricate arrays of micro Cylindrical Ion Traps (μCIT) which are integrated into a miniaturized mass spectrometer (MS). The micro μCITs are built from silicon wafers and requires high machining precision, smooth surface, and high dimensional uniformity across the array for optimum mass spectrometer performance. In order to build these 3D miniature structures several MEMS processing techniques were explored and a process was developed and tested. By using the developed MEMS process, the required μCIT 4 x 4 arrays were fabricated. This included a chip design variation in which mechanical locking pits and posts were machined in the Ring Electrode (RE) chip and End Plate (EP) chips respectively, for self-assembly. The size of the assembled μCIT is only 12 mm x 12 mm x 1.5 mm. It is a key component for the miniature mass spectrometer. The micro cylindrical ion trap mass spectrometer has the advantages of low-power operation, simpler electronics and less-stringent vacuum system requirements. The MEMS batch production capabilities will also greatly lower the cost. It is a promising candidate for CubeSat and nanoSats applications for exploration of chemical distributions in space.

  11. Shedding light on the mercury mass discrepancy by weighing Hg 52+ ions in a Penning trap

    NASA Astrophysics Data System (ADS)

    Fritioff, T.; Bluhme, H.; Schuch, R.; Bergström, I.; Björkhage, M.

    2003-07-01

    In their nuclear tables Audi and Wapstra have pointed out a serious mass discrepancy between their extrapolated values for the mercury isotopes and those from a direct measurement by the Manitoba group. The values deviate by as much as 85 ppb from each other with claimed uncertainties of about 16 and 7 ppb, respectively. In order to decide which values are correct the masses of the 198Hg and 204Hg isotopes have been measured in the Stockholm Penning trap mass spectrometer SMILETRAP using 52+ ions. This charge state corresponds to a filled Ni electron configuration for which the electron binding energy can be accurately calculated. The mass values obtained are 197.966 768 44(43) u for 198Hg and 203.973 494 10(39) u for 204Hg. These values agree with those measured by the Manitoba group, with a 3 times lower uncertainty. This measurement was made possible through the implementation of a cooling technique of the highly charged mercury ions during charge breeding in the electron beam ion source used for producing the Hg 52+ ions.

  12. Electrospray ionization ion-trap multiple-stage mass spectrometry of Quillaja saponins.

    PubMed

    Bankefors, Johan; Broberg, Susanna; Nord, Lars I; Kenne, Lennart

    2011-07-01

    Fifteen identified C-18 fatty acyl-containing saponin structures from Quillaja saponaria Molina have been investigated by electrospray ionization ion-trap multiple-stage mass spectrometry (ESI-IT-MS(n)) in positive ion mode. Their MS(1)-MS(3) spectra were analyzed and ions corresponding to useful fragments, important for the structural identification of Quillaja saponins, were recognized. A few key fragments could describe the structural variations in the C-3 and the C-28 oligosaccharides of the Quillaja saponins. A flowchart involving a stepwise procedure based on key fragments from the MS(1)-MS(3) spectra of these saponins, together with key fragments from these saponins and 13 previously investigated saponins, was constructed for the identification of structural elements in Quillaja saponins. Peak intensity ratios in MS(3) spectra were found to be correlated to structural features of the investigated saponins and is therefore of value for the identification of regioisomers.

  13. Automated Gain Control Ion Funnel Trap for Orthogonal Time-of-Flight Mass Spectrometry

    PubMed Central

    Ibrahim, Yehia M.; Belov, Mikhail E.; Liyu, Andrei V.; Smith, Richard D.

    2009-01-01

    Time-of-flight mass spectrometry (TOF MS) is increasingly used in proteomics research. Herein, we report on the development and characterization of a TOF MS instrument with improved sensitivity equipped with an electrodynamic ion funnel trap (IFT) that employs an automated gain control (AGC) capability. The IFT-TOF MS was coupled to a reversed-phase capillary liquid chromatography (RPLC) separation and evaluated in experiments with complex proteolytic digests. When applied to a global tryptic digest of Shewanella oneidensis proteins, an order-of-magnitude increase in sensitivity compared to that of the conventional continuous mode of operation was achieved due to efficient ion accumulation prior to TOF MS analysis. As a result of this sensitivity improvement and related improvement in mass measurement accuracy, the number of unique peptides identified in the AGC-IFT mode was 5-fold greater than that obtained in the continuous mode. PMID:18512944

  14. Collisional and electric-field ionization of laser-prepared Rydberg states in an ion trap mass spectrometer

    SciTech Connect

    Ramsey, J.M.; Whitten, W.B.; Goeringer, D.E.; Buckley, B.T.

    1990-01-01

    Rydberg states of rubidium are selectively generated by one and two photon laser excitation in a quadrupole ion trap mass spectrometer. Collisional and electric-field ionization is investigated in trapping device. CCl{sub 4} is studied as a target for ionization of Rydberg states through electron attachment.

  15. A Proteomics Grade Electron Transfer Dissociation-enabled Hybrid Linear Ion Trap-orbitrap Mass Spectrometer

    PubMed Central

    McAlister, Graeme C.; Berggren, W. Travis; Horning, Stevan; Makarov, Alexander; Phanstiel, Doug; Griep-Raming, Jens; Stafford, George; Swaney, Danielle L.; Syka, John E. P.; Zabrouskov, Vlad

    2008-01-01

    Here we describe the modification of a quadrupole linear ion trap-orbitrap hybrid (QLT-orbitrap) mass spectrometer to accommodate a negative chemical ionization (NCI) source. The NCI source is used to produce fluoranthene radical anions for imparting electron transfer dissociation (ETD). The anion beam is stable, robust, and intense so that a sufficient amount of reagents can be injected into the QLT in only 4 - 8 ms. Following ion/ion reaction in the QLT, ETD product ions are mass-to-charge (m/z) analyzed in either the QLT (for speed and sensitivity) or the orbitrap (for mass resolution and accuracy). Here we describe the physical layout of this device, parametric optimization of anion transport, an evaluation of relevant ETD figures of merit, and the application of this instrument to protein sequence analysis. Described proteomic applications include complex peptide mixture analysis, post-translational modification (PTM) site identification, isotope-encoded quantitation, large peptide characterization, and intact protein analysis. From these experiments we conclude the ETD-enabled orbitrap will provide the proteomic field with several new opportunities and represents an advance in protein sequence analysis technologies. PMID:18613715

  16. Design and Performance Evaluation of a Linear Ion Trap Mass Analyzer Featuring Half Round Rod Electrodes

    NASA Astrophysics Data System (ADS)

    Li, Xiaoxu; Zhang, Xiaohua; Yao, Rujiao; He, Yang; Zhu, Yongyong; Qian, Jie

    2015-05-01

    A novel linear ion trap mass analyzer featuring half round rod electrodes (HreLIT) has been built. It is mainly composed of two pairs of stainless steel electrodes which have a cross-section of half round rod and a pair of end electrodes. The HreLIT has a simple structure and so it could be assembled by hand with relatively high mechanical accuracy. The external dimension of HreLIT is 50 mm × 29.5 mm × 28 mm (length × width × height) and its internal volume is about 3.8 cm3. A home-made HreLIT mass spectrometer with three-stage vacuum system was built and the performance of HreLIT was characterized using reserpine solution and PPG standard solution. When the scan rate was 254 u/s, mass peak with FWHM of 0.14 u was achieved for ions with m/z 609, which corresponds to a mass resolution of 4350. The HreLIT was also operated at a low q value of 0.28 to extend its mass range. The experiment result showed a mass range of over 2800 u and the amplitude of radio frequency (rf) signal was only 1560 V (0-p). Three-stage tandem mass spectrometry was successfully performed in the HreLIT, and the collision-induced dissociation (CID) efficiencies of MS2 (CID of ions with m/z 609) and MS3 (CID of ions with m/z 448) were 78% and 59%, respectively.

  17. Novel control modes to improve the performance of rectilinear ion trap mass spectrometer with dual pressure chambers

    NASA Astrophysics Data System (ADS)

    Huo, Xinming; Tang, Fei; Zhang, Xiaohua; Chen, Jin; Zhang, Yan; Guo, Cheng'an; Wang, Xiaohao

    2016-10-01

    The rectilinear ion trap (RIT) has gradually become one of the preferred mass analyzers for portable mass spectrometers because of its simple configuration. In order to enhance the performance, including sensitivity, quantitation capability, throughput, and resolution, a novel RIT mass spectrometer with dual pressure chambers was designed and characterized. The studied system constituted a quadrupole linear ion trap (QLIT) in the first chamber and a RIT in the second chamber. Two control modes are hereby proposed: Storage Quadrupole Linear Ion Trap-Rectilinear Ion Trap (SQLIT-RIT) mode, in which the QLIT was used at high pressure for ion storage and isolation, and the RIT was used for analysis; and Analysis Quadrupole Linear Ion Trap-Rectilinear Ion Trap (AQLIT-RIT) mode, in which the QLIT was used for ion storage and cooling. Subsequently, synchronous scanning and analysis were carried out by QLIT and RIT. In SQLIT-RIT mode, signal intensity was improved by a factor of 30; the limit of quantitation was reduced more than tenfold to 50 ng mL-1, and an optimal duty cycle of 96.4% was achieved. In AQLIT-RIT mode, the number of ions coexisting in the RIT was reduced, which weakened the space-charge effect and reduced the mass shift. Furthermore, the mass resolution was enhanced by a factor of 3. The results indicate that the novel control modes achieve satisfactory performance without adding any system complexity, which provides a viable pathway to guarantee good analytical performance in miniaturization of the mass spectrometer.

  18. Theoretical calculations for mass resolution of a quadrupole ion trap reflectron time-of-flight mass spectrometer.

    PubMed

    Choi, Chang Min; Heo, Jiyoung; Park, Chang Joon; Kim, Nam Joon

    2010-02-01

    We have developed a theoretical method of predicting the mass resolution for a quadrupole ion trap reflectron time-of-flight (QIT-reTOF) mass spectrometer as a function of the spatial and velocity distributions of ions, voltages applied to the electrodes, and dimensions of the instrument. The flight times of ions were calculated using theoretical equations derived with an assumption of uniform electric fields inside the QIT and with the analytical description of the potential including the monopole, dipole, and quadrupole components. The mass resolution was then estimated from the flight-time spread of the ions with finite spatial and velocity distributions inside the QIT. The feasibility of the theoretical method was confirmed by the reasonable agreement of the theoretical resolution with the experimental one measured by varying the extraction voltage of the QIT or the deceleration voltage of the reflectron. We found that the theoretical resolution estimated with the assumption of the uniform electric fields inside the QIT reproduced the experimental one better than that with the analytical description of the potential. The possible applications of this theoretical method include the optimization of the experimental parameters of a given QIT-reTOF mass spectrometer and the design of new instruments with higher mass resolution.

  19. Electrospray liquid chromatography quadrupole ion trap mass spectrometry determination of phenyl urea herbicides in water.

    PubMed

    Draper, W M

    2001-06-01

    Phenyl urea herbicides were determined in water by electrospray quadrupole ion trap liquid chromatography-mass spectrometry (ES-QIT-LC-MS). Over a wide concentration range [M - H](-) and MH(+) ions were prominent in ES spectra. At high concentrations dimer and trimer ions appeared, and sodium, potassium, and ammonium adducts also were observed. In the case of isopturon, source collision-induced dissociation (CID) fragmentation with low offset voltages increased the ion current associated with MH(+) and diminished dimer and trimer ion abundance. In the mass analyzer CID involved common pathways, for example, daughter ions of [M - H](-) resulted from loss of R(2)NH in N',N'-dialkyl ureas or loss of C(3)H(5)NO(2) (87 amu) in N'-methoxy ureas. A 2 mm (i.d.) x 15 cm C(18) reversed phase column was used for LC-MS with a linear methanol/water gradient and 0.5 mL/min flow rate. Between 1 and 100 pg/microg/L the response was highly linear with instrument detection limits ranging from <10 to 50 pg injected. Whereas the positive ES signal intensity was greater for each of the compounds except fluometuron, negative ion monitoring gave the highest signal-to-noise ratio. Analysis of spiked Colorado River water, a source high in total dissolved solids and total organic carbon, demonstrated that ES-QIT-LC-MS was routinely capable of quantitative analysis at low nanogram per liter concentrations in conjunction with a published C(18) SPE method. Under these conditions experimental method detection limits were between 8.0 and 36 ng/L, and accuracy for measurements in the 20-50 parts per trillion range was from 77 to 96%. Recoveries were slightly lower in surface water (e.g., 39-76%), possibly due to suppression of ionization. PMID:11409961

  20. Rapid determination of nicotine in urine by direct thermal desorption ion trap mass spectrometry

    SciTech Connect

    Wise, M.B.; Ilgner, R.H.; Guerin, M.R.

    1990-01-01

    The measurement of nicotine and cotinine in physiological fluids (urine, blood serum, and saliva) is widely used as a means of assessing human exposure to environmental tobacco smoke (ETS). Although numerous analytical methods exist for these measurements, they generally involve extensive sample preparation which increases cost and decreases sample throughput. We report the use of thermal desorption directly into an ion trap mass spectrometer (ITMS) for the rapid determination of nicotine and cotinine in urine. A 1{mu}L aliquot of urine is injected into a specially designed inlet and flash vaporized directly into an ITMS through an open-split capillary restrictor interface. Isobutane chemical ionization is used to generate (M+H){sup +} ions of the analytes and collision induced dissociation is used to generate characteristic fragment ions which are used to confirm their identity. Quantification is achieved by integrating the ion current for the characteristic ions and comparing with an external working curve. Detection limits are approximately 50 pg per analyte and the sample turnaround time is approximately 3 minutes without the need for extensive sample preparation. 12 refs., 5 figs.

  1. Resonance activation and collision-induced-dissociation of ions using rectangular wave dipolar potentials in a digital ion trap mass spectrometer.

    PubMed

    Xu, Fuxing; Wang, Liang; Dai, Xinhua; Fang, Xiang; Ding, Chuan-Fan

    2014-04-01

    Collision-induced dissociation (CID) of ions by resonance activation in a quadrupole ion trap is usually accomplished by resonance exciting the ions to higher kinetic energy, whereby the high kinetic energy ions collide with a bath gas, such as helium or argon, inside the trap and dissociate to fragments. A new ion activation method using a well-defined rectangular wave dipolar potential formed by dividing down the trapping rectangular waveform is developed and examined herein. The mass-selected parent ions are resonance excited to high kinetic energies by simply changing the frequency of the rectangular wave dipolar potential and dissociation proceeds. A relationship between the ion mass and the activation waveform frequency is also identified and described. This highly efficient (CID) procedure can be realized by simply changing the waveform frequency of the dipolar potential, which could certainly simplify tandem mass spectrometry analysis methods.

  2. Rapid determination of drugs and semivolatile organics by direct thermal desorption ion trap mass spectrometry

    SciTech Connect

    Wise, M.B.; Ilgner, R.H.; Buchanan, M.V.; Guerin, M.R.

    1991-01-01

    Direct thermal desorption of analytes into an ion trap mass spectrometer (ITMS) is being investigated as a technique for the rapid screening of a wide variety of samples for target semivolatile organic compounds. This includes the direct detection of drugs in physiological fluids, semivolatile organic pollutants in water and waste samples, and air pollutants collected on sorbent cartridges. In order to minimize the analysis time, chromatographic separation is not performed on the sample prior to introduction into the ITMS. Instead, selective chemical ionization and tandem mass spectrometry (MS/MS) are used achieve the specificity required for the target analytes. Detection limits are typically 10--50 ppb using a 1 uL aliquot of a liquid sample without preconcentration. Sample turn-around time is 2 to 5 minutes and 3 to 5 target analytes can be quantitatively determined simultaneously. 6 figs.

  3. Screening volatile organics by direct sampling ion trap and glow discharge mass spectrometry

    SciTech Connect

    Wise, M.B.; Hurst, G.B.; Thompson, C.V.; Buchanan, M.V.; Guerin, M.R.

    1991-01-01

    Two different types of direct sampling mass spectrometers are currently being evaluated in our laboratory for use as rapid screening tools for volatile organics in a wide range of environmental matrices. These include a commercially available ITMS ion trap mass spectrometer and a specially designed tandem source glow discharge quadrupole mass spectrometer. Both of these instruments are equipped with versatile sampling interfaces which enable direct monitoring of volatile organics at part-per-billion (ppb) levels in air, water, and soil samples. Direct sampling mass spectrometry does not utilize chromatographic or other separation steps prior to admission of samples into the analyzer. Instead, individual compounds are measured using one or more of the following methods: spectral subtraction, selective chemical ionization, and tandem mass spectroscopy (MS/MS). For air monitoring applications, an active sniffer'' probe is used to achieve instantaneous response. Water and soil samples are analyzed by means of high speed direct purge into the mass spectrometer. Both instruments provide a range of ionization options for added selectivity and the ITMS can also provide high efficiency collision induced dissociation MS/MS for target compound analysis. Detection limits and response factors have been determined for a large number volatile organics in air, water, and number of different soil types. 4 refs., 14 figs., 3 tabs.

  4. Direct Monitoring of Trace Atmospheric Species via Ion Trap Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Palmer, P. T.; Pearson, Richard; Saimonson, Jay D.; Wong, Carla M.; Lawless, James G. (Technical Monitor)

    1994-01-01

    There is an ever-increasing emphasis on the part of government agencies, academia, and industry on enhancing our understanding of atmospheric processes and assessing the impact of human activities on these processes. While issues such as the ozone hole and rising levels of greenhouse gases have received major attention. relatively little is known about the types, concentrations, sources, and sinks of hydrocarbons in the troposphere and stratosphere. Such information would be of tremendous utility in assessing the roles of various anthropogenic and biogenic processes on global carbon cycles. An ion trap mass spectrometer has been developed for monitoring trace levels of hydrocarbons in the atmosphere on NASA's DC-8 "flying laboratory". This aircraft is used to provide measurements in support of a number of "Mission to Planet Earth" activities and tropospheric chemistry experiments. In past missions, specific compounds have been monitored via highly specialized instrumentation, fast GO, or collection of whole air samples for subsequent ground-based analysis. The ion trap has several features. including small size. excellent sensitivity, and broad applicability, which make it highly atttrat:ive for atmospheric monitoring. The design of this instrument, its air sampling interface. and the various complications associated with aircraft-deployment will be described. Data showing the sensitivity of the instrument for detecting hydrocarbons at mixing ratios below one part-per-billion, and the use of MS/MS for direct, on-line, real-time monitoring will be presented.

  5. Ion funnel ion trap and process

    DOEpatents

    Belov, Mikhail E [Richland, WA; Ibrahim, Yehia M [Richland, WA; Clowers, Biran H [West Richland, WA; Prior, David C [Hermiston, OR; Smith, Richard D [Richland, WA

    2011-02-15

    An ion funnel trap is described that includes a inlet portion, a trapping portion, and a outlet portion that couples, in normal operation, with an ion funnel. The ion trap operates efficiently at a pressure of .about.1 Torr and provides for: 1) removal of low mass-to-charge (m/z) ion species, 2) ion accumulation efficiency of up to 80%, 3) charge capacity of .about.10,000,000 elementary charges, 4) ion ejection time of 40 to 200 .mu.s, and 5) optimized variable ion accumulation times. Ion accumulation with low concentration peptide mixtures has shown an increase in analyte signal-to-noise ratios (SNR) of a factor of 30, and a greater than 10-fold improvement in SNR for multiply charged analytes.

  6. Microfabricated linear Paul-Straubel ion trap

    DOEpatents

    Mangan, Michael A.; Blain, Matthew G.; Tigges, Chris P.; Linker, Kevin L.

    2011-04-19

    An array of microfabricated linear Paul-Straubel ion traps can be used for mass spectrometric applications. Each ion trap comprises two parallel inner RF electrodes and two parallel outer DC control electrodes symmetric about a central trap axis and suspended over an opening in a substrate. Neighboring ion traps in the array can share a common outer DC control electrode. The ions confined transversely by an RF quadrupole electric field potential well on the ion trap axis. The array can trap a wide array of ions.

  7. An expert system/ion trap mass spectrometry approach for life support systems monitoring

    NASA Technical Reports Server (NTRS)

    Palmer, Peter T.; Wong, Carla M.; Yost, Richard A.; Johnson, Jodie V.; Yates, Nathan A.; Story, Michael

    1992-01-01

    Efforts to develop sensor and control system technology to monitor air quality for life support have resulted in the development and preliminary testing of a concept based on expert systems and ion trap mass spectrometry (ITMS). An ITMS instrument provides the capability to identify and quantitate a large number of suspected contaminants at trace levels through the use of a variety of multidimensional experiments. An expert system provides specialized knowledge for control, analysis, and decision making. The system is intended for real-time, on-line, autonomous monitoring of air quality. The key characteristics of the system, performance data and analytical capabilities of the ITMS instrument, the design and operation of the expert system, and results from preliminary testing of the system for trace contaminant monitoring are described.

  8. Fast Screening of Polycyclic Aromatic Hydrocarbons using Trapped Ion Mobility Spectrometry - Mass Spectrometry

    PubMed Central

    Castellanos, A.; Benigni, P.; Hernandez, D. R.; DeBord, J. D.; Ridgeway, M. E.; Park, M. A.

    2014-01-01

    In the present paper, we showed the advantages of trapped ion mobility spectrometry coupled too mass spectrometry (TIMS-MS) combined with theoretical calculations for fast identification (millisecond timescale) of polycyclic aromatic hydrocarbons (PAH) compounds from complex mixtures. Accurate PAH collision cross sections (CCS, in nitrogen as a bath gas) are reported for the most commonly encountered PAH compounds and the ability to separate PAH geometric isomers is shown for three isobaric pairs with mobility resolution exceeding 150 (3–5 times higher than conventional IMS devices). Theoretical candidate structures (optimized at the DFT/B3LYP level) are proposed for the most commonly encountered PAH compounds showing good agreement with the experimental CCS values (<5%). The potential of TIMS-MS for the separation and identification of PAH compounds from complex mixtures without the need of lengthy pre-separation steps is illustrated for the case of a complex soil mixture. PMID:25558291

  9. Using metal complex ion-molecule reactions in a miniature rectilinear ion trap mass spectrometer to detect chemical warfare agents.

    PubMed

    Graichen, Adam M; Vachet, Richard W

    2013-06-01

    The gas-phase reactions of a series of coordinatively unsaturated [Ni(L)n](y+) complexes, where L is a nitrogen-containing ligand, with chemical warfare agent (CWA) simulants in a miniature rectilinear ion trap mass spectrometer were investigated as part of a new approach to detect CWAs. Results show that upon entering the vacuum system via a poly(dimethylsiloxane) (PDMS) membrane introduction, low concentrations of several CWA simulants, including dipropyl sulfide (simulant for mustard gas), acetonitrile (simulant for the nerve agent tabun), and diethyl phosphite (simulant for nerve agents sarin, soman, tabun, and VX), can react with metal complex ions generated by electrospray ionization (ESI), thereby providing a sensitive means of detecting these compounds. The [Ni(L)n](2+) complexes are found to be particularly reactive with the simulants of mustard gas and tabun, allowing their detection at low parts-per-billion (ppb) levels. These detection limits are well below reported exposure limits for these CWAs, which indicates the applicability of this new approach, and are about two orders of magnitude lower than electron ionization detection limits on the same mass spectrometer. The use of coordinatively unsaturated metal complexes as reagent ions offers the possibility of further tuning the ion-molecule chemistry so that desired compounds can be detected selectively or at even lower concentrations.

  10. A new sheathless electrospray interface for coupling of capillary electrophoresis to ion-trap mass spectrometry.

    PubMed

    Bendahl, Lars; Hansen, Steen Honoré; Olsen, Jørgen

    2002-01-01

    A simple laboratory-made sheathless electrospray interface for coupling of capillary electrophoresis to ion-trap mass spectrometry (CE/MS) was developed. The interface was machined in-house and it was designed to be freely interchangeable with the commercially available ionization sources for the mass spectrometer. Sharpened fused-silica capillaries were coated with nickel by a simple electrodeless plating procedure and were used as all-in-one columns/emitters. The electrodeless plating produced a 2-5- micro m thick smooth nickel layer that lasted for more than 8 h of continuous electrospraying. The performance of the CE/MS interface was examined by using four cationic imipramine derivatives as test substances. Relative detection limits were calculated on the basis of the extracted ion electrophorograms and were in the range 6-130 nmol/L, corresponding to absolute detection limits in the range of 20-400 amol. The system was applied for analysis of impurities in an impure imipramine N-oxide preparation, and two of the impurities could be identified on the basis of online-MS(MS) spectra recorded in scan-dependent mode. PMID:12478579

  11. Optimized precursor ion selection for labile ions in a linear ion trap mass spectrometer and its impact on quantification using selected reaction monitoring.

    PubMed

    Lee, Hyun-Seok; Shin, Kyong-Oh; Jo, Sung-Chan; Lee, Yong-Moon; Yim, Yong-Hyeon

    2014-12-01

    The fragmentation of fragile ions during the application of an isolation waveform for precursor ion selection and the resulting loss of isolated ion intensity is well-known in ion trap mass spectrometry (ITMS). To obtain adequate ion intensity in the selected reaction monitoring (SRM) of fragile precursor ions, a wider ion isolation width is required. However, the increased isolation width significantly diminishes the selectivity of the channels chosen for SRM, which is a serious problem for samples with complex matrices. The sensitive and selective quantification of many lipid molecules, including ceramides from real biological samples, using a linear ion trap mass spectrometer is also hindered by the same problem because of the ease of water loss from protonated ceramide ions. In this study, a method for the reliable quantification of ceramides using SRM with near unity precursor ion isolation has been developed for ITMS by utilizing alternative precursor ions generated by in-source dissociation. The selected precursor ions allow the isolation of ions with unit mass width and the selective analysis of ceramides using SRM with negligible loss of sensitivity. The quantification of C18:0-, C24:0- and C24:1-ceramides using the present method shows excellent linearity over the concentration ranges from 6 to 100, 25 to 1000 and 25 to 1000 nM, respectively. The limits of detection of C18:0-, C24:0- and C24:1-ceramides were 0.25, 0.25 and 5 fmol, respectively. The developed method was successfully applied to quantify ceramides in fetal bovine serum.

  12. Radial stratification of ions as a function of mass to charge ratio in collisional cooling radio frequency multipoles used as ion guides or ion traps.

    PubMed

    Tolmachev, A V; Udseth, H R; Smith, R D

    2000-01-01

    Collisional cooling in radio frequency (RF) ion guides has been used in mass spectrometry as an intermediate step during the transport of ions from high pressure regions of an ion source into high vacuum regions of a mass analyzer. Such collisional cooling devices are also increasingly used as 'linear', two-dimensional (2D) ion traps for ion storage and accumulation to achieve improved sensitivity and dynamic range. We have used the effective potential approach to study m/z dependent distribution of ions in the devices. Relationships obtained for the ideal 2D multipole demonstrate that after cooling the ion cloud forms concentric cylindrical layers, each of them composed of ions having the same m/z ratio; the higher the m/z, the larger is the radial position occupied by the ions. This behavior results from the fact that the effective RF focusing is stronger for ions of lower m/z, pushing these ions closer to the axis. Radial boundaries of the layers are more distinct for multiply charged ions, compared to singly charged ions having the same m/z and charge density. In the case of sufficiently high ion density and low ion kinetic energy, we show that each m/z layer is separated from its nearest neighbor by a radial gap of low ion density. The radial gaps of low ion population between the layers are formed due to the space charge repulsion. Conditions for establishing the m/z stratified structure include sufficiently high charge density and adequate collisional relaxation. These conditions are likely to occur in collisional RF multipoles operated as ion guides or 2D ion traps for external ion accumulation. When linear ion density increases, the maximum ion cloud radius also increases, and outer layers of high m/z ions approach the multipole rods and may be ejected. This 'overfilling' of the multipole capacity results in a strong discrimination against high m/z ions. A relationship is reported for the maximum linear ion density of a multipole that is not overfilled.

  13. Tailored noise waveform/collision-induced dissociation of ions stored in a linear ion trap combined with liquid chromatography/Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Vilkov, Andrey N; Bogdanov, Bogdan; Pasa-Tolić, Ljiljana; Prior, Dave C; Anderson, Gordon A; Masselon, Christophe D; Moore, Ronald J; Smith, Richard D

    2004-01-01

    A new collision-induced dissociation (CID) technique based on broadband tailored noise waveform (TNW) excitation of ions stored in a linear ion trap has been developed. In comparison with the conventional sustained off-resonance irradiation (SORI) CID method commonly used in Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), this MS/MS technique increases throughput by eliminating the long pump-down delay associated with gas introduction into the high vacuum ICR cell region. In addition, the TNW-CID method speeds spectrum acquisition since it does not require Fourier transformation, calculation of resonant frequencies and generation of the excitation waveforms. We demonstrate TNW-CID coupled with on-line capillary reverse-phase liquid chromatography separations for the identification of peptides. The experimental results are compared with data obtained using conventional quadrupole ion trap MS/MS and SORI-CID MS/MS in an ICR cell.

  14. Automated gas-phase purification for accurate, multiplexed quantification on a stand-alone ion trap mass spectrometer

    PubMed Central

    Vincent, Catherine E.; Rensvold, Jarred W.; Westphall, Michael S.; Pagliarini, David J.; Coon, Joshua J.

    2012-01-01

    Isobaric tagging enables the acquisition of highly-multiplexed proteome quantification but is hindered by the pervasive problem of precursor interference. The elimination of co-isolated contaminants prior to reporter tag generation can be achieved through the use of gas-phase purification via proton transfer ion/ion reactions (QuantMode); however, the original QuantMode technique was implemented on the high resolution linear ion trap-Orbitrap hybrid mass spectrometer enabled with electron transfer dissociation (ETD). Here we extend this technology to stand-alone linear ion trap systems (trapQuantMode). Facilitated by the use of inlet beam-type activation (i.e., trapHCD) for production and observation of the low mass-to-charge reporter region, this scan sequence comprises three separate events to maximize peptide identifications, minimize duty cycle requirements, and increase quantitative accuracy, precision, and dynamic range. Significant improvements in quantitative accuracy were attained over standard methods when using trapQuantMode (trapQM) to analyze an interference model system comprising tryptic peptides of yeast that we contaminated with human peptides. Finally, we demonstrate practical benefits of this method by analysis of the proteomic changes that occur during mouse skeletal muscle myoblast differentiation. While trapQM’s reduced duty cycle led to the identification of fewer proteins than conventional operation (4,050 vs. 2,964), trapQM identified more significant differences (>1.5 fold, 1,362 vs 1,132, respectively; P<0.05) between the proteomes of undifferentiated myoblasts and differentiated myotubes and nearly ten-fold more differences with changes greater than 5-fold (96 vs. 12). We further show that our trapQM dataset is superior for identifying changes in protein abundance that are consistent with the metabolic and structural changes known to accompany myotube formation. PMID:23046161

  15. Miniaturized system of a gas chromatograph coupled with a Paul ion trap mass spectrometer

    NASA Technical Reports Server (NTRS)

    Shortt, B. J.; Darrach, M. R.; Holland, Paul M.; Chutjian, A.

    2005-01-01

    Miniature gas chromatography (GC) and miniature mass spectrometry (MS) instrumentation has been developed to identify and quantify the chemical compounds present in complex mixtures of gases. The design approach utilizes micro-GC components coupled with a Paul quadrupole ion trap (QIT) mass spectrometer. Inherent to the system are high sensitivity, good dynamic range, good QIT resolution, low GC flow-rates to minimize vacuum requirements and the need for consumables; and the use of a modular approach to adapt to volatile organic compounds dissolved in water or present in sediment. Measurements are reported on system response to gaseous species at concentrations varying over four orders of magnitude. The ability of the system to deal with complicated mixtures is demonstrated, and future improvements are discussed. The GC/QIT system described herein has a mass, volume and power that are, conservatively, one-twentieth of those of commercial off-the-shelf systems. Potential applications are to spacecraft cabin-air monitoring, robotic planetary exploration and trace-species detection for residual gas analysis and environmental monitoring.

  16. Development of a Linear Ion Trap Mass Spectrometer (LITMS) Investigation for Future Planetary Surface Missions

    NASA Technical Reports Server (NTRS)

    Brinckerhoff, W.; Danell, R.; Van Ameron, F.; Pinnick, V.; Li, X.; Arevalo, R.; Glavin, D.; Getty, S.; Mahaffy, P.; Chu, P.; Zacny, K.; Rogacki, S.; Grubisic, A.; Cornish, T.

    2014-01-01

    Future surface missions to Mars and other planetary bodies will benefit from continued advances in miniature sensor and sample handling technologies that enable high-performance chemical analyses of natural samples. Fine-scale (approx.1 mm and below) analyses of rock surfaces and interiors, such as exposed on a drill core, will permit (1) the detection of habitability markers including complex organics in association with their original depositional environment, and (2) the characterization of successive layers and gradients that can reveal the time-evolution of those environments. In particular, if broad-based and highly-sensitive mass spectrometry techniques could be brought to such scales, the resulting planetary science capability would be truly powerful. The Linear Ion Trap Mass Spectrometer (LITMS) investigation is designed to conduct fine-scale organic and inorganic analyses of short (approx.5-10 cm) rock cores such as could be acquired by a planetary lander or rover arm-based drill. LITMS combines both pyrolysis/gas chromatograph mass spectrometry (GCMS) of sub-sampled core fines, and laser desorption mass spectrometry (LDMS) of the intact core surface, using a common mass analyzer, enhanced from the design used in the Mars Organic Molecule Analyzer (MOMA) instrument on the 2018 ExoMars rover. LITMS additionally features developments based on the Sample Analysis at Mars (SAM) investigation on MSL and recent NASA-funded prototype efforts in laser mass spectrometry, pyrolysis, and precision subsampling. LITMS brings these combined capabilities to achieve its four measurement objectives: (1) Organics: Broad Survey Detect organic molecules over a wide range of molecular weight, volatility, electronegativity, concentration, and host mineralogy. (2) Organic: Molecular Structure Characterize internal molecular structure to identify individual compounds, and reveal functionalization and processing. (3) Inorganic Host Environment Assess the local chemical

  17. Identification and quantification of glucosinolates in rapeseed using liquid chromatography-ion trap mass spectrometry.

    PubMed

    Millán, Silvia; Sampedro, M Carmen; Gallejones, Patricia; Castellón, Ander; Ibargoitia, Maria L; Goicolea, M Aranzazu; Barrio, Ramón J

    2009-07-01

    A rapid and sensitive method for the speciation and quantification of glucosinolates in rapeseed is described. The method combines liquid chromatography (LC) with ion trap mass spectrometry (ITMS) detection. Electrospray ionization (ESI) has been chosen as the ionization technique for the on-line coupling of LC with ITMS. Glucosinolates are extracted from different rapeseeds with MeOH and the extracts are cleaned-up by solid phase extraction with Florisil cartridges. Aqueous extracts are injected into LC system coupled to an ITMS, leading to accurately quantify eight of the most important glucosinolates in rapeseed, by MS2 mode and confirming their structure by MS3 acquisition. All the glucosinolates found in rapeseeds provide good signals corresponding to the deprotonated precursor ion [M-H]-. The method is reliable and reproducible, and detection limits range from 0.5 nmol g(-1) to 3.7 nmol g(-1) when 200 mg of dried seeds of certified reference material are analyzed. Within-day and between-day RSD percentages range between 2.4-14.1% and 3.9-16.9%, respectively. The LC-ESI-ITMS-MS method described here allows for a rapid assessment of these metabolites in rapeseed without a desulfatation step. The overall process has been successfully applied to identify and quantify glucosinolates in rapeseed samples.

  18. Gas Chromatographic-Ion Trap Mass Spectrometric Analysis of Volatile Organic Compounds by Ion-Molecule Reactions Using the Electron-Deficient Reagent Ion CCl{3/+}

    NASA Astrophysics Data System (ADS)

    Wang, Cheng-Zhong; Su, Yue; Wang, Hao-Yang; Guo, Yin-Long

    2011-10-01

    When using tetrachloromethane as the reagent gas in gas chromatography-ion trap mass spectrometry equipped with hybrid ionization source, the cation CCl{3/+} was generated in high abundance and further gas-phase experiments showed that such an electron-deficient reagent ion CCl{3/+} could undergo interesting ion-molecule reactions with various volatile organic compounds, which not only present some informative gas-phase reactions, but also facilitate qualitative analysis of diverse volatile compounds by providing unique mass spectral data that are characteristic of particular chemical structures. The ion-molecule reactions of the reagent ion CCl{3/+} with different types of compounds were studied, and results showed that such reactions could give rise to structurally diagnostic ions, such as [M + CCl3 - HCl]+ for aromatic hydrocarbons, [M - OH]+ for saturated cyclic ether, ketone, and alcoholic compounds, [M - H]+ ion for monoterpenes, M·+ for sesquiterpenes, [M - CH3CO]+ for esters, as well as the further fragment ions. The mechanisms of ion-molecule reactions of aromatic hydrocarbons, aliphatic ketones and alcoholic compounds with the reagent ion CCl{3/+} were investigated and proposed according to the information provided by MS/MS experiments and theoretical calculations. Then, this method was applied to study volatile organic compounds in Dendranthema indicum var. aromaticum and 20 compounds, including monoterpenes and their oxygen-containing derivatives, aromatic hydrocarbon and sesquiterpenes were identified using such ion-molecule reactions. This study offers a perspective and an alternative tool for the analysis and identification of various volatile compounds.

  19. Real-Time Quantitative Analysis of H2, He, O2, and Ar by Quadrupole Ion Trap Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Ottens, Andrew K.; Harrison, W. W.; Griffin, Timothy P.; Helms, William R.; Voska, N. (Technical Monitor)

    2002-01-01

    The use of a quadrupole ion trap mass spectrometer for quantitative analysis of hydrogen and helium as well as other permanent gases is demonstrated. The customized instrument utilizes the mass selective instability mode of mass analysis as with commercial instruments; however, this instrument operates at a greater RF trapping frequency and without a buffer gas. With these differences, a useable mass range from 2 to over 50 Da is achieved, as required by NASA for monitoring the Space Shuttle during a launch countdown. The performance of the ion trap is evaluated using part-per-million concentrations of hydrogen, helium, oxygen and argon mixed into a nitrogen gas stream. Relative accuracy and precision when quantitating the four analytes were better than the NASA-required minimum of 10% error and 5% deviation, respectively. Limits of detection were below the NASA requirement of 25-ppm hydrogen and 100-ppm helium; those for oxygen and argon were slightly higher than the requirement. The instrument provided adequate performance at fast data recording rates, demonstrating the utility of an ion trap mass spectrometer as a real-time quantitative monitoring device for permanent gas analysis.

  20. Identification of the related substances of tilmicosin by liquid chromatography/ion trap mass spectrometry.

    PubMed

    Stoev, Georgi; Nazarov, Valeri

    2008-06-01

    Structures of seven impurities of the veterinary drug tilmicosin have been elucidated by multiple fragmentation with ion trap tandem mass spectrometry. All related compounds possess the main lactone ring of tilmicosin. The differences in their structures are due to the hydroxyl, mycaminose, 3,5-dimethylpiperidine and mycinose groups connected to C(3), C(5), C(6), C(14) of the lactone ring, respectively. The following compounds of the impurity profile of tilmicosin were identified: B - tilmicosin with a hydroxyl group at C(3); C - tilmicosin without a methyl group at the N-atom connected to C(3) of the mycaminose ring; D - tilmicosin with a hydroxyl group at C(6) of the mycaminose ring; E - tilmicosin with a methoxy group at C(3), F - desmicosin; G - 20-dihydrodesmicosin; and H - tilmicosin without a mycaminose ring. Isomers of the compounds B, C, D, E and H were identified by their mass chromatograms and retention times. The concentrations of the impurities varied in the range of 0.1% to 2.9%. PMID:18491285

  1. Identification of the related substances of tilmicosin by liquid chromatography/ion trap mass spectrometry.

    PubMed

    Stoev, Georgi; Nazarov, Valeri

    2008-06-01

    Structures of seven impurities of the veterinary drug tilmicosin have been elucidated by multiple fragmentation with ion trap tandem mass spectrometry. All related compounds possess the main lactone ring of tilmicosin. The differences in their structures are due to the hydroxyl, mycaminose, 3,5-dimethylpiperidine and mycinose groups connected to C(3), C(5), C(6), C(14) of the lactone ring, respectively. The following compounds of the impurity profile of tilmicosin were identified: B - tilmicosin with a hydroxyl group at C(3); C - tilmicosin without a methyl group at the N-atom connected to C(3) of the mycaminose ring; D - tilmicosin with a hydroxyl group at C(6) of the mycaminose ring; E - tilmicosin with a methoxy group at C(3), F - desmicosin; G - 20-dihydrodesmicosin; and H - tilmicosin without a mycaminose ring. Isomers of the compounds B, C, D, E and H were identified by their mass chromatograms and retention times. The concentrations of the impurities varied in the range of 0.1% to 2.9%.

  2. MSM, an Efficient Workflow for Metabolite Identification Using Hybrid Linear Ion Trap Orbitrap Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Cho, Robert; Huang, Yingying; Schwartz, Jae C.; Chen, Yan; Carlson, Timothy J.; Ma, Ji

    2012-05-01

    Identification of drug metabolites can often yield important information regarding clearance mechanism, pharmacologic activity, or toxicity for drug candidate molecules. Additionally, the identification of metabolites can provide beneficial structure-activity insight to help guide lead optimization efforts towards molecules with optimal metabolic profiles. There are challenges associated with detecting and identifying metabolites in the presence of complex biological matrices, and new LC-MS technologies have been developed to meet these challenges. In this report, we describe the development of an experimental approach that applies unique features of the hybrid linear ion trap Orbitrap mass spectrometer to streamline in vitro and in vivo metabolite identification experiments. The approach, referred to as MSM, utilizes multiple collision cells, dissociation methods, mass analyzers, and detectors. With multiple scan types and different dissociation modes built into one experimental method, along with flexible post-acquisition analysis options, the MSM workflow offers an attractive option to fast and reliable identification of metabolites in different kinds of in vitro and in vivo samples. The MSM workflow was successfully applied to metabolite identification analysis of verapamil in both in vitro rat hepatocyte incubations and in vivo rat bile samples.

  3. Ion trap device

    DOEpatents

    Ibrahim, Yehia M.; Smith, Richard D.

    2016-01-26

    An ion trap device is disclosed. The device includes a series of electrodes that define an ion flow path. A radio frequency (RF) field is applied to the series of electrodes such that each electrode is phase shifted approximately 180 degrees from an adjacent electrode. A DC voltage is superimposed with the RF field to create a DC gradient to drive ions in the direction of the gradient. A second RF field or DC voltage is applied to selectively trap and release the ions from the device. Further, the device may be gridless and utilized at high pressure.

  4. Selective injection and isolation of ions in quadrupole ion trap mass spectrometry using notched waveforms created using the inverse Fourier transform

    SciTech Connect

    Soni, M.H.; Cooks, R.G. )

    1994-08-01

    Broad-band excitation of ions is accomplished in the quadrupole ion trap mass spectrometer using notched waveforms created by the SWIFT (stored waveform inverse Fourier transform) technique. A series of notched SWIFT pulses are applied during the period of ion injection from an external Cs[sup +] source to resonantly eject all ions whose resonance frequencies fall within the frequency range of the pulse while injecting only those analyte ions whose resonance frequencies fall within the limits of the notch. This allows selective injection and accumulation of the ions of interest and continuous ejection of the unwanted ions. This is shown to result in significant improvement in S/N ratio, resolution, and sensitivity for the analyte ions of interest. Selective ion injection is demonstrated by injecting the protonated molecules of peptides VSV and gramicidin S and the intact cation of l-carnitine hydrochloride, using singly notched SWIFT pulses. Multiply notched SWIFT pulses are used to simultaneously inject ions of different m/z values of l-carnitine hydrochloride into the ion trap. A new coarse/fine ion isolation procedure, which employs a doubly notched SWIFT pulse, is demonstrated for isolating ions of a single m/z value of 4-bromobiphenyl from a population of trapped ions. 36 refs., 10 figs., 2 tabs.

  5. Separation and characterization of oxaliplatin dinucleotides from DNA using HPLC-ESI ion trap mass spectrometry.

    PubMed

    Mowaka, Shereen; Linscheid, Michael

    2008-11-01

    Oxaliplatin is a third-generation platinum complex, and has a broad spectrum of antitumor activity. Such platinum complexes with the DACH carrier ligand have recently received increasing attention since they show efficacy against cisplatin-resistant cell lines. As the foremost indication of antitumor activity of platinum drugs is the formation of adducts with genomic DNA, calf thymus DNA-oxaliplatin adducts were the major target in this study. Calf thymus DNA was incubated with oxaliplatin, resulting in the formation of a large number of platinum-DNA adducts. Treated DNA was digested into the dinucleotides with a combination of enzymes, namely, benzonase, alkaline phosphatase, and nuclease S1. Using a high-performance liquid chromatography, we carried out the separation of individual platinum-DNA adducts which were concurrently identified using electrospray ionization ion trap mass spectrometry (MS). Both 1,2-intrastrand and 1,2-interstrand cross-linked adducts were found; however, those of the intrastrand nature have a considerably higher abundance than those of the interstrand cross-links. Among them, d(GpG)-oxaliplatin was the most abundant bifuctional adduct. To a lesser extent, a few monofunctional adducts were detected as well. MS(n) experiments served to ascertain the detailed structures of oxaliplatin adducts of dinucleoside monophosphates and of dinucleotides.

  6. [Determination of 21 fragrance allergens in toys by gas chromatography-ion trap mass spectrometry].

    PubMed

    Lü, Qing; Zang, Qing; Bai, Hua; Li, Haiyu; Kang, Suyuan; Wang, Chao

    2012-05-01

    A method of gas chromatography-ion trap mass spectrometry (GC-IT-MS) was developed for the determination of 21 fragrance allergens in sticker toys, plush toys and plastic toys. The experimental conditions, such as sample pretreatment conditions, and the analytical conditions of GC-IT-MS, were optimized. The sticker toy samples and plush toy samples were extracted with acetone by ultrasonic wave, and the extracts were separated on an Agilent HP-1 MS column (50 m x 0.2 mm x 0.5 microm), then determined by IT-MS and quantified by external standard method. The plastic toy samples were extracted by the dissolution-precipitation approach, cleaned up with an Envi-carb solid phase extraction column and concentrated by rotary evaporation and nitrogen blowing, then determined by GC-IT-MS and quantified by external standard method. The calibration curves showed good linearity in the range of 0.002-50 mg/L with the correlation coefficients greater than 0.996 8. The limits of quantification (LOQ, S/N > 10) were 0.02-40 mg/kg. The average recoveries of the target compounds spiked in the sample at three concentration levels were in the range of 82.2%-110.8% with the relative standard deviations (RSDs) of 0.6%-10.5%. These results show that this method is accurate and sensitive for the qualitative and quantitative determination of the 21 fragrance allergens in the 3 types of toys.

  7. A Dual Source Ion Trap Mass Spectrometer for the Mars Organic Molecule Analyzer of ExoMars 2018

    NASA Technical Reports Server (NTRS)

    Brickerhoff, William B.; vanAmerom, F. H. W.; Danell, R. M.; Arevalo, R.; Atanassova, M.; Hovmand, L.; Mahaffy, P. R.; Cotter, R. J.

    2011-01-01

    We present details on the objectives, requirements, design and operational approach of the core mass spectrometer of the Mars Organic Molecule Analyzer (MOMA) investigation on the 2018 ExoMars mission. The MOMA mass spectrometer enables the investigation to fulfill its objective of analyzing the chemical composition of organic compounds in solid samples obtained from the near surface of Mars. Two methods of ionization are realized, associated with different modes of MOMA operation, in a single compact ion trap mass spectrometer. The stringent mass and power constraints of the mission have led to features such as low voltage and low frequency RF operation [1] and pulse counting detection.

  8. Improved Linear-Ion-Trap Frequency Standard

    NASA Technical Reports Server (NTRS)

    Prestage, John D.

    1995-01-01

    Improved design concept for linear-ion-trap (LIT) frequency-standard apparatus proposed. Apparatus contains lengthened linear ion trap, and ions processed alternately in two regions: ions prepared in upper region of trap, then transported to lower region for exposure to microwave radiation, then returned to upper region for optical interrogation. Improved design intended to increase long-term frequency stability of apparatus while reducing size, mass, and cost.

  9. Characterization of the chemical composition of white chrysanthemum flowers of Hangzhou by using high-performance ion trap mass spectrometry.

    PubMed

    Zhou, Xiahui; Chen, Xiaocheng; Wu, Xin; Cao, Gang; Zhang, Junjie

    2016-04-01

    In this study, high-performance liquid chromatography coupled with amaZon SL high-performance ion trap mass spectrometry was used to analyze the target components in white chrysanthemum flowers of Hangzhou. Twenty-one components were detected and identified in both white chrysanthemum flowers of Hangzhou samples by using target compound analysis. Furthermore, seven new compounds in white chrysanthemum flowers of Hangzhou were found and identified by analyzing the fragment ion behavior in the mass spectra. The established method can be expedient for the global quality investigation of complex components in herbal medicines and food. PMID:26843262

  10. Nonlinear integrable ion traps

    SciTech Connect

    Nagaitsev, S.; Danilov, V.; /SNS Project, Oak Ridge

    2011-10-01

    Quadrupole ion traps can be transformed into nonlinear traps with integrable motion by adding special electrostatic potentials. This can be done with both stationary potentials (electrostatic plus a uniform magnetic field) and with time-dependent electric potentials. These potentials are chosen such that the single particle Hamilton-Jacobi equations of motion are separable in some coordinate systems. The electrostatic potentials have several free adjustable parameters allowing for a quadrupole trap to be transformed into, for example, a double-well or a toroidal-well system. The particle motion remains regular, non-chaotic, integrable in quadratures, and stable for a wide range of parameters. We present two examples of how to realize such a system in case of a time-independent (the Penning trap) as well as a time-dependent (the Paul trap) configuration.

  11. Gas chromatographic-ion trap mass spectrometric analysis of volatile organic compounds by ion-molecule reactions using the electron-deficient reagent ion CCl3(+).

    PubMed

    Wang, Cheng-Zhong; Su, Yue; Wang, Hao-Yang; Guo, Yin-Long

    2011-10-01

    When using tetrachloromethane as the reagent gas in gas chromatography-ion trap mass spectrometry equipped with hybrid ionization source, the cation CCl(3)(+) was generated in high abundance and further gas-phase experiments showed that such an electron-deficient reagent ion CCl(3)(+) could undergo interesting ion-molecule reactions with various volatile organic compounds, which not only present some informative gas-phase reactions, but also facilitate qualitative analysis of diverse volatile compounds by providing unique mass spectral data that are characteristic of particular chemical structures. The ion-molecule reactions of the reagent ion CCl(3)(+) with different types of compounds were studied, and results showed that such reactions could give rise to structurally diagnostic ions, such as [M+CCl(3) - HCl](+) for aromatic hydrocarbons, [M - OH](+) for saturated cyclic ether, ketone, and alcoholic compounds, [M - H](+) ion for monoterpenes, M(·+) for sesquiterpenes, [M - CH(3)CO](+) for esters, as well as the further fragment ions. The mechanisms of ion-molecule reactions of aromatic hydrocarbons, aliphatic ketones and alcoholic compounds with the reagent ion CCl(3)(+) were investigated and proposed according to the information provided by MS/MS experiments and theoretical calculations. Then, this method was applied to study volatile organic compounds in Dendranthema indicum var. aromaticum and 20 compounds, including monoterpenes and their oxygen-containing derivatives, aromatic hydrocarbon and sesquiterpenes were identified using such ion-molecule reactions. This study offers a perspective and an alternative tool for the analysis and identification of various volatile compounds. PMID:21952897

  12. Characterizing the gas phase ion chemistry of an ion trap mobility spectrometry based explosive trace detector using a tandem mass spectrometer.

    PubMed

    Kozole, Joseph; Tomlinson-Phillips, Jill; Stairs, Jason R; Harper, Jason D; Lukow, Stefan R; Lareau, Richard T; Boudries, Hacene; Lai, Hanh; Brauer, Carolyn S

    2012-09-15

    A commercial-off-the-shelf (COTS) ion trap mobility spectrometry (ITMS) based explosive trace detector (ETD) has been interfaced to a triple quadrupole mass spectrometer (MS/MS) for the purpose of characterizing the gas phase ion chemistry intrinsic to the ITMS instrument. The overall objective of the research is to develop a fundamental understanding of the gas phase ionization processes in the ITMS based ETD to facilitate the advancement of its operational effectiveness as well as guide the development of next generation ETDs. Product ion masses, daughter ion masses, and reduced mobility values measured by the ITMS/MS/MS configuration for a suite of nitro, nitrate, and peroxide containing explosives are reported. Molecular formulas, molecular structures, and ionization pathways for the various product ions are inferred using the mass and mobility data in conjunction with density functional theory. The predominant product ions are identified as follows: [TNT-H](-) for trinitrotoluene (TNT), [RDX+Cl](-) for cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), [NO(3)](-) for ethylene glycol dinitrate (EGDN), [NG+NO(3)](-) for nitroglycerine (NG), [PETN+NO(3)](-) for pentaerythritol tetranitrate (PETN), [HNO(3)+NO(3)](-) for ammonium nitrate (NH(4)NO(3)), [HMTD-NC(3)H(6)O(3)+H+Cl](-) for hexamethylene triperoxide diamine (HMTD), and [(CH(3))(2)CNH(2)](+) for triacetone triperoxide (TATP). The predominant ionization pathways for the formation of the various product ions are determined to include proton abstraction, ion-molecule attachment, autoionization, first-order and multi-order thermolysis, and nucleophilic substitution. The ion trapping scheme in the reaction region of the ITMS instrument is shown to increase predominant ion intensities relative to the secondary ion intensities when compared to non-ion trap operation. PMID:22967626

  13. Linear ion-trap mass spectrometric characterization of human pituitary nitrotyrosine-containing proteins

    NASA Astrophysics Data System (ADS)

    Zhan, Xianquan; Desiderio, Dominic M.

    2007-01-01

    The nitric oxide-mediated Tyr-nitration of endogenous proteins is associated with several pathological and physiological processes. In order to investigate the presence - and potential roles - of Tyr-nitration in the human pituitary, a large-format two-dimensional gel separation plus a Western blot against a specific anti-3-nitrotyrosine antibody were used to separate and detect nitroproteins from a human pituitary proteome. The nitroproteins were subjected to in-gel trypsin digestion, and high-sensitivity vacuum matrix-assisted laser desorption/ionization (vMALDI) linear ion-trap tandem mass spectrometry was used to analyze the tryptic peptides. Those MS/MS data were used to determine the amino acid sequence and the specific nitration site of each tryptic nitropeptide, and were matched to corresponding proteins with Bioworks TuboSEQUEST software. Compared to our previous study, 16 new nitrotyrosine-immunoreactive positive Western blot spots were found within the area pI 3.0-10 and Mr 10-100 kDa. Four new nitroproteins were discovered: the stanniocalcin 1 precursor--involved in calcium and phosphate metabolism; mitochondrial co-chaperone protein HscB, which might act as a co-chaperone in iron-sulfur cluster assembly in mitochrondria; progestin and adipoQ receptor family member III--a seven-transmembrane receptor; proteasome subunit alpha type 2--involved in an ATP/ubiquitin-dependent non-lysosomal proteolytic pathway. Those data demonstrate that nitric oxide-mediated Tyr-nitration might participate in various biochemical, metabolic, and pathological processes in the human pituitary.

  14. Detection of Chemical/Biological Agents and Stimulants using Quadrupole Ion Trap Mass Spectrometry

    SciTech Connect

    Harmon, S.H.; Hart, K.J.; Vass, A.A.; Wise, M.B.; Wolf, D.A.

    1999-06-14

    expanded with additional bacteria and fungi. These spectra were acquired on a Finnigan Magnum ion trap using helium buffer gas. A new database of Cl spectra of microorganisms is planned using the CBMS Block II instrument and air as the buffer gas. Using the current database, the fatty acid composition of the organisms was compared using the percentage of the ion current attributable to fatty acids. The data presented suggest promising rules for discrimination of these organisms. Strain, growth media and vegetative state do contribute to some of the distributions observed in the data. However, the data distributions observed in the current study only reflect our experience to date and do not fully represent the variability that might be expected in practice: Acquisition of MS/ MS spectra has begun (using He and air buffer gas) of the protonated molecular ion of a variety of fatty acids and for a number of ions nominally assigned as fatty acids from microorganisms. These spectra will be used to help verify fatty acid .

  15. A differentially pumped dual linear quadrupole ion trap (DLQIT) mass spectrometer: a mass spectrometer capable of MS(n) experiments free from interfering reactions.

    PubMed

    Owen, Benjamin C; Jarrell, Tiffany M; Schwartz, Jae C; Oglesbee, Rob; Carlsen, Mark; Archibold, Enada F; Kenttämaa, Hilkka I

    2013-12-01

    A novel differentially pumped dual linear quadrupole ion trap (DLQIT) mass spectrometer was designed and built to facilitate tandem MS experiments free from interfering reactions. The instrument consists of two differentially pumped Thermo Scientific linear quadrupole ion trap (LQIT) systems that have been connected via an ion transfer octupole encased in a machined manifold. Tandem MS experiments can be performed in the front trap and then the resulting product ions can be transferred via axial ejection into the back trap for further, independent tandem MS experiments in a differentially pumped area. This approach allows the examination of consecutive collision-activated dissociation (CAD) and ion-molecule reactions without unwanted side reactions that often occur when CAD and ion-molecule reactions are examined in the same space. Hence, it greatly facilitates investigations of ion structures. In addition, the overall lower pressure of the DLQIT, as compared to commercial LQIT instruments, results in a reduction of unwanted side reactions with atmospheric contaminants, such as water and oxygen, in CAD and ion-molecule experiments. PMID:24171553

  16. Asymmetric ion trap

    DOEpatents

    Barlow, Stephan E.; Alexander, Michael L.; Follansbee, James C.

    1997-01-01

    An ion trap having two end cap electrodes disposed asymmetrically about a center of a ring electrode. The inner surface of the end cap electrodes are conformed to an asymmetric pair of equipotential lines of the harmonic formed by the application of voltages to the electrodes. The asymmetry of the end cap electrodes allows ejection of charged species through the closer of the two electrodes which in turn allows for simultaneously detecting anions and cations expelled from the ion trap through the use of two detectors charged with opposite polarity.

  17. Asymmetric ion trap

    DOEpatents

    Barlow, S.E.; Alexander, M.L.; Follansbee, J.C.

    1997-12-02

    An ion trap having two end cap electrodes disposed asymmetrically about a center of a ring electrode is disclosed. The inner surface of the end cap electrodes are conformed to an asymmetric pair of equipotential lines of the harmonic formed by the application of voltages to the electrodes. The asymmetry of the end cap electrodes allows ejection of charged species through the closer of the two electrodes which in turn allows for simultaneously detecting anions and cations expelled from the ion trap through the use of two detectors charged with opposite polarity. 4 figs.

  18. Determination of vanillin, ethyl vanillin, and coumarin in infant formula by liquid chromatography-quadrupole linear ion trap mass spectrometry.

    PubMed

    Shen, Yan; Han, Chao; Liu, Bin; Lin, Zhengfeng; Zhou, Xiujin; Wang, Chengjun; Zhu, Zhenou

    2014-02-01

    A simple, precise, accurate, and validated liquid chromatography-quadrupole linear ion trap mass spectrometry method was developed for the determination of vanillin, ethyl vanillin, and coumarin in infant formula samples. Following ultrasonic extraction with methanol/water (1:1, vol/vol), and clean-up on an HLB solid-phase extraction cartridge (Waters Corp., Milford, MA), samples were separated on a Waters XSelect HSS T3 column (150 × 2.1-mm i.d., 5-μm film thickness; Waters Corp.), with 0.1% formic acid solution-acetonitrile as mobile phase at a flow rate of 0.25 mL/min. Quantification of the target was performed by the internal standard approach, using isotopically labeled compounds for each chemical group, to correct matrix effects. Data acquisition was carried out in multiple reaction monitoring transitions mode, monitoring 2 multiple reaction monitoring transitions to ensure an accurate identification of target compounds in the samples. Additional identification and confirmation of target compounds were performed using the enhanced product ion modus of the linear ion trap. The novel liquid chromatography-quadrupole linear ion trap mass spectrometry platform offers the best sensitivity and specificity for characterization and quantitative determination of vanillin, ethyl vanillin, and coumarin in infant formula and fulfills the quality criteria for routine laboratory application.

  19. Collision induced dissociation of protonated N-nitrosodimethylamine by ion trap mass spectrometry: Ultimate carcinogens in gas phase

    NASA Astrophysics Data System (ADS)

    Kulikova, Natalia; Baker, Michael; Gabryelski, Wojciech

    2009-12-01

    Collision induced dissociation of protonated N-nitrosodimethylamine (NDMA) and isotopically labeled N-nitrosodimethyl-d6-amine (NDMA-d6) was investigated by sequential ion trap mass spectrometry to establish mechanisms of gas phase reactions leading to intriguing products of this potent carcinogen. The fragmentation of (NDMA + H+) occurs via two dissociation pathways. In the alkylation pathway, homolytic cleavage of the N-O bond of N-dimethyl, N'-hydroxydiazenium ion generates N-dimethyldiazenium distonic ion which reacts further by a CH3 radical loss to form methanediazonium ion. Both methanediazonium ion and its precursor are involved in ion/molecule reactions. Methanediazonium ion showed to be capable of methylating water and methanol molecules in the gas phase of the ion trap and N-dimethyldiazenium distonic ion showed to abstract a hydrogen atom from a solvent molecule. In the denitrosation pathway, a tautomerization of N-dimethyl, N'-hydroxydiazenium ion to N-nitrosodimethylammonium intermediate ion results in radical cleavage of the N-N bond of the intermediate ion to form N-dimethylaminium radical cation which reacts further through [alpha]-cleavage to generate N-methylmethylenimmonium ion. Although the reactions of NDMA in the gas phase are different to those for enzymatic conversion of NDMA in biological systems, each activation method generates the same products. We will show that collision induced dissociation of N-nitrosodiethylamine (NDEA) and N-nitrosodipropylamine (NDPA) is also a feasible approach to gain information on formation, stability, and reactivity of alkylating agents originating from NDEA and NDPA. Investigating such biologically relevant, but highly reactive intermediates in the condensed phase is hampered by the short life-times of these transient species.

  20. Automated software-guided identification of new buspirone metabolites using capillary LC coupled to ion trap and TOF mass spectrometry.

    PubMed

    Fandiño, Anabel S; Nägele, Edgar; Perkins, Patrick D

    2006-02-01

    The identification and structure elucidation of drug metabolites is one of the main objectives in in vitro ADME studies. Typical modern methodologies involve incubation of the drug with subcellular fractions to simulate metabolism followed by LC-MS/MS or LC-MS(n) analysis and chemometric approaches for the extraction of the metabolites. The objective of this work was the software-guided identification and structure elucidation of major and minor buspirone metabolites using capillary LC as a separation technique and ion trap MS(n) as well as electrospray ionization orthogonal acceleration time-of-flight (ESI oaTOF) mass spectrometry as detection techniques. Buspirone mainly underwent hydroxylation, dihydroxylation and N-oxidation in S9 fractions in the presence of phase I co-factors and the corresponding glucuronides were detected in the presence of phase II co-factors. The use of automated ion trap MS/MS data-dependent acquisition combined with a chemometric tool allowed the detection of five small chromatographic peaks of unexpected metabolites that co-eluted with the larger chromatographic peaks of expected metabolites. Using automatic assignment of ion trap MS/MS fragments as well as accurate mass measurements from an ESI oaTOF mass spectrometer, possible structures were postulated for these metabolites that were previously not reported in the literature.

  1. Sympathetic cooling of a mass-mismatched two-ion chain in a double-well trap potential

    SciTech Connect

    Hasegawa, Taro

    2011-05-15

    Sympathetic cooling of two-ion system, in which one is laser-cooled and the other is sympathetically cooled and their masses are mismatched, in a linear rf trap with a double-well potential is proposed. The double-well potential consists of two wells, and there is one ion in each well. The axial frequencies of the two wells and the spatial interval between them are experimentally controllable. By theoretical analysis, the normal modes of the small oscillations around the equilibrium are derived, and a measure of the sympathetic cooling rate is obtained. As a result, it is found that the sympathetic cooling rate is fast when the frequency of the axial motion of the sympathetically cooled ion is close to that of the laser-cooled ion. In the double-well potential, the sympathetic cooling rate of the ion species whose mass is much heavier or lighter than that of the laser-cooled ion can be fast. The sympathetic cooling rate of C{sub 60}{sup +} by the laser-cooled Ba{sup +} in the double-well potential is estimated to be about 80 times faster than in the conventional setup. The double-well potential may be made by the microfabricated electrode configuration or by the optical dipole force trap.

  2. Determination of anabolic steroids with gas chromatography-ion trap mass spectrometry using hydrogen as carrier gas.

    PubMed

    Impens, S; De Wasch, K; De Brabander, H

    2001-01-01

    Helium is considered to be the ideal carrier gas for gas chromatography/mass spectrometry (GC/MS) in general, and for use with an ion trap in particular. Helium is an inert gas, can be used without special precautions for security and, moreover, it is needed as a damping gas in the trap. A disadvantage of helium is the high viscosity resulting in long GC run times. In this work hydrogen was tested as an alternative carrier gas for GC in performing GC/MS analyses. A hydrogen generator was used as a safe source of hydrogen gas. It is demonstrated that hydrogen can be used as a carrier gas for the gas chromatograph in combination with helium as make-up gas for the trap. The analysis time was thus shortened and the chromatographic performance was optimized. Although hydrogen has proven useful as a carrier gas in gas chromatography coupled to standard detectors such as ECD or FID, its use is not mentioned extensively in the literature concerning gas chromatography-ion trap mass spectrometry. However, it is worth considering as a possibility because of its chromatographic advantages and its advantageous price when using a hydrogen generator.

  3. An improved thin-layer chromatography/mass spectrometry coupling using a surface sampling probe electrospray ion trap system

    SciTech Connect

    Ford, Michael J; Van Berkel, Gary J

    2004-01-01

    A combined surface sampling probe/electrospray emitter coupled with an ion trap mass spectrometer was used for the direct read out of unmodified reversed-phase C18 thin-layer chromatography (TLC) plates. The operation of the surface sampling electrospray ionization interface in positive and negative ionization modes was demonstrated through the direct analysis of TLC plates on which a commercial test mix comprised of four dye compounds viz., rhodamine B, fluorescein, naphthol blue black, and fast green FCF, and an extract of the caffeine-containing plant Ilex vomitoria, were spotted and developed. Acquisition of full-scan mass spectra and automated collection of MS/MS product ion spectra while scanning a development lane along the surface of a TLC plate demonstrated the advantages of using an ion trap in this combination. Details of the sampling system, benefits of analyzing a developed lane in both positive ion and negative ion modes, levels of detection while surface scanning, surface scan speed effects, and the utility of three-dimensional data display, are also discussed.

  4. Broad-Spectrum Drug Screening Using Liquid Chromatography-Hybrid Triple-Quadrupole Linear Ion Trap Mass Spectrometry.

    PubMed

    Stone, Judy

    2016-01-01

    Urine is processed with a simple C18 solid-phase extraction (SPE) and reconstituted in mobile phase. The liquid chromatography system (LC) injects 10 μL of extracted sample onto a reverse-phase LC column for gradient analysis with ammonium formate/acetonitrile mobile phases. Drugs in the column eluent become charged in the ion source using positive electrospray ionization (ESI). Pseudomolecular ions (M + H) are analyzed by a hybrid triple-quadrupole linear ion trap (QqQ and QqLIT) mass spectrometer using an SRM-IDA-EPI acquisition. An initial 125 compound selected ion monitoring (SRM) survey scan (triple quadrupole or QqQ mode) is processed by the information-dependent acquisition (IDA) algorithm. The IDA algorithm selects SRM signals from the survey scan with a peak height above the threshold (the three most abundant SRM signals above 1000 cps) to define precursor ions for subsequent dependent scanning. In the dependent QqLIT scan(s), selected precursor ion(s) are passed through the first quadrupole (Q1), fragmented with three different collision energies in the collision cell (Q2 or q), and product ions are collected in the third quadrupole (Q3), now operating as a linear ion trap (LIT). The ions are scanned out of the LIT in a mass dependent manner to produce a full-scan product ion spectrum (m/z 50-700) defined as an Enhanced (meaning acquired in LIT mode) Product Ion (EPI) spectrum (Mueller et al., Rapid Commun Mass Spectrom 19:1332-1338, 2005). Each EPI spectrum is linked to its precursor ion and to the associated SRM peak from the survey scan. EPI spectra are automatically searched against a 125 drug library of reference EPI spectra for identification. When the duty cycle is complete (one survey scan of 125 SRMs plus 0-3 dependent IDA-EPI scans) the mass spectrometer begins another survey scan of the 125 SRMs. PMID:26660183

  5. Finnigan ion trap mass spectrometer detection limits and thermal energy analyzer interface status report and present capabilities

    SciTech Connect

    Alcaraz, A.; Andresen, B.; Martin, W.

    1990-10-18

    A new Finnigan ion trap mass spectrometer was purchased and installed at LLNL. Over a period of several months the instrument was tested under a variety of conditions utilizing a capillary gas chromatography interface which allowed separated organic compounds to be carried directly into the ion source of the mass spectrometer. This direct interface allowed maximum analytical sensitivity. A variety of critical tests were performed in order to optimize the sensitivity of the system under a variety of analysis conditions. These tests altered the critical time cycles of the ionization, ion trapping, and detection. Various carrier gas pressures were also employed in order to ascertain the overall sensitivity of the instrument. In addition we have also interfaced a thermal energy analyzer (TEA) to the gas chromatograph in order to simultaneously detect volatile nitrogen containing compounds while mass spectral data is being acquired. This is the first application at this laboratory of simultaneous ultra-trace detections while utilizing two orthogonal analytical techniques. In particular, explosive-related compound and/or residues are of interest to the general community in water, soil and gas sampler. In this paper are highlighted a few examples of the analytical power of this new GC-TEA-ITMS technology.

  6. Development of an automated cylindrical ion trap mass spectrometer for the determination of atmospheric volatile organic compounds.

    PubMed

    Edwards, Gavin D; Shepson, P B; Grossenbacher, J W; Wells, J M; Patterson, G E; Barket, D J; Pressley, S; Karl, T; Apel, E

    2007-07-01

    Volatile organic compounds released from the biosphere are known to have a large impact on atmospheric chemistry. Field instruments for the detection of these trace gases are often limited by the lack of instrument portability and the inability to distinguish compounds of interest from background or other interfering compounds. We have developed an automated sampling and preconcentration system, coupled to a lightweight, low-power cylindrical ion trap mass spectrometer. The instrument was evaluated by measuring isoprene concentrations during a field campaign at the University of Michigan Biological Station PROPHET lab. Isoprene was preconcentrated by sampling directly into a short capillary column precooled without the aid of cryogens. The capillary column was then rapidly heated by moving the column to a preheated region to obtain fast separation of isoprene from other components, followed by detection with a cylindrical ion trap. This combination yielded a detection limit of approximately 80 ppt (parts per trillion) for isoprene with a measurement frequency of one sample every 11 min. The data obtained by the automated sampling and preconcentration system during the PROPHET 2005 campaign were compared to those of other field instruments measuring isoprene at this site in an intercomparison exercise. The intercomparisons suggest the new inlet system, when coupled with this ion trap detector, provides a viable field instrument for the fast, precise, and quantitative determination of isoprene and other trace gases over a variety of atmospheric conditions.

  7. Arsenosugar identification in seaweed extracts using high-performance liquid chromatography/electrospray ion trap mass spectrometry.

    PubMed

    Miguens-Rodriguez, Maria; Pickford, Russell; Thomas-Oates, Jane E; Pergantis, Spiros A

    2002-01-01

    The development of analytical techniques suitable for providing structural information on a wide range of elemental species is a growing necessity. For arsenic speciation a variety of mass spectrometric techniques, mainly inductively coupled plasma mass spectrometry (ICP-MS) and electrospray tandem mass spectrometry (ES-MS/MS) coupled on-line with high-performance liquid chromatography (HPLC), are in use. In this paper we report the identification of arsenic species present in samples of marine origin (seaweed extracts) using ES ion trap mass spectrometry (IT) multistage mass spectrometry (MS(n)). Both reversed-phase and anion-exchange HPLC have been coupled on-line to ES-ITMS. Product ion scans with multiple stages of tandem MS (MS(n); n=2-4) were used to acquire diagnostic data for each arsenosugar. The spectra contain structurally characteristic fragment ions for each of the arsenosugars examined. In addition it was observed that upon successive stages of collision-induced dissociation (CID) a common product ion (m/z 237) was formed from all four arsenosugars examined. This product ion has the potential to be used as an indicator for the presence of dimethylated arsenosugars (dimethylarsinoylribosides). The HPLC/ES-ITMS(n) method developed allows the sensitive identification of arsenosugars present in crude seaweed extracts without the need for extended sample preparation. In fact, sample preparation requirements are identical to those typically employed for HPLC/ICP-MS analysis. Additionally, the resulting product ions are structurally diagnostic of the arsenosugars examined, and tandem mass spectra are reproducible and correspond well to those obtained using other low-energy CID techniques. As a result, the HPLC/ES-ITMS(n) approach minimises the potential for arsenic species misidentification and has great potential as a means of overcoming the need for characterised standards.

  8. Mass Spectrometry Parameters Optimization for the 46 Multiclass Pesticides Determination in Strawberries with Gas Chromatography Ion-Trap Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Fernandes, Virgínia C.; Vera, Jose L.; Domingues, Valentina F.; Silva, Luís M. S.; Mateus, Nuno; Delerue-Matos, Cristina

    2012-12-01

    Multiclass analysis method was optimized in order to analyze pesticides traces by gas chromatography with ion-trap and tandem mass spectrometry (GC-MS/MS). The influence of some analytical parameters on pesticide signal response was explored. Five ion trap mass spectrometry (IT-MS) operating parameters, including isolation time (IT), excitation voltage (EV), excitation time (ET), maximum excitation energy or " q" value (q), and isolation mass window (IMW) were numerically tested in order to maximize the instrument analytical signal response. For this, multiple linear regression was used in data analysis to evaluate the influence of the five parameters on the analytical response in the ion trap mass spectrometer and to predict its response. The assessment of the five parameters based on the regression equations substantially increased the sensitivity of IT-MS/MS in the MS/MS mode. The results obtained show that for most of the pesticides, these parameters have a strong influence on both signal response and detection limit. Using the optimized method, a multiclass pesticide analysis was performed for 46 pesticides in a strawberry matrix. Levels higher than the limit established for strawberries by the European Union were found in some samples.

  9. Characterization of dihydrostreptomycin-related substances by liquid chromatography coupled to ion trap mass spectrometry.

    PubMed

    Pendela, Murali; Hoogmartens, Jos; Van Schepdael, Ann; Adams, Erwin

    2009-06-01

    Dihydrostreptomycin sulphate (DHS) is a water-soluble, broad-spectrum aminoglycoside antibiotic. For quantitative analysis, the European Pharmacopoeia (Ph. Eur.) prescribes an ion-pairing liquid chromatography/ultraviolet (LC/UV) method using a C18 stationary phase. Several unknown compounds were detected in commercial samples. Hence, for characterization of these unknown peaks in a commercial DHS sample, the Ph. Eur. method was coupled to mass spectrometry (MS). However, since the Ph. Eur. method uses a non-volatile mobile phase, each peak eluted was collected and desalted before introduction into the mass spectrometer. The desalting procedure was applied to remove the non volatile salt, buffer and ion-pairing reagent in the collected fraction. In total, 20 impurities were studied and 14 of them were newly characterized. Five impurities which are already reported in the literature were also traced in this LC/UV method. PMID:19449319

  10. Structural Distinction of Diacyl-, Alkylacyl, and Alk-1-Enylacyl Glycerophosphocholines as [M - 15]- Ions by Multiple-Stage Linear Ion-Trap Mass Spectrometry with Electrospray Ionization

    NASA Astrophysics Data System (ADS)

    Hsu, Fong-Fu; Lodhi, Irfan J.; Turk, John; Semenkovich, Clay F.

    2014-08-01

    We describe a linear ion-trap (LIT) multiple-stage (MSn) mass spectrometric approach towards differentiation of alkylacyl, alk-1-enylacyl- and diacyl-glycerophoscholines (PCs) as the [M - 15]- ions desorbed by electrospray ionization (ESI) in the negative-ion mode. The MS4 mass spectra of the [M - 15 - R2'CH = CO]- ions originated from the three PC subfamilies are readily distinguishable, resulting in unambiguous distinction of the lipid classes. This method is applied to two alkyl ether rich PC mixtures isolated from murine bone marrow neutrophils and kidney, respectively, to explore its utility in the characterization of complex PC mixture of biological origin, resulting in the realization of the detailed structures of the PC species, including various classes and many minor isobaric isomers.

  11. Advanced stored waveform inverse Fourier transform technique for a matrix-assisted laser desorption/ionization quadrupole ion trap mass spectrometer.

    PubMed

    Doroshenko, V M; Cotter, R J

    1996-01-01

    The stored waveform inverse Fourier transform (SWIFT) technique is used for broadband excitation of ions in an ion-trap mass spectrometer to perform mass-selective accumulation, isolation, and fragmentation of peptide ions formed by matrix-assisted laser desorption/ionization. Unit mass resolution is achieved for isolation of ions in the range of m/z up to 1300 using a two-step isolation technique with stretched-in-time narrow band SWIFT pulses at the second stage. The effect of 'stretched-in-time' waveforms is similar to that observed previously for mass-scan-rate reduction. The asymmetry phenomenon resulting from the stretched ion-trap electrode geometry is observed during application of normal and time-reversed waveforms and is similar to the asymmetry effects observed for forward and reverse mass scans in the resonance ejection mode. Mass-selective accumulation of ions from multiple laser shots was accomplished using a method described earlier that involves increasing the trapping voltage during ion introduction for more efficient trapping of ions.

  12. Determination of triacylglycerol regioisomers using electrospray ionization-quadrupole ion trap mass spectrometry with a kinetic method.

    PubMed

    Leveque, Nathalie L; Acheampong, Akwasi; Heron, Sylvie; Tchapla, Alain

    2012-04-13

    The kinetic method was applied to differentiate and quantify mixtures of regioisomeric triacylglycerols (TAGs) by generating and mass selecting alkali ion bound metal dimeric clusters with a TAG chosen as reference (ref) and examining their competitive dissociations in a quadrupole ion trap mass spectrometer. This methodology readily distinguished pairs of regioisomers (AAB/ABA) such as LLO/LOL, OOP/OPO and SSP/SPS and consequently distinguished sn-1/sn-3, sn-2 substituents on the glycerol backbone. The dimeric complex ions [ref, Li, TAG((AAB and/or ABA))](+) generated by electrospray ionization mass spectrometry were subjected to collision induced dissociation causing competitive loss of either the neutral TAG reference (ref) leading to [Li(AAB and/or ABA)](+) or the neutral TAG molecule (TAG((AAB and/or ABA))) leading to [ref, Li](+). The ratio of the two competitive dissociation rates, defined by the product ion branching ratio (R(iso)), was related via the kinetic method to the regioisomeric composition of the investigated TAG mixture. In this work, a linear correlation was established between composition of the mixture of each TAG regioisomer and the logarithm of the branching ratio for competitive fragmentation. Depending on the availability of at least one TAG regioisomer as standard, the kinetic method and the standard additions method led to the quantitative analysis of natural TAG mixtures. PMID:22444537

  13. Some Rare Earth Elements Analysis by Microwave Plasma Torch Coupled with the Linear Ion Trap Mass Spectrometry

    PubMed Central

    Xiong, Xiaohong; Jiang, Tao; Qi, Wenhao; Zuo, Jun; Yang, Meiling; Fei, Qiang; Xiao, Saijin; Yu, Aimin; Zhu, Zhiqiang; Chen, Huanwen

    2015-01-01

    A sensitive mass spectrometric analysis method based on the microwave plasma technique is developed for the fast detection of trace rare earth elements (REEs) in aqueous solution. The plasma was produced from a microwave plasma torch (MPT) under atmospheric pressure and was used as ambient ion source of a linear ion trap mass spectrometer (LTQ). Water samples were directly pneumatically nebulized to flow into the plasma through the central tube of MPT. For some REEs, the generated composite ions were detected in both positive and negative ion modes and further characterized in tandem mass spectrometry. Under the optimized conditions, the limit of detection (LOD) was at the level 0.1 ng/mL using MS2 procedure in negative mode. A single REE analysis can be completed within 2~3 minutes with the relative standard deviation ranging between 2.4% and 21.2% (six repeated measurements) for the 5 experimental runs. Moreover, the recovery rates of these REEs are between the range of 97.6%–122.1%. Two real samples have also been analyzed, including well and orange juice. These experimental data demonstrated that this method is a useful tool for the field analysis of REEs in water and can be used as an alternative supplement of ICP-MS. PMID:26421013

  14. Some Rare Earth Elements Analysis by Microwave Plasma Torch Coupled with the Linear Ion Trap Mass Spectrometry.

    PubMed

    Xiong, Xiaohong; Jiang, Tao; Qi, Wenhao; Zuo, Jun; Yang, Meiling; Fei, Qiang; Xiao, Saijin; Yu, Aimin; Zhu, Zhiqiang; Chen, Huanwen

    2015-01-01

    A sensitive mass spectrometric analysis method based on the microwave plasma technique is developed for the fast detection of trace rare earth elements (REEs) in aqueous solution. The plasma was produced from a microwave plasma torch (MPT) under atmospheric pressure and was used as ambient ion source of a linear ion trap mass spectrometer (LTQ). Water samples were directly pneumatically nebulized to flow into the plasma through the central tube of MPT. For some REEs, the generated composite ions were detected in both positive and negative ion modes and further characterized in tandem mass spectrometry. Under the optimized conditions, the limit of detection (LOD) was at the level 0.1 ng/mL using MS(2) procedure in negative mode. A single REE analysis can be completed within 2~3 minutes with the relative standard deviation ranging between 2.4% and 21.2% (six repeated measurements) for the 5 experimental runs. Moreover, the recovery rates of these REEs are between the range of 97.6%-122.1%. Two real samples have also been analyzed, including well and orange juice. These experimental data demonstrated that this method is a useful tool for the field analysis of REEs in water and can be used as an alternative supplement of ICP-MS. PMID:26421013

  15. Imaging MS Methodology for More Chemical Information in Less Data Acquisition Time Utilizing a Hybrid Linear Ion Trap-Orbitrap Mass Spectrometer

    SciTech Connect

    Perdian, D. C.; Lee, Young Jin

    2010-11-15

    A novel mass spectrometric imaging method is developed to reduce the data acquisition time and provide rich chemical information using a hybrid linear ion trap-orbitrap mass spectrometer. In this method, the linear ion trap and orbitrap are used in tandem to reduce the acquisition time by incorporating multiple linear ion trap scans during an orbitrap scan utilizing a spiral raster step plate movement. The data acquisition time was decreased by 43-49% in the current experiment compared to that of orbitrap-only scans; however, 75% or more time could be saved for higher mass resolution and with a higher repetition rate laser. Using this approach, a high spatial resolution of 10 {micro}m was maintained at ion trap imaging, while orbitrap spectra were acquired at a lower spatial resolution, 20-40 {micro}m, all with far less data acquisition time. Furthermore, various MS imaging methods were developed by interspersing MS/MS and MSn ion trap scans during orbitrap scans to provide more analytical information on the sample. This method was applied to differentiate and localize structural isomers of several flavonol glycosides from an Arabidopsis flower petal in which MS/MS, MSn, ion trap, and orbitrap images were all acquired in a single data acquisition.

  16. Quantitative analysis of [Dmt(1)]DALDA in ovine plasma by capillary liquid chromatography-nanospray ion-trap mass spectrometry.

    PubMed

    Wan, Haibao; Umstot, Edward S; Szeto, Hazel H; Schiller, Peter W; Desiderio, Dominic M

    2004-04-15

    The synthetic opioid peptide analog Dmt-D-Arg-Phe-Lys-NH(2) ([Dmt(1)]DALDA; [Dmt= 2',6'-dimethyltyrosine) is a highly potent and selective mu opioid-receptor agonist. A very sensitive and robust capillary liquid chromatography/nanospray ion-trap (IT) mass spectrometry method has been developed to quantify [Dmt(1)]DALDA in ovine plasma, using deuterated [Dmt(1)]DALDA as the internal standard. The standard MS/MS spectra of d(0)- and d(5)-[Dmt(1)]DALDA were obtained, and the collision energy was experimentally optimized to 25%. The product ion [ M + 2H-NH(3)](2+) (m/z 312.2) was used to identify and to quantify the synthetic opioid peptide analog in ovine plasma samples. The MS/MS detection sensitivity for [Dmt(1)]DALDA was 625 amol. A calibration curve was constructed, and quantitative analysis was performed on a series of ovine plasma samples.

  17. Ion trap in a semiconductor chip

    NASA Astrophysics Data System (ADS)

    Stick, D.; Hensinger, W. K.; Olmschenk, S.; Madsen, M. J.; Schwab, K.; Monroe, C.

    2006-01-01

    The electromagnetic manipulation of isolated atoms has led to many advances in physics, from laser cooling and Bose-Einstein condensation of cold gases to the precise quantum control of individual atomic ions. Work on miniaturizing electromagnetic traps to the micrometre scale promises even higher levels of control and reliability. Compared with `chip traps' for confining neutral atoms, ion traps with similar dimensions and power dissipation offer much higher confinement forces and allow unparalleled control at the single-atom level. Moreover, ion microtraps are of great interest in the development of miniature mass-spectrometer arrays, compact atomic clocks and, most notably, large-scale quantum information processors. Here we report the operation of a micrometre-scale ion trap, fabricated on a monolithic chip using semiconductor micro-electromechanical systems (MEMS) technology. We confine, laser cool and measure heating of a single 111Cd+ ion in an integrated radiofrequency trap etched from a doped gallium-arsenide heterostructure.

  18. Negative electrospray, ion trap multistage mass spectrometry of synthetic fragments of the O-PS of Vibrio cholerae O:1.

    PubMed

    Bekesová, Slávka; Kovácik, Vladimír; Chmelík, Josef; Kovác, Pavol

    2006-01-01

    Saccharides (mono through hexasaccharides) that mimic the terminal epitopes of O-antigens of Vibrio cholerae O:1, serotypes Ogawa and Inaba, were studied by electrospray ion trap (ESI IT) mass spectrometry (MS) in the negative mode. Anionized adducts are the characteristic ions formed by the capture of H(3)O(2)(-) under the condition of ESI MS analysis. The reactive species are produced by reaction of hydroxyl anions with the molecule of water. Thus the [M + H(3)O(2)](-) have the highest m/z value in the ESI IT negative mass spectra. After dissociation of adducts by loss of 2H(2)O the [M-H](-) ions are produced. The fragmentation pathways were confirmed by multistage measurements (MS(n)). The predominant pathway of fragmentation of the mono- and oligomers is the elimination of a molecule of alpha- hydroxy--gammabutyrolactone from the 4-(3-deoxy-L-glycero-tetronamido) group. The other characteristic pathway occurs by shortening the length of oligosaccharides. In this way, conversion of the Ogawa to Inaba fragments takes place under the conditions of measurement. Negative ESI MS/MS provided sufficient information about molecular mass, the number of saccharide residues, basic structure of saccharides, about the tetronamide part of the compounds investigated and allowed Ogawa and Inaba serotypes to be distinguished.

  19. Rapid characterization of the sucrose esters from oriental tobacco using liquid chromatography/ion trap mass spectrometry.

    PubMed

    Ding, Li; Xie, Fuwei; Zhao, Mingyue; Xie, Jianping; Xu, Guowang

    2006-01-01

    Sucrose esters (SEs) from oriental tobacco are normally characterized by gas chromatography/mass spectrometry (GC/MS) after a long saponification and derivatization procedure. To simplify the process, a rapid method has been developed by using liquid chromatography coupled with electrospray ion trap mass spectrometry (LC/ESI-MSn). Using the characteristic fragmentation behavior of abundant SEs identified by GC/MS after purification by gel permeation chromatography (GPC) from cuticular waxes of green oriental tobacco leaf, two types of SEs from green and cured oriental tobacco were identified by MSn analysis. The first is one of three types reported formerly and has 13 SE homologues. However, the presence of unsaturation in one of the acyl substituents of this first type gave rise to a new series with three homologues. The other was found to be a new type and had three homologues. The proposed method enables the rapid and sensitive characterization of SEs from oriental tobacco.

  20. Analysis of environmental contaminates in hair using an ion trap mass spectrometer with a filtered noise field waveboard

    SciTech Connect

    Alcaraz, A.; Hulsey, S.S.; Frantz, C.E.; Andresen, B.D.

    1994-12-31

    A variety of methods have been established using mass spectrometry (MS) for the analysis of chemicals in hair. Much of this past work has been focused on the detection of drugs of abuse. Human hair has been analyzed either directly by probe distillation (DIP) with some preliminary clean-up using HPLC or solid phase extraction (SPE). However, established drug analysis methods do not apply for the detection of some environmental contaminates. In this study, the authors selected 2,4,6-trinitrotoluene (TNT) and malathion as the target compounds. In addition two types of hair samples were analyzed: (1) human hair fortified with either TNT or malathion and (2) hair from mice who ingested the same analytes. The analytical method was DIP-EI-MS/MS with an ion trap mass spectrometer equipped with a filtered noise field wave board.

  1. Differentiation of regioisomeric aromatic ketocarboxylic acids by positive mode atmospheric pressure chemical ionization collision-activated dissociation tandem mass spectrometry in a linear quadrupole ion trap mass spectrometer.

    PubMed

    Amundson, Lucas M; Owen, Benjamin C; Gallardo, Vanessa A; Habicht, Steven C; Fu, Mingkun; Shea, Ryan C; Mossman, Allen B; Kenttämaa, Hilkka I

    2011-04-01

    Positive-mode atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS(n)) was tested for the differentiation of regioisomeric aromatic ketocarboxylic acids. Each analyte forms exclusively an abundant protonated molecule upon ionization via positive-mode APCI in a commercial linear quadrupole ion trap (LQIT) mass spectrometer. Energy-resolved collision-activated dissociation (CAD) experiments carried out on the protonated analytes revealed fragmentation patterns that varied based on the location of the functional groups. Unambiguous differentiation between the regioisomers was achieved in each case by observing different fragmentation patterns, different relative abundances of ion-molecule reaction products, or different relative abundances of fragment ions formed at different collision energies. The mechanisms of some of the reactions were examined by H/D exchange reactions and molecular orbital calculations.

  2. Single CdSe/ZnS nanocrystals in an ion trap: charge and mass determination and photophysics evolution with changing mass, charge, and temperature.

    PubMed

    Bell, David M; Howder, Collin R; Johnson, Ryan C; Anderson, Scott L

    2014-03-25

    We report measurements of fluorescence intermittency (blinking) and spectral behavior for single semiconductor nanocrystal quantum dots (QDs) isolated in the gas phase and discuss the effects on fluorescence of the QD charge state and heating to the point of sublimation. Core-shell CdSe/ZnS QDs were trapped in a quadrupole ion trap and detected by laser-induced fluorescence. The mass (M) and charge (Q) were determined nondestructively, and both were followed continuously over the course of hours or days. Emission spectra of the trapped QDs are significantly red-shifted relative to the solution-phase emission from the same particles. The temperature of the trapped QDs is determined by the balance between laser heating and collisional cooling and thermal emission, and it is possible to heat the particles to remove ligands or to the point of sublimation. QDs are observed to be emissive during sublimation, for up to 85% mass loss, with emission intensity roughly proportional to the surface area. Eventually, the fluorescence quantum yield drops suddenly, and the QDs begin to blink. The method used is versatile and will allow studies of quantum dot optical properties as a function of size, ligand removal, heating, surface oxidation, and other manipulations, where these properties are continuously correlated with the mass and charge.

  3. A Quadrupole Ion Trap Mass Spectrometer for Quantitative Analysis of Nitrogen-Purged Compartments within the Space Shuttle

    NASA Technical Reports Server (NTRS)

    Ottens, Andrew K.; Griffin, Timothy P.; Helms, William R.; Yost, Richard A.; Steinrock, T. (Technical Monitor)

    2001-01-01

    To enter orbit, the Space Shuttle burns 1.8 million liters of liquid hydrogen combined with 0.8 million liters of liquid oxygen through three rocket engines mounted in the aft. NASA monitors the nitrogen-purged aft compartment for increased levels of hydrogen or oxygen in order to detect and determine the severity of a cryogenic fuel leak. Current monitoring is accomplished with a group of mass spectrometer systems located as much as 400 feet away from the Shuttle. It can take up to 45 seconds for gas to reach the mass spectrometer, which precludes monitoring for leaks in the final moments before liftoff (the orbiter engines are started at T-00:06 seconds). To remedy the situation, NASA is developing a small rugged mass spectrometer to be used as point-sensors around the Space Shuttle. As part of this project, numerous mass analyzer technologies are being investigated. Presented here are the preliminary results for one such technology, quadrupole ion trap mass spectrometry (QITMS). A compact QITMS system has been developed in-house at the University of Florida for monitoring trace levels of four primary gases, hydrogen, helium, oxygen, and argon, all in a nitrogen background. Since commercially available QITMS systems are incapable of mass analysis at m/z(exp 2), the home-built system is preferred for the evaluation of QITMS technology.

  4. Liquid chromatography and ion trap mass spectrometry for simultaneous and multiclass analysis of antimicrobial residues in feed water.

    PubMed

    Ardsoongnearn, Chusak; Boonbanlu, Ongart; Kittijaruwattana, Sunan; Suntornsuk, Leena

    2014-01-15

    This work firstly reported the development of liquid chromatography coupled to an ion trap mass spectrometer (LC-MS ion trap) for the simultaneous determination of nitrofurans (e.g. nitrofurazone (NFZ), nitrofurantoin (NFT), furazolidone (FZD) and furaltadone (FTD)), nitroimidazoles (e.g. metronidazole (MNZ), ronidazole (RNZ) and dimetridazole (DMZ)) and chloramphenicol (CAP) in feed water. Isotope-labeled internal standards for the corresponding target analytes were employed to prevent matrix effects that might lead to signal suppression/enhancement. High performance liquid chromatography (HPLC) analysis was performed on a Prodigy ODS-3 column, 2.0mm×150mm, 5μm with a guard cartridge at a flow rate of 0.2mL/min, column oven temperature of 40°C, and an injection volume of 10μL. Solid phase extraction (SPE) procedures, factors affecting HPLC separation (e.g. buffer pH and concentrations) and mass spectrometry (MS) parameters were optimized. After an off-line SPE by the OASIS HLB cartridges (with an enrichment factor of 400), the eight antimicrobial agents were separated in 18min using a gradient elution of acetonitrile in acidified water (pH 5.0). MS detection was by an ion trap MS coupled with electrospray ionization (ESI) in tandem mass spectrometry mode (MS/MS) using the nebulizer gas at 35psi, drying gas at 9L/min and drying temperature of 325°C. Method linearity was good (r(2)=0.979-0.999) with acceptable precision (% RSDs=3.4-26.6%) and accuracy (%recovery=88.4-110.1%). Very low limits of detection (LOD) and quantitation (LOQ) were achieved in ranges of 0.002-0.06μg/L and 0.005-0.25μg/L, respectively. The established method is successfully employed by the Department of Livestock Development of Thailand for the monitoring of the drug residues in feed waterbecause of its convenience, reliability and high sensitivity.

  5. Characterization of column packing materials in high-performance liquid chromatography by charge-detection quadrupole ion trap mass spectrometry.

    PubMed

    Xiong, Caiqiao; Zhou, Xiaoyu; Chen, Rui; Zhang, Yiming; Peng, Wen-Ping; Nie, Zongxiu; Chang, Huan-Cheng; Liu, Huwei; Chen, Yi

    2011-07-01

    This article reports an application of charge-detection quadrupole ion trap mass spectrometry (CD-ITMS) to characterize the column packing materials in high-performance liquid chromatography (HPLC). Both the mean mass and the mass distribution of the packing materials are obtained and used to calculate the specific surface area of unbonded silica, the carbon load of the bonded silica, and their particle size distributions. The obtained specific surface areas and carbon loads are consistent with those measured independently by nitrogen sorption and elemental analysis respectively, whereas the derived size distributions show better resolution than that measured by a laser particle size analyzer. Furthermore, we evaluate the uniformity of particle size, which is the key parameter for column efficiency of the liquid chromatography by analyzing the mass distribution of the packing materials at the top and bottom of the column. A broader mass distribution, which yields decreased column efficiency, is observed for the column top because of the excessive use of the column. Our results suggest that CD-ITMS can serve as an alternative means for the characterization of the packing materials in HPLC and is potentially useful for column quality control.

  6. Quantum computing with trapped ions

    SciTech Connect

    Hughes, R.J.

    1998-01-01

    The significance of quantum computation for cryptography is discussed. Following a brief survey of the requirements for quantum computational hardware, an overview of the ion trap quantum computation project at Los Alamos is presented. The physical limitations to quantum computation with trapped ions are analyzed and an assessment of the computational potential of the technology is made.

  7. Ion Behavior in an Electrically Compensated Ion Cyclotron Resonance Trap

    PubMed Central

    Brustkern, Adam M.; Rempel, Don L.; Gross, Michael L.

    2010-01-01

    We recently described a new electrically compensated trap in FT ion cyclotron resonance mass spectrometry and developed a means of tuning traps of this general design. Here, we describe a continuation of that research by comparing the ion transient lifetimes and the resulting mass resolving powers and signal-to-noise (S/N) ratios that are achievable in the compensated vs. uncompensated modes of this trap. Transient lifetimes are ten times longer under the same conditions of pressure, providing improved mass resolving power and S/N ratios. The mass resolving power as a function of m/z is linear (log-log plot) and nearly equal to the theoretical maximum. Importantly, the ion cyclotron frequency as a function of ion number decreases linearly in accord with theory, unlike its behavior in the uncompensated mode. This linearity should lead to better control in mass calibration and increased mass accuracy than achievable in the uncompensated mode. PMID:21499521

  8. Ion cloud model for a linear quadrupole ion trap.

    PubMed

    Douglas, Don J; Konenkov, Nikolai V

    2012-01-01

    If large numbers of ions are stored in a linear quadrupole ion trap, space charge causes the oscillation frequencies of ions to decrease. Ions then appear at higher apparent masses when resonantly ejected for mass analysis. In principle, to calculate mass shifts requires calculating the positions of all ions, interacting with each other, at all times, with a self-consistent space charge field. Here, we propose a simpler model for the ion cloud in the case where mass shifts and frequency shifts are relatively small (ca 0.2% and 0.4%, respectively), the trapping field is much stronger (ca × 10(2)) than the space charge field and space charge only causes small perturbations to the ion motion. The self-consistent field problem need not be considered. As test ions move with times long compared to a cycle of the trapping field, the motion of individual ions can be ignored. Static positions of the ions in the cloud are used. To generate an ion cloud, trajectories of N (ca 10,000) ions are calculated for random times between 10 and 100 cycles of the trapping radio frequency field. The ions are then distributed axially randomly in a trap four times the field radius, r(0) in length. The potential and electric field from the ion cloud are calculated from the ion positions. Near the trap center (distances r< 1r(0)), the potential and electric fields from space charge are not cylindrically symmetric, but are quite symmetric for greater values of r. Trajectories of test ions, oscillation frequencies and mass shifts can then be calculated in the trapping field, including the space charge field. Mass shifts are in good agreement with experiments for reasonable values of the initial positions and speeds of the ions. Agreement with earlier analytical models for the ion cloud, based on a uniform occupation of phase space, or a thermal (Boltzmann) distribution of ions trapped in the effective potential [D. Douglas and N.V. Konenkov, Rapid Commun. Mass Spectrom. 26, 2105 (2012)] is

  9. Detection of lysergic acid diethylamide (LSD) in urine by gas chromatography-ion trap tandem mass spectrometry.

    PubMed

    Sklerov, J H; Kalasinsky, K S; Ehorn, C A

    1999-10-01

    A confirmatory method for the detection and quantitation of lysergic acid diethylamide (LSD) is presented. The method employs gas chromatography-tandem mass spectrometry (GC-MS-MS) using an internal ionization ion trap detector for sensitive MS-MS-in-time measurements of LSD extracted from urine. Following a single-step solid-phase extraction of 5 mL of urine, underivatized LSD can be measured with limits of quantitation and detection of 80 and 20 pg/mL, respectively. Temperature-programmed on-column injections of urine extracts were linear over the concentration range 20-2000 pg/mL (r2 = 0.999). Intraday and interday coefficients of variation were < 6% and < 13%, respectively. This procedure has been applied to quality-control specimens and LSD-positive samples in this laboratory. Comparisons with alternate GC-MS methods and extraction procedures are discussed.

  10. Comprehensive identification of walnut polyphenols by liquid chromatography coupled to linear ion trap-Orbitrap mass spectrometry.

    PubMed

    Regueiro, Jorge; Sánchez-González, Claudia; Vallverdú-Queralt, Anna; Simal-Gándara, Jesús; Lamuela-Raventós, Rosa; Izquierdo-Pulido, Maria

    2014-01-01

    Epidemiologic studies and clinical trials have demonstrated consistent benefits of walnut consumption on coronary heart disease risk and other chronic diseases. Walnuts (Juglans regia L.) have been described previously as a rich source of polyphenols with a broad array of different structures. However, an accurate screening of its complete phenolic profile is still lacking. In the present work, liquid chromatography coupled with electrospray ionization hybrid linear trap quadrupole-Orbitrap mass spectrometry (LC-LTQ-Orbitrap) was applied for a comprehensive identification of phenolic compounds in walnuts. A total of 120 compounds, including hydrolysable and condensed tannins, flavonoids and phenolic acids were identified or tentatively identified on the base of their retention times, accurate mass measurements and subsequent mass fragmentation data, or by comparing with reference substances and literature. The peak area of each signal in mass chromatograms was used to provide semiquantitative information for comparison purposes. The most abundant ions were observed for ellagitannins, ellagic acid and its derivatives. Furthermore, the high-resolution MS analysis revealed the presence of eight polyphenols that have never been reported in walnuts: stenophyllanin C, malabathrin A, eucalbanin A, cornusiin B, heterophylliin E, pterocarinin B, reginin A and alienanin B.

  11. Improved characterization of tomato polyphenols using liquid chromatography/electrospray ionization linear ion trap quadrupole Orbitrap mass spectrometry and liquid chromatography/electrospray ionization tandem mass spectrometry.

    PubMed

    Vallverdú-Queralt, Anna; Jáuregui, Olga; Medina-Remón, Alexander; Andrés-Lacueva, Cristina; Lamuela-Raventós, Rosa M

    2010-10-30

    Tomato (Lycopersicon esculentum Mill.) is the second most important fruit crop worldwide. Tomatoes are a key component in the Mediterranean diet, which is strongly associated with a reduced risk of chronic degenerative diseases. In this work, we use a combination of mass spectrometry (MS) techniques with negative ion detection, liquid chromatography/electrospray ionization linear ion trap quadrupole-Orbitrap-mass spectrometry (LC/ESI-LTQ-Orbitrap-MS) and liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) on a triple quadrupole, for the identification of the constituents of tomato samples. First, we tested for the presence of polyphenolic compounds through generic MS/MS experiments such as neutral loss and precursor ion scans on the triple quadrupole system. Confirmation of the compounds previously identified was accomplished by injection into the high-resolution system (LTQ-Orbitrap) using accurate mass measurements in MS, MS(2) and MS(3) modes. In this way, 38 compounds were identified in tomato samples with very good mass accuracy (<2 mDa), three of them, as far as we know, not previously reported in tomato samples.

  12. Improved analysis of melamine-formaldehyde resins by capillary zone electrophoresis-mass spectrometry using ion-trap and quadrupole-time-of-flight mass spectrometers.

    PubMed

    Vo, Thuy Diep Thanh; Himmelsbach, Markus; Haunschmidt, Manuela; Buchberger, Wolfgang; Schwarzinger, Clemens; Klampfl, Christian W

    2008-12-01

    An improved method based on capillary zone electrophoresis (CZE) coupled to either ion-trap (IT) mass spectrometry (MS) or quadrupole-time-of-flight (Q-TOF) MS for the analysis of melamine-formaldehyde condensates is presented. Employing a formic acid-based electrolyte containing 50% acetonitrile (ACN) and MS detection up to 13 compounds could be determined in lab-made resins, synthesized by mixing formaldehyde and melamine in different ratios ranging from 1:1.5 to 1:4. The use of a Q-TOF-MS for detection allowed the assignment of molecular formulas for all 13 substances with high accuracy.

  13. Action spectroscopy of SrCl{sup +} using an integrated ion trap time-of-flight mass spectrometer

    SciTech Connect

    Puri, Prateek Schowalter, Steven J.; Hudson, Eric R.; Kotochigova, Svetlana; Petrov, Alexander

    2014-07-07

    The photodissociation cross-section of SrCl{sup +} is measured in the spectral range of 36 000–46 000 cm{sup −1} using a modular time-of-flight mass spectrometer (TOF-MS). By irradiating a sample of trapped SrCl{sup +} molecular ions with a pulsed dye laser, X{sup 1}Σ{sup +} state molecular ions are electronically excited to the repulsive wall of the A{sup 1}Π state, resulting in dissociation. Using the TOF-MS, the product fragments are detected and the photodissociation cross-section is determined for a broad range of photon energies. Detailed ab initio calculations of the SrCl{sup +} molecular potentials and spectroscopic constants are also performed and are found to be in good agreement with experiment. The spectroscopic constants for SrCl{sup +} are also compared to those of another alkaline earth halogen, BaCl{sup +}, in order to highlight structural differences between the two molecular ions. This work represents the first spectroscopy and ab initio calculations of SrCl{sup +}.

  14. Characterization of Compounds in Psoralea corylifolia Using High-Performance Liquid Chromatography Diode Array Detection, Time-of-Flight Mass Spectrometry and Quadrupole Ion Trap Mass Spectrometry.

    PubMed

    Tan, Guangguo; Yang, Tiehong; Miao, Huayan; Chen, Hao; Chai, Yifeng; Wu, Hong

    2015-10-01

    High-performance liquid chromatography with diode array detection (HPLC-DAD), time-of-flight mass spectrometry (HPLC-TOFMS) and quadrupole ion trap mass spectrometry (HPLC-QITMS) were used for separation and identification of multi-components in Psoralea corylifolia. Benefiting from combining the accurate mass measurement of HPLC-TOFMS to generate elemental compositions, the complementary multilevel structural information provided by HPLC-QITMS and the characteristic UV spectra obtained from HPLC-DAD, 24 components in P. corylifolia were identified. The five groups of isomers were differentiated based on the fragmentation behaviors in QITMS and UV spectra. It can be concluded that an effective method based on the combination of HPLC-DAD, HPLC-TOFMS and HPLC-QITMS for identification of chemical components in P. corylifolia was established. The results provide essential data for further pharmacological and clinical studies of P. corylifolia and facilitate the rapid quality control of the crude drug.

  15. High Pressure Mass Spectrometry: The Generation of Mass Spectra at Operating Pressures Exceeding 1 Torr in a Microscale Cylindrical Ion Trap.

    PubMed

    Blakeman, Kenion H; Wolfe, Derek W; Cavanaugh, Craig A; Ramsey, J Michael

    2016-05-17

    We present the first demonstration of high pressure mass spectrometry (HPMS), which we define as mass spectrometry performed at pressures greater than 100 mTorr. Mass analysis is shown at operational pressures exceeding 1 Torr of helium buffer gas. A differentially pumped MS system was constructed for HPMS development consisting of two chambers. The first chamber (mass analysis chamber) was operated at pressures up to 1.2 Torr and contained the ionization source and a microscale cylindrical ion trap (CIT) mass analyzer. The CIT had critical dimensions of r0 = 500 μm and z0 = 650 μm. The second chamber was held at a lower pressure (≤10 mTorr) and contained an electron multiplier for detection. Mass spectra for xenon, 2-chloroethyl ethyl sulfide (CEES), and octane were acquired with helium buffer gas pressures ranging from 0.04 to 1.2 Torr in the mass analysis chamber. Full-width at half-maximum of mass spectral peaks was found to increase 143% for xenon, 40% for CEES, and 77% for octane over this pressure range, with maximum peak widths of 1.19, 1.26, and 0.82 Da, respectively. Data were fitted with an algebraic model that factors in ion-neutral collision peak broadening effects at high pressures. Experimental and theoretical peak broadening slopes showed good agreement at buffer gas pressures greater than 0.2 Torr. Experiments presented here demonstrate mass spectrometry at pressures orders of magnitude higher than conventionally practiced with any type of mass analyzer. The use of HPMS provides a way to eliminate turbo pumping requirements, leading to significant reduction in MS system size, weight, and power and facilitating a path toward compact/hand-held mass spectrometers with numerous potential applications.

  16. High Pressure Mass Spectrometry: The Generation of Mass Spectra at Operating Pressures Exceeding 1 Torr in a Microscale Cylindrical Ion Trap.

    PubMed

    Blakeman, Kenion H; Wolfe, Derek W; Cavanaugh, Craig A; Ramsey, J Michael

    2016-05-17

    We present the first demonstration of high pressure mass spectrometry (HPMS), which we define as mass spectrometry performed at pressures greater than 100 mTorr. Mass analysis is shown at operational pressures exceeding 1 Torr of helium buffer gas. A differentially pumped MS system was constructed for HPMS development consisting of two chambers. The first chamber (mass analysis chamber) was operated at pressures up to 1.2 Torr and contained the ionization source and a microscale cylindrical ion trap (CIT) mass analyzer. The CIT had critical dimensions of r0 = 500 μm and z0 = 650 μm. The second chamber was held at a lower pressure (≤10 mTorr) and contained an electron multiplier for detection. Mass spectra for xenon, 2-chloroethyl ethyl sulfide (CEES), and octane were acquired with helium buffer gas pressures ranging from 0.04 to 1.2 Torr in the mass analysis chamber. Full-width at half-maximum of mass spectral peaks was found to increase 143% for xenon, 40% for CEES, and 77% for octane over this pressure range, with maximum peak widths of 1.19, 1.26, and 0.82 Da, respectively. Data were fitted with an algebraic model that factors in ion-neutral collision peak broadening effects at high pressures. Experimental and theoretical peak broadening slopes showed good agreement at buffer gas pressures greater than 0.2 Torr. Experiments presented here demonstrate mass spectrometry at pressures orders of magnitude higher than conventionally practiced with any type of mass analyzer. The use of HPMS provides a way to eliminate turbo pumping requirements, leading to significant reduction in MS system size, weight, and power and facilitating a path toward compact/hand-held mass spectrometers with numerous potential applications. PMID:27109864

  17. Ion parking during ion/ion reactions in electrodynamic ion traps.

    PubMed

    McLuckey, Scott A; Reid, Gavin E; Wells, J Mitchell

    2002-01-15

    Under appropriate ion density conditions, it is possible to selectively inhibit rates of ion/ion reactions in a quadrupole ion trap via the application of oscillatory voltages to one or more electrodes of the ion trap. The phenomenon is demonstrated using dipolar resonance excitation applied to the end-cap electrodes of a three-dimensional quadrupole ion trap. The application of a resonance excitation voltage tuned to inhibit the ion/ion reaction rate of a specific range of ion mass-to-charge ratios is referred to as "ion parking". The bases for rate inhibition are (i) an increase in the relative velocity of the ion/ion reaction pair, which reduces the cross section for ion/ion capture and, at least in some cases, (ii) reduction in the time of physical overlap of positively charged and negatively charged ion clouds. The efficiency and specificity of the ion parking experiment is highly dependent upon ion densities, trapping conditions, ion charge states, and resonance excitation conditions. The ion parking experiment is illustrated herein along with applications to the concentration of ions originally present over a range of charge states into a selected charge state and in the selection of a particular ion from a set of ions derived from a simple protein mixture.

  18. Electrospray Ionization/Ion Mobility Spectrometer/Cylindrical Ion Trap Mass Spectrometer System for In-Situ Detection of Organic Compounds

    NASA Technical Reports Server (NTRS)

    Kanik, I.; Johnson, P. V.; Beegle, L. W.; Cooks, R. G.; Laughlin, B. C.; Hill, H. H.

    2003-01-01

    The potential of an Electrospray Ionization/Ion Mobility Spectrometer/Cylindrical Ion Trap Mass Spectrometer (ESI/IMS/CIT-MS) as an analytical instrument for analyzing material extracted from rock and soil samples as part of a suite of instruments on the proposed 2009 Mars Science Lander (MSL) will be demonstrated. This instrument will be able to identify volatile compounds as well as resident organic molecules on the parts-per-billion (ppb) level. Also, it will be able to obtain an inventory of chemical species on the surface of Mars which will result in a better understanding of ongoing surface chemistry. Finally, questions relevant to biological processes will be answered with the complete inventory of surface and near surface organic molecules that the ESI/IMS/CIT is capable of performing.

  19. A Generic Multiple Reaction Monitoring Based Approach for Plant Flavonoids Profiling Using a Triple Quadrupole Linear Ion Trap Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Yan, Zhixiang; Lin, Ge; Ye, Yang; Wang, Yitao; Yan, Ru

    2014-06-01

    Flavonoids are one of the largest classes of plant secondary metabolites serving a variety of functions in plants and associating with a number of health benefits for humans. Typically, they are co-identified with many other secondary metabolites using untargeted metabolomics. The limited data quality of untargeted workflow calls for a shift from the breadth-first to the depth-first screening strategy when a specific biosynthetic pathway is focused on. Here we introduce a generic multiple reaction monitoring (MRM)-based approach for flavonoids profiling in plants using a hybrid triple quadrupole linear ion trap (QTrap) mass spectrometer. The approach includes four steps: (1) preliminary profiling of major aglycones by multiple ion monitoring triggered enhanced product ion scan (MIM-EPI); (2) glycones profiling by precursor ion triggered EPI scan (PI-EPI) of major aglycones; (3) comprehensive aglycones profiling by combining MIM-EPI and neutral loss triggered EPI scan (NL-EPI) of major glycone; (4) in-depth flavonoids profiling by MRM-EPI with elaborated MRM transitions. Particularly, incorporation of the NH3 loss and sugar elimination proved to be very informative and confirmative for flavonoids screening. This approach was applied for profiling flavonoids in Astragali radix ( Huangqi), a famous herb widely used for medicinal and nutritional purposes in China. In total, 421 flavonoids were tentatively characterized, among which less than 40 have been previously reported in this medicinal plant. This MRM-based approach provides versatility and sensitivity that required for flavonoids profiling in plants and serves as a useful tool for plant metabolomics.

  20. A generic multiple reaction monitoring based approach for plant flavonoids profiling using a triple quadrupole linear ion trap mass spectrometry.

    PubMed

    Yan, Zhixiang; Lin, Ge; Ye, Yang; Wang, Yitao; Yan, Ru

    2014-06-01

    Flavonoids are one of the largest classes of plant secondary metabolites serving a variety of functions in plants and associating with a number of health benefits for humans. Typically, they are co-identified with many other secondary metabolites using untargeted metabolomics. The limited data quality of untargeted workflow calls for a shift from the breadth-first to the depth-first screening strategy when a specific biosynthetic pathway is focused on. Here we introduce a generic multiple reaction monitoring (MRM)-based approach for flavonoids profiling in plants using a hybrid triple quadrupole linear ion trap (QTrap) mass spectrometer. The approach includes four steps: (1) preliminary profiling of major aglycones by multiple ion monitoring triggered enhanced product ion scan (MIM-EPI); (2) glycones profiling by precursor ion triggered EPI scan (PI-EPI) of major aglycones; (3) comprehensive aglycones profiling by combining MIM-EPI and neutral loss triggered EPI scan (NL-EPI) of major glycone; (4) in-depth flavonoids profiling by MRM-EPI with elaborated MRM transitions. Particularly, incorporation of the NH3 loss and sugar elimination proved to be very informative and confirmative for flavonoids screening. This approach was applied for profiling flavonoids in Astragali radix (Huangqi), a famous herb widely used for medicinal and nutritional purposes in China. In total, 421 flavonoids were tentatively characterized, among which less than 40 have been previously reported in this medicinal plant. This MRM-based approach provides versatility and sensitivity that required for flavonoids profiling in plants and serves as a useful tool for plant metabolomics.

  1. Improving IRMPD in a quadrupole ion trap.

    PubMed

    Newsome, G Asher; Glish, Gary L

    2009-06-01

    A focused laser is used to make infrared multiphoton photodissociation (IRMPD) more efficient in a quadrupole ion trap mass spectrometer. Efficient (up to 100%) dissociation at the standard operating pressure of 1 x 10(-3) Torr can be achieved without any supplemental ion activation and with shorter irradiation times. The axial amplitudes of trapped ion clouds are measured using laser tomography. Laser flux on the ion cloud is increased six times by focusing the laser so that the beam waist approximates the ion cloud size. Unmodified peptide ions from 200 Da to 3 kDa are completely dissociated in 2.5-10 ms at a bath gas pressure of 3.3 x 10(-4) Torr and in 3-25 ms at 1.0 x 10(-3) Torr. Sequential dissociation of product ions is increased by focusing the laser and by operating at an increased bath gas pressure to minimize the size of the ion cloud.

  2. Identification of microcystin toxins from a strain of Microcystis aeruginosa by liquid chromatography introduction into a hybrid linear ion trap-Fourier transform ion cyclotron resonance mass spectrometer.

    PubMed

    Diehnelt, Chris W; Dugan, Nicholas R; Peterman, Scott M; Budde, William L

    2006-01-15

    The cyclic heptapeptide microcystin toxins produced by a strain of Microcystis aeruginosa that has not been investigated previously were separated by liquid chromatography and identified by high-accuracy m/z measurements of their [M + H]+ ions and the fragment ions produced by collision-activated dissociation of the [M + H]+ ions. The cyanobacteria B2666 strain was cultured in a standard growth medium, and the toxins were released from the cells, extracted from the aqueous phase, and concentrated using standard procedures. The microcystins were separated by reversed-phase microbore liquid chromatography and introduced directly into a hybrid linear ion trap-Fourier transform ion cyclotron resonance mass spectrometer with electrospray ionization. The known microcystins (MC) MC-LR, MC-LA, [MeSer7]MC-LR, MC-LL, MC-LF, and MC-L(Aba) were identified along with the two previously unreported structural variants [Asp3]MC-LA and [Asp3]MC-LL. In addition to the [M + H]+ ions, accurate m/z measurements were made of 12-18 product ions for each identified microcystin. The mean difference between measured and calculated exact m/z was less than 2 parts per million, which often allowed assignment of unique compositions to the observed ions. A mechanism is presented that accounts for an important collision-activated dissociation process that gives valuable sequence ions from microcystins that do not contain arginine. The analytical technique used in this work is capable of supporting fairly rapid and very reliable identifications of known microcystins when standards are not available and of most structural variants independent of additional information from other analytical techniques.

  3. Evaluating Multiplexed Quantitative Phosphopeptide Analysis on a Hybrid Quadrupole Mass Filter/Linear Ion Trap/Orbitrap Mass Spectrometer

    PubMed Central

    2015-01-01

    As a driver for many biological processes, phosphorylation remains an area of intense research interest. Advances in multiplexed quantitation utilizing isobaric tags (e.g., TMT and iTRAQ) have the potential to create a new paradigm in quantitative proteomics. New instrumentation and software are propelling these multiplexed workflows forward, which results in more accurate, sensitive, and reproducible quantitation across tens of thousands of phosphopeptides. This study assesses the performance of multiplexed quantitative phosphoproteomics on the Orbitrap Fusion mass spectrometer. Utilizing a two-phosphoproteome model of precursor ion interference, we assessed the accuracy of phosphopeptide quantitation across a variety of experimental approaches. These methods included the use of synchronous precursor selection (SPS) to enhance TMT reporter ion intensity and accuracy. We found that (i) ratio distortion remained a problem for phosphopeptide analysis in multiplexed quantitative workflows, (ii) ratio distortion can be overcome by the use of an SPS-MS3 scan, (iii) interfering ions generally possessed a different charge state than the target precursor, and (iv) selecting only the phosphate neutral loss peak (single notch) for the MS3 scan still provided accurate ratio measurements. Remarkably, these data suggest that the underlying cause of interference may not be due to coeluting and cofragmented peptides but instead from consistent, low level background fragmentation. Finally, as a proof-of-concept 10-plex experiment, we compared phosphopeptide levels from five murine brains to five livers. In total, the SPS-MS3 method quantified 38 247 phosphopeptides, corresponding to 11 000 phosphorylation sites. With 10 measurements recorded for each phosphopeptide, this equates to more than 628 000 binary comparisons collected in less than 48 h. PMID:25521595

  4. Multifactorial optimization approach for the determination of polycyclic aromatic hydrocarbons in river sediments by gas chromatography-quadrupole ion trap selected ion storage mass spectrometry.

    PubMed

    Leite, Natalicio Ferreira; Peralta-Zamora, Patricio; Grassi, Marco Tadeu

    2008-05-30

    A procedure for the determination of very low polycyclic aromatic hydrocarbons (PAHs) concentrations in sediment samples has been developed by gas chromatography-quadrupole ion trap mass spectrometry (GC-QIT MS) after extraction with dichloromethane and purification by using silica gel cleanup. Identification and quantification of analytes were based on the selected ion storage (SIS) strategy using deuterated PAHs as internal standards. In order to search out the main factors affecting the SIS mass spectrometry efficiency, four MS parameters, including target total ion count (TTIC), waveform amplitude (WA), transfer line (XLT) and ion trap temperatures (ITT) were subjected to a complete multifactorial design. The most relevant parameters obtained (TTIC and WA) were optimized by a rotatable and orthogonal composite design. Optimum values for these parameters were selected for the development of the method involving PAH determination in sediment samples. The optimized method exhibited a range of 111-760% higher signal-to-noise (S/N) ratios for PAHs in comparison with the method operated by the default conditions, demonstrating that the multifactorial optimization contributed to substantially improve the sensitivity of the GC-QIT MS determination. The accuracy of the method was verified by analyzing NWRI EC-3 certified reference material (Lake Ontario sediment). The selectivity, sensitivity (limits of quantification were in the range of 0.02-11.0 ng g(-1)), accuracy (recoveries >or=77%) and precision (RSD

  5. POLAR ORGANIC CHEMICAL INTEGRATIVE SAMPLING AND LIQUID CHROMATOGRAPHY-ELECTROSPRAY/ION-TRAP MASS SPECTROMETRY FOR ASSESSING SELECTED PRESCRIPTION AND ILLICIT DRUGS IN TREATED SEWAGE EFFLUENTS

    EPA Science Inventory

    The purpose of the research presented in this paper is two-fold: (1) to demonstrate the 4 coupling of two state-of-the-art techniques: a time-weighted polar organic integrative sampler (POCIS) and micro-liquid chromatography-electrospray/ion trap mass spectrometry (u-LC-6 ES/ITMS...

  6. Trapping low-energy antiprotons in an ion trap

    SciTech Connect

    Fei, Xiang.

    1990-01-01

    A fraction of antiprotons from the Low Energy Antiproton Ring (LEAR) of CERN are slowed from 5.9 MeV to below 3 keV as they pass through thin foils. Transmitted particle energy distribution and low energy antiproton yield are measured by a time-of-flight technique. The difference in the range of protons and antiprotons (known as the Barkas effect) is observed. While still in flight, up to 1.3 {times} 10{sup 5} antiprotons with energies between 0 eV to 3 keV are stored in an ion trap from a single pulse of 5.9 MeV antiprotons leaving LEAR, thus a trapping efficiency exceeding of 4 {times} 10{sup {minus}4} is established. Trapped antiprotons maintain their initial energy distribution unless allowed to collide with a cloud of trapped electrons, whereupon they slow and cool below 1 meV in 10 s, and fall into a harmonic potential well suited for precision mass measurements. The slowing, trapping and cooling of antiprotons are the main focus of this thesis. The stored antiprotons are in thermal equilibrium at 4.2 K. In this ion trap, the antiproton cyclotron frequency is measured and compared with the proton (or electron) cyclotron frequency. The new measured ratio of the antiproton and proton inertial masses, with its 4 {times} 10{sup {minus}8} uncertainty, is more than three orders of magnitude more accurate than previous measurements using exotic atoms. This is a most precise test of CPT invariance with baryons. The antiproton lifetime in an ion trap was measured to be more than 103 days by trapping a cloud of antiprotons for 59 days. The indicates the number density of atoms is less than 100/cm{sup 3} which corresponds to the pressure in the vacuum chamber being less than 5 {times} 10{sup {minus}17} Torr at 4.2 K if we apply the ideal gas law.

  7. Progress at the Penning Trap Mass Spectrometer ``THe-Trap''

    NASA Astrophysics Data System (ADS)

    Hoecker, Martin; Eronen, Tommi; Ketter, Jochen; Streubel, Sebastian; Blaum, Klaus; van Dyck, Robert S.

    2012-03-01

    In 2008, the ``University of Washington Penning-Trap Mass Spectrometer'' (UW-PTMS), originally designed and built by the Van Dyck group, was moved to the Max-Planck-Insitute for Nuclear Physics in Heidelberg, Germany. It was set up in a dedicated laboratory that meets both the radiation-safety requirements, and the environment-stabilization demands for a high-precision measurement of the tritium/helium-3 mass ratio. Our goal is to measure this mass ratio with a relative uncertainty of 10-11, which would be more than an order of magnitude better than the previous best measurement. It would decrease the uncertainty in the tritium beta decay Q-value (an important parameter in the ongoing search for the neutrino mass by experiments such as KATRIN) by the same factor. In order to emphasize the specialization of our experiment with regard to Tritium and ^3Helium, it was renamed to ``THe-Trap''. THe-Trap features a double Penning-trap for rapid ion exchange, an external ion source to minimize trap contamination, a novel Zener-based voltage source, and active as well as passive stabilization of temperature, pressure and the magnetic field of the superconducting magnet. An overview of the project and a report on the recent progress will be given.

  8. Structure analysis of triterpene saponins in Polygala tenuifolia by electrospray ionization ion trap multiple-stage mass spectrometry.

    PubMed

    Liu, Jiangyun; Yang, Xuedong; He, Jiuming; Xia, Min; Xu, Lizhen; Yang, Shilin

    2007-07-01

    Eighteen different triterpene saponins isolated from Polygala tenuifolia were investigated by electrospray ionization ion trap multiple-stage mass spectrometry (ESI-ITMS(n)) in positive and negative ion modes. MS(1)-MS(3)/MS(4) spectra of the both modes were analyzed, and they all gave fragments in line and shared common fragmentation patterns. Key fragments from MS(n) spectra of both the modes and their proposed fragmentation pathways were constructed with examples illustrated for the formation of characteristic fragments in the saponins. Two special fragmentation patterns were proposed: (1) the formation of fragments by cleavage of CH(2)O from Delta(12)-14alpha-CH(2)OH of the oleanene-type saponin aglycone in both positive and negative MS(n) (n > or = 2) modes; (2) the occurrence of fragments by cleavage of CO(2) and 3-glucose as the characteristic structure feature of 23-COOH at the oleanene-type saponin aglycones coupled with 3-Glc substitutes in the negative MS(n) (n > or = 2) modes. Peak intensities in MS(n) spectra were also correlated with structural features and fragmentation preferences of the investigated saponins, which are discussed in detail. In general, fragments formed predominantly by cleavages of glycosidic bonds in the positive mode, while selective cleavages of acyl bonds preceded that of glycosidic bonds in negative MS(n) (n > or = 2) mode, both of which could well be applied to the structural analysis of these saponins. Interpretation of MS(n) spectra presented here provided diagnostic key fragment ions important for the structural elucidation of saponins in P.tenuifolia.

  9. Mass trapping for Anastrepha suspensa

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Mass trapping has been found to be highly effective for control of pest fruit flies when populations are low and a highly effective lure is available for the target species. Successful population control through mass trapping is an indicator that attract-and-kill bait stations may be equally succes...

  10. Liquid chromatography quadrupole linear ion trap mass spectrometry for multiclass screening and identification of lipophilic marine biotoxins in bivalve mollusks.

    PubMed

    Wu, Haiyan; Guo, Mengmeng; Tan, Zhijun; Cheng, Haiyan; Li, Zhaoxin; Zhai, Yuxiu

    2014-09-01

    A liquid chromatography quadrupole linear ion trap mass spectrometry method with fast polarity switching and a scheduled multiple reaction monitoring algorithm mode was developed for multiclass screening and identification of lipophilic marine biotoxins in bivalve molluscs. A major advantage of the method is that it can detect members of all six groups of lipophilic marine biotoxins [okadaic acid (OA), yessotoxins (YTX), azaspiracids (AZA), pectenotoxins (PTX), cyclic imines (CI), and brevetoxins (PbTx)], thereby allowing quantification and high confidence identification from a single liquid chromatography tandem mass spectrometry (LC-MS/MS) injection. An enhanced product ion (EPI) library was constructed after triggered collection of data via information-dependent acquisition (IDA) of EPI spectra from standard samples. A separation method for identifying 17 target toxins in a single analysis within 12min was developed and tested. Different solid phase extraction sorbents, the matrix effect (for oyster, scallop, and mussel samples), and stability of the standards also were evaluated. Matrix-matched calibration was used for quantification of the toxins. The limits of detection were 0.12-13.6μg/kg, and the limits of quantification were 0.39-45.4μg/kg. The method was used to analyze 120 shellfish samples collected from farming areas along the coast of China, and 7% of the samples were found to be contaminated with toxins. The library search identified PbTx-3, YTX, OA, PTX2, AZA1, AZA2, and desmethylspirolide C (SPX1). Overall, the method exhibited excellent sensitivity and reproducibility, and it will have broad applications in the monitoring of lipophilic marine biotoxins.

  11. Liquid chromatography quadrupole linear ion trap mass spectrometry for multiclass screening and identification of lipophilic marine biotoxins in bivalve mollusks.

    PubMed

    Wu, Haiyan; Guo, Mengmeng; Tan, Zhijun; Cheng, Haiyan; Li, Zhaoxin; Zhai, Yuxiu

    2014-09-01

    A liquid chromatography quadrupole linear ion trap mass spectrometry method with fast polarity switching and a scheduled multiple reaction monitoring algorithm mode was developed for multiclass screening and identification of lipophilic marine biotoxins in bivalve molluscs. A major advantage of the method is that it can detect members of all six groups of lipophilic marine biotoxins [okadaic acid (OA), yessotoxins (YTX), azaspiracids (AZA), pectenotoxins (PTX), cyclic imines (CI), and brevetoxins (PbTx)], thereby allowing quantification and high confidence identification from a single liquid chromatography tandem mass spectrometry (LC-MS/MS) injection. An enhanced product ion (EPI) library was constructed after triggered collection of data via information-dependent acquisition (IDA) of EPI spectra from standard samples. A separation method for identifying 17 target toxins in a single analysis within 12min was developed and tested. Different solid phase extraction sorbents, the matrix effect (for oyster, scallop, and mussel samples), and stability of the standards also were evaluated. Matrix-matched calibration was used for quantification of the toxins. The limits of detection were 0.12-13.6μg/kg, and the limits of quantification were 0.39-45.4μg/kg. The method was used to analyze 120 shellfish samples collected from farming areas along the coast of China, and 7% of the samples were found to be contaminated with toxins. The library search identified PbTx-3, YTX, OA, PTX2, AZA1, AZA2, and desmethylspirolide C (SPX1). Overall, the method exhibited excellent sensitivity and reproducibility, and it will have broad applications in the monitoring of lipophilic marine biotoxins. PMID:25086754

  12. Triterpenoid saponins profiling by adducts-targeted neutral loss triggered enhanced resolution and product ion scanning using triple quadrupole linear ion trap mass spectrometry.

    PubMed

    Yan, Zhixiang; Lin, Ge; Ye, Yang; Wang, Yitao; Yan, Ru

    2014-03-28

    Triterpenoid saponins (TSs) are a unique class of high molecular weight glycosides and have been frequently used in cosmetic and phytotherapy industry. There is a great need to comprehensively profile these plant metabolites for studying their functions. In the present study, a novel adducts targeted neutral loss (NL), triggered enhanced resolution (ER) and enhanced product ion (EPI) scanning approach were described for TSs profiling using a triple quadrupole linear ion trap mass spectrometry. This approach circumvented the disadvantages of poor glycosidic bond cleavage of TSs by monitoring the NH3 (NL17) and HCOOH (NL46) loss of their abundant ammonium and formate adducts, respectively. The sugar-loss independent NL scanning served as a sensitive survey scan and triggered information-dependent ER and EPI scans to increase peak assignment confidence. NL17 was superior to NL46 for TSs characterization due to the better fragmentation of ammonium adducts than formate adducts. For those TSs undetectable by NL17, precursor ion (PI) scan for sapogenin fragments could be used to screen out non-adducted TSs. The NL/PI-ER-EPI approach was applied for TSs profiling in Astragali Radix, a famous medicinal and nutritional plant widely used in Asian countries and United States. In total, 136 TSs were detected while previous research using high resolution mass spectrometry based full scan only detected 22 TSs in this herb.

  13. Quantification of Tryptic Peptides in Quadrupole Ion Trap Using High-Mass Signals Derived from Isotope-Coded N-Acetyl Dipeptide Tags

    NASA Astrophysics Data System (ADS)

    Seo, Jongcheol; Yoon, Hye-Joo; Shin, Seung Koo

    2011-09-01

    Isotope-labeled N-acetyl dipeptides (Ac-Xxx-Ala) are coupled to the primary amines of tryptic peptides and then analyzed by tandem mass spectrometry. Amide bond cleavage between Xxx and Ala provides both low- and high-mass isotope-coded signals for quantification of peptides. Especially, facile cleavage at the modified lysine side chain yields very strong high-mass quantitation signals in a noise-free region. Tagging tryptic peptides with isobaric N-acetyl dipeptides is a viable strategy for accurate quantification of proteins, which can be used with most quadrupole ion trap mass spectrometers carrying the 1/3 mass cut-off problem.

  14. Sensitive and comprehensive detection of chemical warfare agents in air by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow introduction.

    PubMed

    Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Yamashiro, Shigeharu; Sano, Yasuhiro; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Sekiguchi, Hiroyuki; Iura, Kazumitsu; Nagashima, Hisayuki; Nagoya, Tomoki; Tsuge, Kouichiro; Ohsawa, Isaac; Okumura, Akihiko; Takada, Yasuaki; Ezawa, Naoya; Watanabe, Susumu; Hashimoto, Hiroaki

    2014-05-01

    A highly sensitive and specific real-time field-deployable detection technology, based on counterflow air introduction atmospheric pressure chemical ionization, has been developed for a wide range of chemical warfare agents (CWAs) comprising gaseous (two blood agents, three choking agents), volatile (six nerve gases and one precursor agent, five blister agents), and nonvolatile (three lachrymators, three vomiting agents) agents in air. The approach can afford effective chemical ionization, in both positive and negative ion modes, for ion trap multiple-stage mass spectrometry (MS(n)). The volatile and nonvolatile CWAs tested provided characteristic ions, which were fragmented into MS(3) product ions in positive and negative ion modes. Portions of the fragment ions were assigned by laboratory hybrid mass spectrometry (MS) composed of linear ion trap and high-resolution mass spectrometers. Gaseous agents were detected by MS or MS(2) in negative ion mode. The limits of detection for a 1 s measurement were typically at or below the microgram per cubic meter level except for chloropicrin (submilligram per cubic meter). Matrix effects by gasoline vapor resulted in minimal false-positive signals for all the CWAs and some signal suppression in the case of mustard gas. The moisture level did influence the measurement of the CWAs.

  15. Sensitive and comprehensive detection of chemical warfare agents in air by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow introduction.

    PubMed

    Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Yamashiro, Shigeharu; Sano, Yasuhiro; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Sekiguchi, Hiroyuki; Iura, Kazumitsu; Nagashima, Hisayuki; Nagoya, Tomoki; Tsuge, Kouichiro; Ohsawa, Isaac; Okumura, Akihiko; Takada, Yasuaki; Ezawa, Naoya; Watanabe, Susumu; Hashimoto, Hiroaki

    2014-05-01

    A highly sensitive and specific real-time field-deployable detection technology, based on counterflow air introduction atmospheric pressure chemical ionization, has been developed for a wide range of chemical warfare agents (CWAs) comprising gaseous (two blood agents, three choking agents), volatile (six nerve gases and one precursor agent, five blister agents), and nonvolatile (three lachrymators, three vomiting agents) agents in air. The approach can afford effective chemical ionization, in both positive and negative ion modes, for ion trap multiple-stage mass spectrometry (MS(n)). The volatile and nonvolatile CWAs tested provided characteristic ions, which were fragmented into MS(3) product ions in positive and negative ion modes. Portions of the fragment ions were assigned by laboratory hybrid mass spectrometry (MS) composed of linear ion trap and high-resolution mass spectrometers. Gaseous agents were detected by MS or MS(2) in negative ion mode. The limits of detection for a 1 s measurement were typically at or below the microgram per cubic meter level except for chloropicrin (submilligram per cubic meter). Matrix effects by gasoline vapor resulted in minimal false-positive signals for all the CWAs and some signal suppression in the case of mustard gas. The moisture level did influence the measurement of the CWAs. PMID:24678766

  16. Trace analysis of explosives in seawater using solid-phase microextraction and gas chromatography/ion trap mass spectrometry

    SciTech Connect

    Barshick, S.A.; Griest, W.H.

    1998-07-15

    Complex matrices typically cannot be analyzed directly to obtain the selectivity and sensitivity required for most trace analysis applications. To circumvent this problem, solid-phase microextraction (SPME) techniques were used to preconcentrate analytes selectively prior to gas chromatographic/ion trap mass spectrometric analysis. This approach was applied to the trace analysis of explosives and their metabolites in seawater. The choice of SPME sorbent phase was shown to be important especially for the amino metabolites of trinitrotoluene (TNT) and RDX, which were extracted better on polar phases. Although equilibration times were quite lengthy, on the order of 30 min or greater, a sampling time of only 10 min was shown to be sufficient for achieving low part-per-billion (ppb) to part-per-trillion (ppt) detection limits for TNT and the amino metabolites in real seawater samples. While SPME was ideal for rapid screening of explosives in seawater samples, methods for improving the reproducibility and accuracy of quantification are still being investigated.

  17. Phenolic profile characterization of Chemlali olive stones by liquid chromatography-ion trap mass spectrometry.

    PubMed

    Ben Mansour, Amir; Porter, Elaine A; Kite, Geoffrey C; Simmonds, Monique S J; Abdelhedi, Ridha; Bouaziz, Mohamed

    2015-02-25

    Aqueous methanol extracts of Chemlali olive stones were analyzed by reverse phase high-performance liquid chromatography (HPLC) with diode array detection and mass spectrometry [LC-MS/MS]. Oleoside, oleoside 11-methyl ester, nuezhenide, oleoside 11-methyloleoside, nuezhenide 11-methyloleoside, oleuropein, and glycosides of tryosol and hydroxytyrosol glycosides were identified in stones of Chemali olives. The antioxidant activity observed for the extract of the olive stones (IC50 = 13.84 μg/mL, TEAC = 0.436 mM) may be due to the high content of phenolic compounds, of which the main compounds are nuezhenide (325.78 mg/100g), methoxy derivative of nuezhenide (132.46 mg/100g), and nuezhenide-11-methyloleoside (82.91 mg/100g). These results suggest the use of olive stones as sources of natural antioxidants.

  18. Improved 6-Plex Tandem Mass Tags Quantification Throughput Using a Linear Ion Trap-High-Energy Collision Induced Dissociation MS(3) Scan.

    PubMed

    Liu, Jane M; Sweredoski, Michael J; Hess, Sonja

    2016-08-01

    The use of tandem mass tags (TMT) as an isobaric labeling strategy is a powerful method for quantitative proteomics, yet its accuracy has traditionally suffered from interference. This interference can be largely overcome by selecting MS(2) fragment precursor ions for high-energy collision induced dissociation (HCD) MS(3) analysis in an Orbitrap scan. While this approach minimizes the interference effect, sensitivity suffers due to the high AGC targets and long acquisition times associated with MS(3) Orbitrap detection. We investigated whether acquiring the MS(3) scan in a linear ion trap with its lower AGC target would increase overall quantification levels with a minimal effect on precision and accuracy. Trypsin-digested proteins from Saccharomyces cerevisiae were tagged with 6-plex TMT reagents. The sample was subjected to replicate analyses using either the Orbitrap or the linear ion trap for the HCD MS(3) scan. HCD MS(3) detection in the linear ion trap vs Orbitrap increased protein identification by 66% with minor loss in precision and accuracy. Thus, the use of a linear ion trap-HCD MS(3) scan during a 6-plex TMT experiment can improve overall identification levels while maintaining the power of multiplexed quantitative analysis. PMID:27377715

  19. Ion trapping in Recycler Ring

    SciTech Connect

    K.Y. Ng

    2004-06-28

    Transverse instabilities have been observed in the antiproton beam stored in the Fermilab Recycler Ring, resulting in a sudden increase in the transverse emittances and a small beam loss. The instabilities appear to occur a few hours after a change in the ramping pattern of the Main Injector which shares the same tunnel. The phenomena have been studied by inducing similar instabilities. However, the mechanism is still unknown. A possible explanation is that the ions trapped in the beam reach such an intensity that collective coupled transverse oscillation occurs. However, there is no direct evidence of the trapped ions at this moment.

  20. Experimental investigation of planar ion traps

    SciTech Connect

    Pearson, C. E.; Leibrandt, D. R.; Bakr, W. S.; Mallard, W. J.; Brown, K. R.; Chuang, I. L.

    2006-03-15

    Chiaverini et al. [Quantum Inf. Comput. 5, 419 (2005)] recently suggested a linear Paul trap geometry for ion-trap quantum computation that places all of the electrodes in a plane. Such planar ion traps are compatible with modern semiconductor fabrication techniques and can be scaled to make compact, many-zone traps. In this paper we present an experimental realization of planar ion traps using electrodes on a printed circuit board to trap linear chains of tens of charged particles of 0.44 {mu}m diameter in a vacuum of 15 Pa (10{sup -1} torr). With these traps we address concerns about the low trap depth of planar ion traps and develop control electrode layouts for moving ions between trap zones without facing some of the technical difficulties involved in an atomic ion-trap experiment. Specifically, we use a trap with 36 zones (77 electrodes) arranged in a cross to demonstrate loading from a traditional four-rod linear Paul trap, linear ion movement, splitting and joining of ion chains, and movement of ions through intersections. We further propose an additional dc-biased electrode above the trap which increases the trap depth dramatically, and a planar ion-trap geometry that generates a two-dimensional lattice of point Paul traps.

  1. Nano-electrospray and microbore liquid chromatography-ion trap mass spectrometry studies of copper complexation with MHC restricted peptides.

    PubMed

    Creaser, C S; Lill, J R; Bonner, P L; Hill, S C; Rees, R C

    2000-04-01

    The formation of copper/peptide complex ions by nano-electrospray and microbore HPLC-electrospray mass spectrometry has been investigated for major histocompatibility complex (MHC) class I and class II restricted peptides. Post-column addition of copper(II) acetate following microbore HPLC-MS separation was carried out using a mixing T-piece or via the sheath flow inlet of the electrospray source. Optimal analytical conditions for copper complex ion formation were determined by variation of copper concentration, pH, nebulization gas supply and spray voltage. Tandem mass spectrometry of copper/peptide complex ions provides peptide sequence information and insight into the peptide chelation sites. Copper associated y fragment ions dominate the product ion spectrum for non-histidine containing peptides, but both b and y copper complex ions were observed for the histidine containing MHC class I associated peptide gp70. PMID:10892016

  2. Multiresidue analysis of 50 pesticides in grape, pomegranate, and mango by gas chromatography-ion trap mass spectrometry.

    PubMed

    Savant, Rahul H; Banerjee, Kaushik; Utture, Sagar C; Patil, Sangram H; Dasgupta, Soma; Ghaste, Manoj S; Adsule, Pandurang G

    2010-02-10

    A selective and sensitive multiresidue analysis method is reported for simultaneous determination of 50 pesticides of different chemical classes in three commercially important fruits of different nature viz. grape, pomegranate, and mango. The sample preparation method involves extraction of a 10 g sample with 10 mL of ethyl acetate; cleanup by dispersive solid phase extraction with primary secondary amine (PSA, 25 mg) for grape and PSA + graphitized carbon black (25 + 5 mg) for pomegranate and mango; and determination by gas chromatography-ion trap mass spectrometry through multiple reaction monitoring (MRM). Sample preparation under acidified (pH 4) and cold (<4 degrees C) conditions, use of PTV-large volume injection (20 microL) through multibaffled liner and chromatographic separation on a short 10 m VF-5MS capillary column gave a satisfactory response for all of the analytes including relatively unstable compounds such as captan, captafol, folpet, endrine, and iprodione within 31.8 min. The limit of quantification (LOQ) of most of the compounds was

  3. Assignment of acetyl groups to O-2 and/or O-3 of pectic oligogalacturonides using negative electrospray ionization ion trap mass spectrometry.

    PubMed

    Quéméner, Bernard; Cabrera Pino, Juan Carlos; Ralet, Marie-Christine; Bonnin, Estelle; Thibault, Jean-François

    2003-06-01

    Partially acetylated and methylated oligogalacturonides produced by enzymatic hydrolysis of sugar beet pectin were analysed by negative electrospray ionization ion trap mass spectrometry (ESI-ITMS). The (18)O labelling of the oligomer reducing end allowed the precise assignment of the fragments resulting from glycosidic bond and cross-ring cleavages. The collisional-induced dissociation of the C(i) and Z(j) fragment ions through sequential MS(n) experiments always displayed (0, 2)A-type cross-ring cleavage ions which were related to C(2)H(4)O(2) losses. These (0, 2)A ions appeared to be highly diagnostic ions allowing the precise location of the acetyl groups to the O-2 and/or O-3 of the acetylated galacturonic acid residues.

  4. EDITORIAL: Modern applications of trapped ions Modern applications of trapped ions

    NASA Astrophysics Data System (ADS)

    Knoop, Martina; Hilico, Laurent; Eschner, Jürgen

    2009-08-01

    Ion traps are fantastic tools to explore the world of electrons, atomic and molecular ions, or charged clusters, in the classical as well as in the quantum regime. Extremely long storage times allow probing even of single particles with very high precision. The mass selectivity of the trapping devices is exploited in many experiments, in particular for mass metrology. An overwhelming part of the experiments and ideas rely on the very high level of parameter control which is offered by the ion trap. Manipulation of individual ions and engineering of well defined quantum states are the fundamental techniques to take the experiments beyond existing frontiers and to unprecedented precision. This special issue presents state-of-the-art theory and experiments in a variety of tutorials, reviews and research papers. More than half of these contributions form a follow-up to the first workshop on Modern Applications of Trapped Ions held in Les Houches, France, in May 2008. A great number of topics is covered in atomic and molecular physics, with ion traps as a common tool. The variety of approaches is meant to make this digest a helpful resource to the whole ion trapping community. Among the contributions, four major - while still overlapping - domains can be identified. Novel ion trap design is the motor of future developments and applications. Spectacular progress has been made in the domain of quantum information processing, such as the realization of planar traps, which opens the way to large-scale quantum computation. In this issue, this enthralling subject is introduced by a tutorial and two review articles, completed by contributions on different experimental realizations. Precision measurements belong to a more traditional domain which nevertheless evolves at the forefront of research: metrology of frequencies and fundamental constants, measurements of g-factors or high-precision mass measurements are the foundations of atomic and molecular physics. The creation and

  5. Direct analysis of volatile organic compounds in human breath using a miniaturized cylindrical ion trap mass spectrometer with a membrane inlet.

    PubMed

    Riter, Leah S; Laughlin, Brian C; Nikolaev, Eugene; Cooks, R Graham

    2002-01-01

    Membrane introduction mass spectrometry (MIMS) coupled to a miniature mass spectrometer equipped with a cylindrical ion trap (CIT) analyzer was used to monitor the flavor components, 3-phenyl-2-propenal and methyl salicylate, found in cinnamon and wintergreen candies, respectively, directly from human breath. The poly(dimethylsiloxane) (PDMS) membrane was operated in a trap-and-release mode, where the temperature of the membrane was cycled during the experiments, which permitted temporal resolution of the two compounds of interest, facilitating their observation in the complex sample. Under these thermally driven conditions, the 10-90% rise times for both compounds are similar (15 s for methyl salicylate, 17 s for 3-phenyl-2-propenal), but the difference in diffusivity means that the signal for 3-phenyl-2-propenal is delayed and the 10% point occurs 6 s later than that for wintergreen. Additional specificity needed for complex samples was gained by using tandem mass spectrometry.

  6. Highly charged ion secondary ion mass spectroscopy

    DOEpatents

    Hamza, Alex V.; Schenkel, Thomas; Barnes, Alan V.; Schneider, Dieter H.

    2001-01-01

    A secondary ion mass spectrometer using slow, highly charged ions produced in an electron beam ion trap permits ultra-sensitive surface analysis and high spatial resolution simultaneously. The spectrometer comprises an ion source producing a primary ion beam of highly charged ions that are directed at a target surface, a mass analyzer, and a microchannel plate detector of secondary ions that are sputtered from the target surface after interaction with the primary beam. The unusually high secondary ion yield permits the use of coincidence counting, in which the secondary ion stops are detected in coincidence with a particular secondary ion. The association of specific molecular species can be correlated. The unique multiple secondary nature of the highly charged ion interaction enables this new analytical technique.

  7. Development of a Kingdon ion trap system for trapping externally injected highly charged ions

    SciTech Connect

    Numadate, Naoki; Okada, Kunihiro; Nakamura, Nobuyuki; Tanuma, Hajime

    2014-10-01

    We have developed a Kingdon ion trap system for the purpose of the laboratory observation of the x-ray forbidden transitions of highly charged ions (HCIs). Externally injected Ar{sup q+} (q = 5–7) with kinetic energies of 6q keV were successfully trapped in the ion trap. The energy distribution of trapped ions is discussed in detail on the basis of numerical simulations. The combination of the Kingdon ion trap and the time-of-flight mass spectrometer enabled us to measure precise trapping lifetimes of HCIs. As a performance test of the instrument, we measured trapping lifetimes of Ar{sup q+} (q = 5–7) under a constant number density of H₂ and determined the charge-transfer cross sections of Ar{sup q+}(q = 5, 6)-H₂ collision systems at binary collision energies of a few eV. It was confirmed that the present cross section data are consistent with previous data and the values estimated by some scaling formula.

  8. Quantum computation with ``hot`` trapped ions

    SciTech Connect

    James, D.F.V.; Schneider, S. |; Milburn, G.J.

    1998-12-31

    The authors describe two methods that have been proposed to circumvent the problem of heating by external electromagnetic fields in ion trap quantum computers. Firstly the higher order modes of ion oscillation (i.e., modes other than the center-of-mass mode) have much slower heating rates, and can therefore be employed as a reliable quantum information bus. Secondly they discuss a recently proposed method combining adiabatic passage and a number-state dependent phase shift which allows quantum gates to be performed using the center-of-mass mode as the information bus, regardless of its initial state.

  9. Miniaturized GC/MS instrumentation for in situ measurements: micro gas chromatography coupled with miniature quadrupole array and paul ion trap mass spectrometers

    NASA Technical Reports Server (NTRS)

    Holland, P.; Chutjian, A.; Darrach, M.; Orient, O.

    2002-01-01

    Miniaturized chemical instrumentation is needed for in situ measurements in planetary exploration and other spaceflight applications where factors such as reduction in payload requirements and enhanced robustness are important. In response to this need, we are 'continuing to develop miniaturized GC/MS instrumentation which combines chemical separations by gas chromatography (GC) with mass spectrometry (MS) to provide positive identification of chemical compounds in complex mixtures of gases, such as those found in the International Space Station's cabin atmosphere. Our design approach utilizes micro gas chromatography components coupled with either a miniature quadrupole mass spectrometer array (QMSA) or compact, high-resolution Paul ion trap.

  10. Identification and fragmentation pathways of caffeine metabolites in urine samples via liquid chromatography with positive electrospray ionization coupled to a hybrid quadrupole linear ion trap (LTQ) and Fourier transform ion cyclotron resonance mass spectrometry and tandem mass spectrometry.

    PubMed

    Bianco, Giuliana; Abate, Salvatore; Labella, Cristiana; Cataldi, Tommaso R I

    2009-04-01

    Liquid chromatography (LC) with positive ion electrospray ionization (ESI+) coupled to a hybrid quadrupole linear ion trap (LTQ) and Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) was employed for the simultaneous determination of caffeine and its metabolites in human urine within a single chromatographic run. LC/ESI-FTICRMS led to the unambiguous determination of the molecular masses of the studied compounds without interference from other biomolecules. A systematic and comprehensive study of the mass spectral behaviour of caffeine and its fourteen metabolites by tandem mass spectrometry (MS/MS) was performed, through in-source ion trap collision-induced dissociation (CID) of the protonated molecules, [M+H](+). A retro-Diels-Alder (RDA) process along with ring-contraction reactions were the major fragmentation pathways observed during CID. The base peak of xanthine precursors originates from the loss of methyl isocyanate (CH(3)NCO, 57 Da) or isocyanic acid (HNCO, 43 Da), which in turn lose a CO unit. Also uric acid derivatives shared a RDA rearrangement as a common fragmentation process and a successive loss of CO(2) or CO. The uracil derivatives showed a loss of a ketene unit (CH(2)CO, 42 Da) from the protonated molecule along with the loss of H(2)O or CO. To assess the potential of the present method three established metabolite ratios to measure P450 CYP1A2, N-acetyltransferase and xanthine oxidase activities were evaluated by a number of identified metabolites from healthy human urine samples after caffeine intake. PMID:19260028

  11. Penning trap mass measurement of 72Br

    NASA Astrophysics Data System (ADS)

    Valverde, A. A.; Bollen, G.; Cooper, K.; Eibach, M.; Gulyuz, K.; Izzo, C.; Morrissey, D. J.; Ringle, R.; Sandler, R.; Schwarz, S.; Sumithrarachchi, C. S.; Villari, A. C. C.

    2015-03-01

    The Low Energy Beam and Ion Trap (LEBIT) Penning trap mass spectrometer was used to perform an improved-precision mass measurement of 72Br and the low-lying isomeric state, Brm72, giving mass excesses of -59 062.2 (1.0 )keV and -58 960.9 (1.2 )keV , respectively. These values are consistent with the values from the 2012 atomic mass evaluation [Chin. Phys. C 36, 1603 (2012), 10.1088/1674-1137/36/12/003] and the Nubase2012 evaluation of nuclear properties [Chin. Phys. C 36, 1157 (2012), 10.1088/1674-1137/36/12/001]. The uncertainties on the mass of the ground state and isomeric state have been reduced by a factor of seven.

  12. A cooler Penning trap for the TITAN mass measurement facility

    SciTech Connect

    Chowdhury, U.; Kootte, B.; Good, M.; Lascar, D.; Schultz, B. E.; Dilling, J.; Gwinner, G.

    2015-01-09

    The TITAN facility at TRIUMF makes use of highly charged ions, charge-bred in an electron beam ion trap, to carry out accurate mass measurements on radioactive isotopes. We report on our progress to develop a cooler Penning trap, CPET, which aims at reducing the energy spread of the ions to ≈ 1 eV/charge prior to injection into the mass measurement trap. In off-line mode, we can now trap electron plasmas for minutes, and we observe the damping of the m = 1 diocotron plasma mode within ≈ 2 s.

  13. Reducing Space Charge Effects in a Linear Ion Trap by Rhombic Ion Excitation and Ejection

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaohua; Wang, Yuzhuo; Hu, Lili; Guo, Dan; Fang, Xiang; Zhou, Mingfei; Xu, Wei

    2016-07-01

    Space charge effects play important roles in ion trap operations, which typically limit the ion trapping capacity, dynamic range, mass accuracy, and resolving power of a quadrupole ion trap. In this study, a rhombic ion excitation and ejection method was proposed to minimize space charge effects in a linear ion trap. Instead of applying a single dipolar AC excitation signal, two dipolar AC excitation signals with the same frequency and amplitude but 90° phase difference were applied in the x- and y-directions of the linear ion trap, respectively. As a result, mass selective excited ions would circle around the ion cloud located at the center of the ion trap, rather than go through the ion cloud. In this work, excited ions were then axially ejected and detected, but this rhombic ion excitation method could also be applied to linear ion traps with ion radial ejection capabilities. Experiments show that space charge induced mass resolution degradation and mass shift could be alleviated with this method. For the experimental conditions in this work, space charge induced mass shift could be decreased by ~50%, and the mass resolving power could be improved by ~2 times at the same time.

  14. Cryogenic ion trapping systems with surface-electrode traps.

    PubMed

    Antohi, P B; Schuster, D; Akselrod, G M; Labaziewicz, J; Ge, Y; Lin, Z; Bakr, W S; Chuang, I L

    2009-01-01

    We present two simple cryogenic rf ion trap systems in which cryogenic temperatures and ultra high vacuum pressures can be reached in as little as 12 h. The ion traps are operated either in a liquid helium bath cryostat or in a low vibration closed cycle cryostat. The fast turn around time and availability of buffer gas cooling made the systems ideal for testing surface-electrode ion traps. The vibration amplitude of the closed cycled cryostat was found to be below 106 nm. We evaluated the systems by loading surface-electrode ion traps with (88)Sr(+) ions using laser ablation, which is compatible with the cryogenic environment. Using Doppler cooling we observed small ion crystals in which optically resolved ions have a trapped lifetime over 2500 min.

  15. The trapped mercury ion frequency standard

    NASA Technical Reports Server (NTRS)

    Mcguire, M. D.

    1977-01-01

    Singly ionized mercury atoms have a structure similar to neutral alkali atoms. They can be maintained as ions for very long times in an RF quadrupole ion trap. Thus, their ground state hyperfine structure can be used to make a frequency standard using optical pumping techniques similar to the well-known rubidium standard. The mass 199 isotope of mercury has an ionic hyperfine structure of 40.5 GHz. In a trap system a linewidth of 10 Hz has been measured. An expression is presented for the short-term stability of a proposed mercury standard as set by the achieved signal to noise ratio. There is prospect of further improvement. Long-term stability is affected by second order doppler effect, and by pressure, light, and Stark shifts. However, these appear either sufficiently small or sufficiently controlable that the proposed mercury ion standard would be competitive with existing standards.

  16. Rapid method for the determination of non-steroidal anti-inflammatory drugs in animal tissue by liquid chromatography-mass spectrometry with ion-trap detector.

    PubMed

    Igualada, Carmen; Moragues, Francisco; Pitarch, Jorge

    2007-03-14

    A rapid and new liquid chromatography-mass spectrometry with ion-trap detection method for the determination of meloxicam (MLX), flunixin meglumine (FLU), carprofen (CPF), and tolfenamic acid (TOLF) in animal tissue is described. MRLs between 10 and 500 microg kg(-1) in muscle and between 65 and 1000 microg kg(-1) in liver, from different animal species have been established in the EU for these compounds. After chemical hydrolysis, an organic extraction from homogenised tissue was performed. Final extract was injected in a liquid chromatograph with an ion-trap mass spectrometer with electrospray interface. Four identification points (one precursor and two product ions) and a minimum of one ion ratio was monitored for each compound. For quantitative purposes flunixin-D3 (FLU-D3) was used as internal standard. The method was validated using fortified blank muscle and liver from different animal species according to the 2002/657/EC European decision criteria. The decision limits (CCalpha) and detection capabilities (CCbeta) were determined and their values were at concentrations near the MRL for each substance.

  17. Rapid separation and identification of furocoumarins in Angelica dahurica by high-performance liquid chromatography with diode-array detection, time-of-flight mass spectrometry and quadrupole ion trap mass spectrometry.

    PubMed

    Zhang, Hai; Gong, Chungui; Lv, Lei; Xu, Yuanjie; Zhao, Liang; Zhu, Zhenyu; Chai, Yifeng; Zhang, Guoqing

    2009-07-01

    High-performance liquid chromatography with diode-array detection (HPLC/DAD), time-of-flight mass spectrometry (HPLC/TOFMS) and quadrupole ion trap mass spectrometry (HPLC/QITMS) were used for separation, identification and structural analysis of furocoumarins in Angelica dahurica. Two furocoumarins (imperatorin and isoimperatorin) in Angelica dahurica extract were identified unambiguously by comparing their relative retention times, characteristic ultraviolet information and accurate mass measurement. A formula database of known furocoumarins in Angelica dahurica was established, against which the other 21 furocoumarins were identified effectively based on the accurate extract masses and formulae acquired by HPLC/TOFMS. In order to distinguish the isomers, multi-stage mass spectrometry (MSn, ion trap mass spectrometry) was used. General fragmentation behavior of the furocoumarins in the ion trap mass spectrometer was studied by the two furocoumarin standards, and their fragmentation rules in MS(n) spectra were summarized. These deduced fragmentation rules of furocoumarins were successfully implemented in distinguishing the three groups of isomers in Angelica dahurica by HPLC/QITMS. By using the three different analytical techniques, 23 furocoumarins in Angelica dahurica were tentatively identified within 30 min. Finally, HPLC/TOFMS fingerprints of Angelica dahurica were established by which it can be concluded that a rapid and effective method based on the three analytical techniques for identification of chemical components was established. This can provide help for further quality control of Angelica dahurica and pharmacology mechanism study of furocoumarins in Angelica dahurica.

  18. Rapid screening and characterization of drug metabolites using multiple ion monitoring dependent product ion scan and postacquisition data mining on a hybrid triple quadrupole-linear ion trap mass spectrometer.

    PubMed

    Yao, Ming; Ma, Li; Duchoslav, Eva; Zhu, Mingshe

    2009-06-01

    Multiple ion monitoring (MIM)-dependent acquisition with a triple quadrupole-linear ion trap mass spectrometer (Q-trap) was previously developed for drug metabolite profiling. In the analysis, multiple predicted metabolite ions are monitored in both Q1 and Q3 regardless of their fragmentations. The collision energy in Q2 is set to a low value to minimize fragmentation. Once an expected metabolite is detected by MIM, enhanced product ion (EPI) spectral acquisition of the metabolite is triggered. To analyze in vitro metabolites, MIM-EPI retains the sensitivity and selectivity similar to that of multiple reaction monitoring (MRM)-EPI in the analysis of in vitro metabolites. Here we present an improved approach utilizing MIM-EPI for data acquisition and multiple data mining techniques for detection of metabolite ions and recovery of their MS/MS spectra. The postacquisition data processing tools included extracted ion chromatographic analysis, product ion filtering and neutral loss filtering. The effectiveness of this approach was evaluated by analyzing oxidative metabolites of indinavir and glutathione (GSH) conjugates of clozapine and 4-ethylphenol in liver microsome incubations. Results showed that the MIM-EPI-based data mining approach allowed for comprehensive detection of metabolites based on predicted protonated molecules, product ions or neutral losses without predetermination of the parent drug MS/MS spectra. Additionally, it enabled metabolite detection and MS/MS acquisition in a single injection. This approach is potentially useful in high-throughout screening of metabolic soft spots and reactive metabolites at the drug discovery stage.

  19. The development of a data system for a combination of liquid chromatography or capillary electrophoresis with an ion trap storage/reflectron time-of-flight mass detector.

    PubMed

    Qian, M G; Wu, J T; Parus, S; Lubman, D M

    1996-01-01

    A data system based upon a 200 MHz transient recorder interface card in a Pentium PC computer is demonstrated for on-line analysis of microbore high-performance liquid chromatography (HPLC), capillary HPLC and capillary electrophoresis (CE) separations using a fast and sensitive ion-trap storage/reflectron time-of-flight mass spectrometric detector (IT-reTOFMS). Under the control of a user-written program, the system is capable of conducting the data acquisition and storage for a minimum of 30 min, at rates exceeding 10 Hz, of individual mass spectra containing 16,000 data points having 10 nsec resolution. The capability is mainly attributed to the use of a data reduction scheme in which only mass intensities higher than a preset threshold are saved as indexed flight-time/intensity pairs. This produces a typical reduction ratio of 30:1 in data set size, yielding faster storage with smaller file size, and permits the complete set of mass spectra to be held in the computer's memory. In addition, the data system is capable of displaying, for real-time evaluation of the analysis, each individual mass spectrum and the total-ion chromatogram. Further, the selected-ion chromatograms of given masses and a 3-dimensional topographic map describing a separation process can be rapidly generated from the collected data for the unambiguous and high fidelity identification of target analytes in a complex mixture.

  20. High-throughput walkthrough detection portal for counter terrorism: detection of triacetone triperoxide (TATP) vapor by atmospheric-pressure chemical ionization ion trap mass spectrometry.

    PubMed

    Takada, Yasuaki; Nagano, Hisashi; Suzuki, Yasutaka; Sugiyama, Masuyuki; Nakajima, Eri; Hashimoto, Yuichiro; Sakairi, Minoru

    2011-09-15

    With the aim of improving security, a high-throughput portal system for detecting triacetone triperoxide (TATP) vapor emitted from passengers and luggage was developed. The portal system consists of a push-pull air sampler, an atmospheric-pressure chemical ionization (APCI) ion source, and an explosives detector based on mass spectrometry. To improve the sensitivity of the explosives detector, a novel linear ion trap mass spectrometer with wire electrodes (wire-LIT) is installed in the portal system. TATP signals were clearly obtained 2 s after the subject under detection passed through the portal system. Preliminary results on sensitivity and throughput show that the portal system is a useful tool for preventing the use of TATP-based improvised explosive devices by screening persons in places where many people are coming and going. PMID:21818804

  1. Simultaneous doping analysis of main urinary metabolites of anabolic steroids in horse by ion-trap gas chromatography-tandem mass spectrometry.

    PubMed

    Yamada, Masayuki; Aramaki, Sugako; Kurosawa, Masahiko; Kijima-Suda, Isao; Saito, Koichi; Nakazawa, Hiroyuki

    2008-09-01

    The use of anabolic steroids in racehorses is strictly regulated. We have developed a method for the simultaneous analysis of 11 anabolic steroids: fluoxymesterone, 17alpha-methyltestosterone, mestanolone, methandienone, methandriol, oxymetholone, boldenone, furazabol, methenolone, nandrolone, and stanozolol, for possible application to a doping test in racehorses. We selected 15 kinds of target substances for a doping test from the main metabolites of these anabolic steroids, and established a method for simultaneous analysis. Urine was hydrolyzed and subjected to solid-phase extraction. Then, the residue from the extracts was derivatized by trimethylsilylation. The derivatized samples were subjected to ion-trap gas chromatography-tandem mass spectrometry, and their mass chromatograms and product ion spectra were obtained. The limit of detection of the target substances was 5-50 ng/mL, and the mean recovery and coefficient of variation were 71.3-104.8% and 1.1-9.5%, respectively.

  2. Profiling of phenolic constituents in Polygonum multiflorum Thunb. by combination of ultra-high-pressure liquid chromatography with linear ion trap-Orbitrap mass spectrometry.

    PubMed

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

    2013-05-31

    A simple and effective method was developed for characterization of phenolic constituents in the roots of Polygonum multiflorum by combination of ultra-high-pressure liquid chromatography with linear ion trap-Orbitrap tandem mass spectrometry (UHPLC-LTQ-Orbitrap). Stilbenes, anthraquinones, tannins and naphthalenes were differentiated by diagnostic fragment ions with accurate mass measurements and characteristic fragmentation pathways. Based on the proposed strategy, fifty-nine constituents were characterized or tentatively identified, of which twenty-two constituents were the first to be reported in P. multiflorum and twelve compounds were characterized as potential new compounds. The identification and structure elucidation of these chemicals provided essential data for further phytochemical studies and quality control of P. multiflorum. The results also demonstrated that our novel method can be extended to screen and characterize other phenolic constituents and their metabolites in botanical extracts.

  3. An improved linear ion trap physics package

    NASA Technical Reports Server (NTRS)

    Prestage, J. D.

    1993-01-01

    This article describes an improvement in the architecture of the physics package used in the Linear Ion Trap (LIT)-based frequency standard recently developed at JPL. This new design is based on the observation that ions can be moved along the axis of an LIT by applied dc voltages. The state selection and interrogation region can be separated from the more critical microwave resonance region where the multiplied local oscillator signal is compared with the stable atomic transition. This separation relaxes many of the design constraints of the present units. Improvements include increased frequency stability and a substantial reduction in size, mass, and cost of the final frequency standard.

  4. Metabonomic Study of Biochemical Changes in Human Hair of Heroin Abusers by Liquid Chromatography Coupled with Ion Trap-Time of Flight Mass Spectrometry.

    PubMed

    Xie, Pu; Wang, Tie-jie; Yin, Guo; Yan, Yan; Xiao, Li-he; Li, Qing; Bi, Kai-shun

    2016-01-01

    Hair analysis is with the advantage of non-invasive collection and long surveillance window. The present study employed a sensitive and reliable liquid chromatography coupled with ion trap-time of flight mass spectrometry method to study the metabonomic characters in the hair of 58 heroin abusers and 72 non-heroin abusers. Results indicated that certain endogenous metabolites, such as sorbitol and cortisol, were accelerated, and the level of arachidonic acid, glutathione, linoleic acid, and myristic acid was decreased in hair of heroin abusers. The metabonomic study is helpful for further understanding of heroin addiction and clinical diagnosis. PMID:26445826

  5. Metabonomic Study of Biochemical Changes in Human Hair of Heroin Abusers by Liquid Chromatography Coupled with Ion Trap-Time of Flight Mass Spectrometry.

    PubMed

    Xie, Pu; Wang, Tie-jie; Yin, Guo; Yan, Yan; Xiao, Li-he; Li, Qing; Bi, Kai-shun

    2016-01-01

    Hair analysis is with the advantage of non-invasive collection and long surveillance window. The present study employed a sensitive and reliable liquid chromatography coupled with ion trap-time of flight mass spectrometry method to study the metabonomic characters in the hair of 58 heroin abusers and 72 non-heroin abusers. Results indicated that certain endogenous metabolites, such as sorbitol and cortisol, were accelerated, and the level of arachidonic acid, glutathione, linoleic acid, and myristic acid was decreased in hair of heroin abusers. The metabonomic study is helpful for further understanding of heroin addiction and clinical diagnosis.

  6. Use of solid-phase microextraction for the detection of acetic acid by ion-trap gas chromatography-mass spectrometry and application to indoor levels in museums.

    PubMed

    Godoi, Ana F L; Van Vaeck, Luc; Van Grieken, René

    2005-03-01

    A simple and efficient method using solid-phase microextraction (SPME) and gas chromatography-ion trap mass spectrometry (GC-ITMS) was developed for the analysis of acetic acid in air. The choice of the SPME fibre revealed to be critical as well as the sampling and desorption time. A dilution vessel was used for calibration. The precision of the method was found to be 4.7% relative standard deviation (RSD) and the detection limit 5.7 microg m(-3). The SPME-GC-MS technique was applied to the analysis of acetic acid in museum atmospheres.

  7. How far can ion trap miniaturization go? Parameter scaling and space-charge limits for very small cylindrical ion traps.

    PubMed

    Tian, Yuan; Higgs, Jessica; Li, Ailin; Barney, Brandon; Austin, Daniel E

    2014-03-01

    A broad effort is underway to make radiofrequency (RF) ion trap mass spectrometers small enough for portable chemical analysis. A variety of trap geometries and fabrication approaches are under development from several research groups. A common issue is the reduced trapping capacity in smaller traps, with the associated reduction in sensitivity. This article explores the key variables that scale with trap size including RF voltage, frequency, electrical capacitance, power and pseudopotential well depth. High-field electric breakdown constrains the maximum RF voltages used in smaller ion traps. Simulations show the effects of space charge and the limits of trapping capacity as a function of trap dimensions for cylindrical ion traps down to the micrometer level. RF amplitudes that scale as the 1/3, 1/2 and 2/3 power of trap radius, r0, were studied. At a fixed level of performance, the number of analyzable ions scales as r0(n), with n ranging from 1.55 to 1.75 depending on the choice of voltage scaling. The implications for miniaturized ion trap mass spectrometry are discussed. PMID:24619549

  8. [Rapid screening and confirming carcinogenic banned azo colorants in textiles by high performance liquid chromatography-linear ion trap/orbitrap high-resolution mass spectrometry].

    PubMed

    Yun, Huan; Liu, Xin; Wang, Jing; Yan, Hua; Cui, Fengyun; Zhang, Zhaohui

    2013-09-01

    A method of high performance liquid chromatography-linear ion trap/orbitrap highresolution mass spectrometry (HPLC-LTP/Orbitrap MS) was ued to screen and confirm-banned azo colorants in textiles rapidly. The analytes were reduced to carcinogenic aromatic amines with sodium dithionite in citrate buffer solution. The reduced solution was extracted bydiatomite, and loadd onto an Acquity UPLC BEH C18 column (50 mm x 2.1 MM. 1.7 microm) with a gradient elution of methanol and 0.1% (v/v) methane acid aqueous solution, and finally detected by linear ion trap/orbitrap high-resolution mass spectrometry in positive ESI mode. In mass spectrometry method, the MS spectrum of high-resolution and the collision induced dissociation (CID) spectrum of data-dependent scan mode were used for screening analysis and conformation, respectively. The calibration curves showed a good linearity in the range of 0.05 -2.00 mg/b, and the correlation coefficients (r) were higher than 0.99. By detecting spiked samples, the limits of quantification were 0.08 mg/kg for all the residues and the recoveries were in the range of 65.5% - 111.5% with the relative standard deviations (RSDs) between 0.87% and 2.49%. The results indicate that the method is simple, rapid, sensitive and suitable for the qualitative and quantitative analysis of carcinogenic aromatic amines in textiles.

  9. Scalable Designs for Planar Ion Trap Arrays

    NASA Astrophysics Data System (ADS)

    Slusher, R. E.

    2007-03-01

    Recent progress in quantum operations with trapped ion qubits has been spectacular for qubit counts up to approximately ten ions. Two qubit quantum gates, quantum error correction, simple quantum algorithms and entanglement of up to 8 qubits have been demonstrated by groups including those at NIST, University of Michigan, University of Innsbruck and Oxford. Interesting problems in quantum information processing including quantum simulations of condensed matter systems and quantum repeaters for long distance quantum communication systems require hundreds or thousands of qubits. Initial designs for an ion trap ``Quantum CCD'' using spatially multiplexed planar ion traps as well as initial experiments using planar ion traps are promising routes to scaling up the number of trapped ions to more interesting levels. We describe designs for planar ion traps fabricated using silicon VLSI techniques. This approach allows the control voltages required for the moving and positioning the ions in the array to be connected vertically through the silicon substrate to underlying CMOS electronics. We have developed techniques that allow the ion trap structures to be fabricated monolithically on top of the CMOS electronics. The planar traps have much weaker trapping depths than the more conventional multi-level traps. However, the trap depths are still adequate for trapping hot ions from many ion sources. The planar traps also involve more complex configurations for laser cooling and micromotion control. Initial solutions to these problems will be presented. Laser access to the ions can be provided by laser beams grazing the trap surface or by using vertical slots through the trap chip. We will also discuss limits imposed by power dissipation and ion transport through trap junctions (e.g. crosses and Ys). We have fabricated these VLSI based traps in a number of configurations. Initial fabrication and packaging challenges will be discussed. D. Kielpinski, C. Monroe, and D.J. Wineland

  10. Quantitation of lysergic acid diethylamide in urine using atmospheric pressure matrix-assisted laser desorption/ionization ion trap mass spectrometry.

    PubMed

    Cui, Meng; McCooeye, Margaret A; Fraser, Catharine; Mester, Zoltán

    2004-12-01

    A quantitative method was developed for analysis of lysergic acid diethylamide (LSD) in urine using atmospheric pressure matrix-assisted laser desorption/ionization ion trap mass spectrometry (AP MALDI-ITMS). Following solid-phase extraction of LSD from urine samples, extracts were analyzed by AP MALDI-ITMS. The identity of LSD was confirmed by fragmentation of the [M + H](+) ion using tandem mass spectrometry. The quantification of LSD was achieved using stable-isotope-labeled LSD (LSD-d(3)) as the internal standard. The [M + H](+) ion fragmented to produce a dominant fragment ion, which was used for a selected reaction monitoring (SRM) method for quantitative analysis of LSD. SRM was compared with selected ion monitoring and produced a wider linear range and lower limit of quantification. For SRM analysis of samples of LSD spiked in urine, the calibration curve was linear in the range of 1-100 ng/mL with a coefficient of determination, r(2), of 0.9917. This assay was used to determine LSD in urine samples and the AP MALDI-MS results were comparable to the HPLC/ ESI-MS results.

  11. Characterization of diacylglycerol isomers in edible oils using gas chromatography-ion trap electron ionization mass spectrometry.

    PubMed

    Zhu, Hanjiang; Clegg, Michael S; Shoemaker, Charles F; Wang, Selina C

    2013-08-23

    Verifying the authenticity of edible oils is of international concern. A new quality control standard for olive oil has been proposed that relates the ratio of 1,2-diacylglycerol (DAG) to 1,3-DAG to sensory aspects of olive oil. DAGs and their isomers are difficult to quantitate and characterize by Flame Ionization Gas Chromatography (GC-FID) due to the lack of suitable standards. Mass detectors offer the advantage of providing structural detail to the eluding DAG(s), thus removing ambiguity to the identification of both resolved and unresolved DAGs in GC chromatograms. In this study, a GC Electron Ionization Mass Spectrometry (GC-EI-MS) method was developed to determine the fatty acid composition and molecular structure of trimethylsilyl (TMS) derivatized DAGs present in edible oils. Twenty-two species of DAG isomers were identified in refined coconut oil and unrefined olive oil utilizing signature fragment ions, [M-15](+), [M-89](+), [M-RCO2](+), [RCO2+58](+) and [M-RCO2CH2](+). The [M-RCO2CH2](+) ion is considered the key diagnostic ion to distinguish between DAG positional isomers. MS/MS spectra of [M-RCO2](+) and [M-15](+) ions obtained from commercial standards containing both 1,2- and 1,3-DAG isomers were used as a model system to confirm the identification of DAG isomers in natural products. Furthermore, a number of reaction mechanisms are proposed to explain the formation of the most abundant mass fragments of DAGs and their isomers.

  12. Ion temperature gradient driven turbulence with strong trapped ion resonance

    SciTech Connect

    Kosuga, Y.; Itoh, S.-I.; Diamond, P. H.; Itoh, K.; Lesur, M.

    2014-10-15

    A theory to describe basic characterization of ion temperature gradient driven turbulence with strong trapped ion resonance is presented. The role of trapped ion granulations, clusters of trapped ions correlated by precession resonance, is the focus. Microscopically, the presence of trapped ion granulations leads to a sharp (logarithmic) divergence of two point phase space density correlation at small scales. Macroscopically, trapped ion granulations excite potential fluctuations that do not satisfy dispersion relation and so broaden frequency spectrum. The line width from emission due only to trapped ion granulations is calculated. The result shows that the line width depends on ion free energy and electron dissipation, which implies that non-adiabatic electrons are essential to recover non-trivial dynamics of trapped ion granulations. Relevant testable predictions are summarized.

  13. [Screening and confirmation of 24 hormones in cosmetics by ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry].

    PubMed

    Li, Zhaoyong; Wang, Fengmei; Niu, Zengyuan; Luo, Xin; Zhang, Gang; Chen, Junhui

    2014-05-01

    A method of ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry (UPLC-LTQ/Orbitrap MS) was established to screen and confirm 24 hormones in cosmetics. Various cosmetic samples were extracted with methanol. The extract was loaded onto a Waters ACQUITY UPLC BEH C18 column (50 mm x 2.1 mm, 1.7 microm) using a gradient elution of acetonitrile/water containing 0.1% (v/v) formic acid for the separation. The accurate mass of quasi-molecular ion was acquired by full scanning of electrostatic field orbitrap. The rapid screening was carried out by the accurate mass of quasi-molecular ion. The confirmation analysis for targeted compounds was performed with the retention time and qualitative fragments obtained by data dependent scan mode. Under the optimal conditions, the 24 hormones were routinely detected with mass accuracy error below 3 x 10(-6) (3 ppm), and good linearities were obtained in their respective linear ranges with correlation coefficients higher than 0.99. The LODs (S/N = 3) of the 24 compounds were < or = 10 microg/kg, which can meet the requirements for the actual screening of cosmetic samples. The developed method was applied to screen the hormones in 50 cosmetic samples. The results demonstrate that the method is a useful tool for the rapid screening and identification of the hormones in cosmetics.

  14. Atomic Clock Based On Linear Ion Trap

    NASA Technical Reports Server (NTRS)

    Prestage, John D.; Dick, G. John

    1992-01-01

    Highly stable atomic clock based on excitation and measurement of hyperfine transition in 199Hg+ ions confined in linear quadrupole trap by radio-frequency and static electric fields. Configuration increases stability of clock by enabling use of enough ions to obtain adequate signal while reducing non-thermal component of motion of ions in trapping field, reducing second-order Doppler shift of hyperfine transition. Features described in NPO-17758 "Linear Ion Trap for Atomic Clock." Frequency standard based on hyperfine transition described in NPO-17456, "Trapped-Mercury-Ion Frequency Standard."

  15. Determination of nitrosamines in water by gas chromatography/chemical ionization/selective ion trapping mass spectrometry.

    PubMed

    Pozzi, Romina; Bocchini, Paola; Pinelli, Francesca; Galletti, Guido C

    2011-04-01

    A gas chromatography/mass spectrometry (GC/MS) method for determination of nine N-nitrosamines (NAs) in water is described. Two ionization modes, electron impact (EI) and chemical ionization (CI) with methanol, as well as different ion analysis techniques, i.e. full scan, selected ion storage (SIS) and tandem mass spectrometry (MS/MS) were tested. Chemical ionization followed by SIS resulted the mass spectrometric method of choice, with detection limits in the range of 1-2ng/L. Solid Phase Extraction (SPE) with coconut charcoal cartridges was applied to extract NAs from real samples, according EPA Method 521. Drinking water samples were collected from seven surface- and two groundwater treatment plants. Three surface water treatment plants were sampled before and after addition of O(3)/ClO(2) to observe the effect of disinfection on NAs' formation. N-nitrosodiethylamine (NDEA), n-nitrosodipropylamine (NDPA), n-nitrosomorpholine (NMOR) and n-nitrosodibutylamine (NDBA) were found up to concentrations exceeding three times the risk level of 10ng/L set by the California Department of Public Health. Because dermal adsorption has been recently indicated as a new contamination route of exposure to NAs for people who practice swimming activity, water samples from five swimming pools in the Bologna (Italy) area were collected. N-nitrosopyrrolidine (NPYR) was detected in all samples at concentrations larger than 50ng/L, likely as a disinfection by-product from the amino acid precursor proline, a main constituent of skin collagen.

  16. METHOD AND APPARATUS FOR TRAPPING IONS IN A MAGNETIC FIELD

    DOEpatents

    Luce, J.S.

    1962-04-17

    A method and apparatus are described for trapping ions within an evacuated container and within a magnetic field utilizing dissociation and/or ionization of molecular ions to form atomic ions and energetic neutral particles. The atomic ions are magnetically trapped as a result of a change of charge-to- mass ratio. The molecular ions are injected into the container and into the path of an energetic carbon arc discharge which dissociates and/or ionizes a portion of the molecular ions into atomic ions and energetic neutrals. The resulting atomic ions are trapped by the magnetic field to form a circulating beam of atomic ions, and the energetic neutrals pass out of the system and may be utilized in a particle accelerator. (AEC)

  17. An integrated approach for profiling oxidative metabolites and glutathione adducts using liquid chromatography coupled with ultraviolet detection and triple quadrupole-linear ion trap mass spectrometry.

    PubMed

    Chen, Guiying; Cheng, Zhongzhe; Zhang, Kerong; Jiang, Hongliang; Zhu, Mingshe

    2016-09-10

    The use of liquid chromatography (LC) coupled with triple quadrupole linear ion trap (Qtrap) mass spectrometry (MS) for both quantitative and qualitative analysis in drug metabolism and pharmacokinetic studies is of great interest. Here, a new Qtrap-based analytical methodology for simultaneous detection, structural characterization and semi-quantitation of in vitro oxidative metabolites and glutathione trapped reactive metabolites was reported. In the current study, combined multiple ion monitoring and multiple reaction monitoring were served as surveying scans to trigger product ion spectral acquisition of oxidative metabolites and glutathione adduct, respectively. Then, detection of metabolites and recovery of their MS/MS spectra were accomplished using multiple data mining approaches. Additionally, on-line ultraviolet (UV) detection was employed to determine relative concentrations of major metabolites. Analyses of metabolites of clozapine and nomifensine in rat liver microsomes not only revealed multiple oxidative metabolites and glutathione adducts, but also identified their major oxidative metabolism and bioactivation pathways. The results demonstrated that the LC/UV/MS method enabled Qtrap to perform the comprehensive profiling of oxidative metabolites and glutathione adducts in vitro. PMID:27497649

  18. An integrated approach for profiling oxidative metabolites and glutathione adducts using liquid chromatography coupled with ultraviolet detection and triple quadrupole-linear ion trap mass spectrometry.

    PubMed

    Chen, Guiying; Cheng, Zhongzhe; Zhang, Kerong; Jiang, Hongliang; Zhu, Mingshe

    2016-09-10

    The use of liquid chromatography (LC) coupled with triple quadrupole linear ion trap (Qtrap) mass spectrometry (MS) for both quantitative and qualitative analysis in drug metabolism and pharmacokinetic studies is of great interest. Here, a new Qtrap-based analytical methodology for simultaneous detection, structural characterization and semi-quantitation of in vitro oxidative metabolites and glutathione trapped reactive metabolites was reported. In the current study, combined multiple ion monitoring and multiple reaction monitoring were served as surveying scans to trigger product ion spectral acquisition of oxidative metabolites and glutathione adduct, respectively. Then, detection of metabolites and recovery of their MS/MS spectra were accomplished using multiple data mining approaches. Additionally, on-line ultraviolet (UV) detection was employed to determine relative concentrations of major metabolites. Analyses of metabolites of clozapine and nomifensine in rat liver microsomes not only revealed multiple oxidative metabolites and glutathione adducts, but also identified their major oxidative metabolism and bioactivation pathways. The results demonstrated that the LC/UV/MS method enabled Qtrap to perform the comprehensive profiling of oxidative metabolites and glutathione adducts in vitro.

  19. Trapped-Mercury-Ion Frequency Standard

    NASA Technical Reports Server (NTRS)

    Prestage, John D.; Dick, G. John; Maleki, Lutfollah

    1991-01-01

    Report describes principle of operation, design, and results of initial measurements on trapped-mercury-ion frequency-standard apparatus at NASA's Jet Propulsion Laboratory. New frequency standard being developed. Based on linear ion trap described in (NPO-17758). Expected to show much better short-term frequency stability because of increased ion-storage capacity.

  20. Determination of non-ionic polyethoxylated surfactants in wastewater and river water by mixed hemimicelle extraction and liquid chromatography-ion trap mass spectrometry.

    PubMed

    Cantero, Manuel; Rubio, Soledad; Pérez-Bendito, Dolores

    2005-03-01

    The capability of hemimicelles-based solid phase extraction (SPE)/liquid chromatography/atmospheric pressure chemical ionisation in positive mode, ion trap mass spectrometry (LC/(APCl+-IT)-MS) for the concentration, separation and quantitation of non-ionic surfactants has been investigated. Concentration was based on the formation of mixed aggregates of analytes [alkylphenol ethoxylates (APE, octyl and nonyl) and alkyl ethoxylates (AE, C12-C16)] with the anionic surfactant sodium dodecyl sulphate (SDS) that is adsorbed on alumina. Parameters affecting SPE were investigated on the basis that hemimicelles are dynamic entities in equilibrium with the aqueous phase. The performance of ion trap mass spectrometry for MS and MS/MS quantitation of non-ionic homologues was assessed. Recoveries of analytes from wastewater influent and effluent and river water samples ranged between 91 and 98% and were found independent on the length of the alkyl chain under the optimised conditions. Anionic surfactants did not interfere to the levels found in environmental samples. The detection limits ranged between 14 and 111 ng/l for wastewater influent, 10 and 40 for wastewater effluent and 4 and 35 for river water, after concentration of 250, 500 and 750 ml of sample, respectively. The approach was applied to the determination of AE and APE in influent and effluent samples from four wastewater treatment plants and four river samples. The concentrations of individual non-ionic surfactants found ranged between 0.3 and 373 microg/l. PMID:15844521

  1. Extraction and Analysis of Disperse Dyes from Colored Polyester Single Fibers Using Liquid Chromatography/Linear Ion Trap Tandem Mass Spectrometry.

    PubMed

    Kato, Takao; Suzuki, Yasuhiro; Handa, Makoto

    2016-01-01

    Nine disperse dyes extracted from colored polyester threads and single fibers of manufactory-supplied textiles by using centrifugal filtration were analyzed using liquid chromatography/linear ion trap tandem mass spectrometry (LC/LIT-MS(n)). Based on diode array detector data, dimethylformamide (DMF) was found to be a more effective extraction solvent than acetonitrile/water (4:3, v/v) or methanol/water (1:1, v/v) mixtures. The precursor, [M+H](+) ions, were detected for the dyes extracted using DMF. The MS(2) and MS(3) spectra also matched those of the standard disperse dyes. Without relying on comparison clothes, disperse dyes extracted from the single fibers (5 mm in length) were successfully identified by LC/LIT-MS(n) and the custom-built database.

  2. Extraction and Analysis of Disperse Dyes from Colored Polyester Single Fibers Using Liquid Chromatography/Linear Ion Trap Tandem Mass Spectrometry.

    PubMed

    Kato, Takao; Suzuki, Yasuhiro; Handa, Makoto

    2016-01-01

    Nine disperse dyes extracted from colored polyester threads and single fibers of manufactory-supplied textiles by using centrifugal filtration were analyzed using liquid chromatography/linear ion trap tandem mass spectrometry (LC/LIT-MS(n)). Based on diode array detector data, dimethylformamide (DMF) was found to be a more effective extraction solvent than acetonitrile/water (4:3, v/v) or methanol/water (1:1, v/v) mixtures. The precursor, [M+H](+) ions, were detected for the dyes extracted using DMF. The MS(2) and MS(3) spectra also matched those of the standard disperse dyes. Without relying on comparison clothes, disperse dyes extracted from the single fibers (5 mm in length) were successfully identified by LC/LIT-MS(n) and the custom-built database. PMID:27682411

  3. New ion trap for frequency standard applications

    NASA Technical Reports Server (NTRS)

    Prestage, J. D.; Dick, G. J.; Maleki, L.

    1989-01-01

    A novel linear ion trap was designed, which permits storage of a large number of ions with reduced susceptibility to the second-order Doppler effect caused by the RF confining fields. This new trap should store about 20 times the number of ions as a conventional RF trap with no corresponding increase in second-order Doppler shift from the confining field. In addition, the sensitivity of this shift to trapping parameters, i.e., RF voltage, RF frequency, and trap size, is greatly reduced.

  4. Highly Charged Ions in Rare Earth Permanent Magnet Penning Traps

    NASA Astrophysics Data System (ADS)

    Guise, Nicholas D.; Brewer, Samuel M.; Tan, Joseph N.

    A newly constructed apparatus at the United States National Institute of Standards and Technology (NIST) is designed for the isolation, manipulation, and study of highly charged ions. Highly charged ions are produced in the NIST electron-beam ion trap (EBIT), extracted through a beamline that selects a single mass/charge species, then captured in a compact Penning trap. The magnetic field of the trap is generated by cylindrical NdFeB permanent magnets integrated into its electrodes. In a room-temperature prototype trap with a single NdFeB magnet, species including Ne10+ and N7+ were confined with storage times of order 1 second, showing the potential of this setup for manipulation and spectroscopy of highly charged ions in a controlled environment. Ion capture has since been demonstrated with similar storage times in a more-elaborate Penning trap that integrates two coaxial NdFeB magnets for improved B-field homogeneity. Ongoing experiments utilize a second-generation apparatus that incorporates this two-magnet Penning trap along with a fast time-of-flight MCP detector capable of resolving the charge-state evolution of trapped ions. Holes in the two-magnet Penning trap ring electrode allow for optical and atomic beam access. Possible applications include spectroscopic studies of one-electron ions in Rydberg states, as well as highly charged ions of interest in atomic physics, metrology, astrophysics, and plasma diagnostics.

  5. Stability studies of propoxur herbicide in environmental water samples by liquid chromatography-atmospheric pressure chemical ionization ion-trap mass spectrometry.

    PubMed

    Sun, Lei; Lee, Hian Kee

    2003-10-01

    Liquid chromatography-atmospheric pressure ionization ion-trap mass spectrometry has been investigated for the analysis of polar pesticides in water. The degradation behavior of propoxur, selected as a model pesticide belonging to the N-methylcarbamate group, in various aqueous matrices (Milli-Q water, drinking water, rain water, seawater and river water) was investigated. Two interfaces of atmospheric pressure ionization, atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI), were compared during the study. Propoxur and its transformation product (N-methylformamide) were best ionized as positive ions with both APCI and ESI, while another transformation product (2-isopropoxyphenol) yielded stronger signals as negative ions only with APCI. In addition, the effects of various pH, matrix type and irradiation sources (sunlight, darkness, indoor lighting and artificial UV lamp) on the chemical degradation (hydrolysis) were also assessed. From the kinetic studies of degradation, it was found that the half-life of propoxur was reduced from 327 to 161 h in Milli-Q water with variation of irradiation conditions from dark to sunlight exposure. Degradation rates largely increased with increasing pH. The half-life of the target compound dissolved in Milli-Q water under darkness decreased from 407 to 3 h when the pH of Milli-Q water was increased from 5 to 8.5. These suggest that hydrolysis of propoxur is light-intensity and pH-dependent. In order to mimic contaminated natural environmental waters, propoxur was spiked into real water samples at 30 microg/l. The degradation of propoxur in such water samples under various conditions were studied in detail and compared. With the ion trap run in a time-scheduled single ion monitoring mode, typical limits of detection of the instrument were in the range of 1-10 microg/l.

  6. Determination of the banned growth promoter moenomycin A in feed stuffs by liquid chromatography coupled to electrospray ion trap mass spectrometry.

    PubMed

    Gallo, Pasquale; Fabbrocino, Serena; Serpe, Luigi; Fiori, Maurizio; Civitareale, Cinzia; Stacchini, Paolo

    2010-04-15

    Flavomycin complex is an antibiotic banned in the European Union as an additive in feed stuffs. As a consequence, the monitoring programmes for official control within the Community require analysis of feeds for possible illegal use of flavomycin. A method for unambiguous identification and quantification of moenomycin A, the main pharmacologically active component of flamomycin complex, in several feeds by liquid chromatography coupled to electrospray ion trap mass spectrometry (LC/ESI-MS/MS) is herein described for the first time. The method was developed to be used as a confirmative analytical tool for the network of Italian official control laboratories; both the singly and doubly charged molecular ions were observed as precursor ions, from which four product ions were selected for both quantitative analysis and unambiguous identification of moenomycin A. The method was in-house validated for feeds in the concentration range 0.50-30.0 microg/g, according to the Regulation 882/2004/EC requirements. Mean recoveries ranging between 83.9-94.2% and relative standard deviations <23% account for method trueness and repeatability, respectively. Moreover, other analytical performance parameters, i.e. method specificity, ruggedness, the linearity of detector response, the limit of quantification (LOQ), the limit of detection (LOD), and measurement uncertainty were evaluated and reported. The ion trap LC/ESI-MS/MS method is highly selective and reliable; high drug recovery, good reproducibility and an LOQ down to 0.10 microg/g guarantee its applicability for confirmatory purposes in the official control activity in Italy. PMID:20213675

  7. Compact toroidal ion-trap design and optimization

    SciTech Connect

    Madsen, M. J.; Gorman, C. H.

    2010-10-15

    We present the design of a type of compact toroidal, or 'halo', ion trap. Such traps may be useful for mass spectrometry, studying small Coulomb cluster rings, quantum-information applications, or other quantum simulations where a ring topology is of interest. We present results from a Monte Carlo optimization of the trap design parameters using finite-element analysis simulations that minimize higher-order anharmonic terms in the trapping pseudopotential, while maintaining complete control over ion placement at the pseudopotential node in three dimensions using static bias fields. These simulations are based on a practical electrode design using readily available parts, yet can be easily scaled to any size trap with similar electrode spacings. We also derive the conditions for a crystal structure transition for two ions in the compact halo trap, the first nontrivial transition for Coulomb crystals in this geometry.

  8. Determination of nitrosamines in water by gas chromatography/chemical ionization/selective ion trapping mass spectrometry.

    PubMed

    Pozzi, Romina; Bocchini, Paola; Pinelli, Francesca; Galletti, Guido C

    2011-04-01

    A gas chromatography/mass spectrometry (GC/MS) method for determination of nine N-nitrosamines (NAs) in water is described. Two ionization modes, electron impact (EI) and chemical ionization (CI) with methanol, as well as different ion analysis techniques, i.e. full scan, selected ion storage (SIS) and tandem mass spectrometry (MS/MS) were tested. Chemical ionization followed by SIS resulted the mass spectrometric method of choice, with detection limits in the range of 1-2ng/L. Solid Phase Extraction (SPE) with coconut charcoal cartridges was applied to extract NAs from real samples, according EPA Method 521. Drinking water samples were collected from seven surface- and two groundwater treatment plants. Three surface water treatment plants were sampled before and after addition of O(3)/ClO(2) to observe the effect of disinfection on NAs' formation. N-nitrosodiethylamine (NDEA), n-nitrosodipropylamine (NDPA), n-nitrosomorpholine (NMOR) and n-nitrosodibutylamine (NDBA) were found up to concentrations exceeding three times the risk level of 10ng/L set by the California Department of Public Health. Because dermal adsorption has been recently indicated as a new contamination route of exposure to NAs for people who practice swimming activity, water samples from five swimming pools in the Bologna (Italy) area were collected. N-nitrosopyrrolidine (NPYR) was detected in all samples at concentrations larger than 50ng/L, likely as a disinfection by-product from the amino acid precursor proline, a main constituent of skin collagen. PMID:21377686

  9. Experimental demonstration of a surface-electrode multipole ion trap

    NASA Astrophysics Data System (ADS)

    Maurice, Mark; Allen, Curtis; Green, Dylan; Farr, Andrew; Burke, Timothy; Hilleke, Russell; Clark, Robert

    2015-08-01

    We report on the design and experimental characterization of a surface-electrode multipole ion trap. Individual microscopic sugar particles are confined in the trap. The trajectories of driven particle motion are compared with a theoretical model, both to verify qualitative predictions of the model and to measure the charge-to-mass ratio of the confined particle. The generation of harmonics of the driving frequency is observed as a key signature of the nonlinear nature of the trap. We remark on possible applications of our traps, including to mass spectrometry.

  10. Three-Rod Linear Ion Traps

    NASA Technical Reports Server (NTRS)

    Janik, Gary R.; Prestage, John D.; Maleki, Lutfollah

    1993-01-01

    Three-parallel-rod electrode structures proposed for use in linear ion traps and possibly for electrostatic levitation of macroscopic particles. Provides wider viewing angle because they confine ions in regions outside rod-electrode structures.

  11. Trapped Ion Optical Clocks at NPL

    SciTech Connect

    Margolis, H. S.; Barwood, G. P.; Hosaka, K.; Klein, H. A.; Lea, S. N.; Walton, B. R.; Webster, S. A.; Gill, P.; Huang, G.; Stannard, A.

    2006-11-07

    Forbidden transitions in single laser-cooled trapped ions provide highly stable and accurate references for optical frequency standards. This paper describes recent progress on strontium and ytterbium ion optical frequency standards under development at NPL.

  12. Quantum Information Processing with Trapped Ions

    NASA Astrophysics Data System (ADS)

    Roos, Christian

    Trapped ions constitute a well-isolated small quantum system that offers low decoherence rates and excellent opportunities for quantum control and measurement by laser-induced manipulation of the ions. These properties make trapped ions an attractive system for experimental investigations of quantum information processing. In the following, the basics of storing, manipulating and measuring quantum information encoded in a string of trapped ions will be discussed. Based on these techniques, entanglement can be created and simple quantum protocols like quantum teleportation be realized. This chapter concludes with a discussion of the use of entangling laser-ion interactions for quantum simulations and quantum logic spectroscopy.

  13. A selective and sensitive method for quantitation of lysergic acid diethylamide (LSD) in whole blood by gas chromatography-ion trap tandem mass spectrometry.

    PubMed

    Libong, Danielle; Bouchonnet, Stéphane; Ricordel, Ivan

    2003-01-01

    A gas chromatography-ion trap tandem mass spectrometry (GC-ion trap MS-MS) method for detection and quantitation of LSD in whole blood is presented. The sample preparation process, including a solid-phase extraction step with Bond Elut cartridges, was performed with 2 mL of whole blood. Eight microliters of the purified extract was injected with a cold on-column injection method. Positive chemical ionization was performed using acetonitrile as reagent gas; LSD was detected in the MS-MS mode. The chromatograms obtained from blood extracts showed the great selectivity of the method. GC-MS quantitation was performed using lysergic acid methylpropylamide as the internal standard. The response of the MS was linear for concentrations ranging from 0.02 ng/mL (detection threshold) to 10.0 ng/mL. Several parameters such as the choice of the capillary column, the choice of the internal standard and that of the ionization mode (positive CI vs. EI) were rationalized. Decomposition pathways under both ionization modes were studied. Within-day and between-day stability were evaluated.

  14. Performance of the Linear Ion Trap Mass Spectrometer for the Mars Organic Molecule Analyzer (MOMA) Investigation on the 2018 Exomars Rover

    NASA Technical Reports Server (NTRS)

    Arevalo, Ricardo, Jr.; Brinckerhoff, William B.; Pinnick, Veronica T.; van Amerom, Friso H. W.; Danell, Ryan M.; Li, Xiang; Getty, Stephanie; Hovmand, Lars; Atanassova, Martina; Mahaffy, Paul R.; Chu, Zhiping; Goesmann, Fred; Steininger, Harald

    2014-01-01

    The 2018 ExoMars rover mission includes the Mars Organic Molecule Analyzer (MOMA) investigation. MOMA will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from degradation derived from cosmic radiation and/or oxidative chemical reactions. When combined with the complement of instruments in the rover's Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds. The MOMA investigation is led by the Max Planck Institute for Solar System Research (MPS) with the mass spectrometer subsystem provided by NASA GSFC. MOMA's linear ion trap mass spectrometer (ITMS) is designed to analyze molecular composition of: (i) gas evolved from pyrolyzed powder samples and separated in a gas chromatograph; and, (ii) ions directly desorbed from crushed solid samples at Mars ambient pressure, as enabled by a pulsed UV laser system, fast-actuating aperture valve and capillary ion inlet. Breadboard ITMS and associated electronics have been advanced to high end-to-end fidelity in preparation for flight hardware delivery to Germany in 2015.

  15. Atomic ion clock with two ion traps, and method to transfer ions

    NASA Technical Reports Server (NTRS)

    Prestage, John D. (Inventor); Chung, Sang K. (Inventor)

    2011-01-01

    An atomic ion clock with a first ion trap and a second ion trap, where the second ion trap is of higher order than the first ion trap. In one embodiment, ions may be shuttled back and forth from one ion trap to the other by application of voltage ramps to the electrodes in the ion traps, where microwave interrogation takes place when the ions are in the second ion trap, and fluorescence is induced and measured when the ions are in the first ion trap. In one embodiment, the RF voltages applied to the second ion trap to contain the ions are at a higher frequency than that applied to the first ion trap. Other embodiments are described and claimed.

  16. Ion traps fabricated in a CMOS foundry

    SciTech Connect

    Mehta, K. K.; Ram, R. J.; Eltony, A. M.; Chuang, I. L.; Bruzewicz, C. D.; Sage, J. M. Chiaverini, J.

    2014-07-28

    We demonstrate trapping in a surface-electrode ion trap fabricated in a 90-nm CMOS (complementary metal-oxide-semiconductor) foundry process utilizing the top metal layer of the process for the trap electrodes. The process includes doped active regions and metal interconnect layers, allowing for co-fabrication of standard CMOS circuitry as well as devices for optical control and measurement. With one of the interconnect layers defining a ground plane between the trap electrode layer and the p-type doped silicon substrate, ion loading is robust and trapping is stable. We measure a motional heating rate comparable to those seen in surface-electrode traps of similar size. This demonstration of scalable quantum computing hardware utilizing a commercial CMOS process opens the door to integration and co-fabrication of electronics and photonics for large-scale quantum processing in trapped-ion arrays.

  17. A Novel Phase-Coherent Programmable Clock for High-Precision Arbitrary Waveform Generation Applied to Digital Ion Trap Mass Spectrometry

    SciTech Connect

    Koizumi, Hideya; Jatko, William Bruce; Andrews Jr, William H; Whitten, William B; Reilly, Pete

    2010-01-01

    Digital ion trap (DIT) mass spectrometry requires the ability to precisely and accurately produce waveforms. The quality of the mass spectra produced in terms of resolution and mass accuracy depend on the resolution and precision of the applied waveforms. This publication reveals a novel method for the production of arbitrary waveforms in general and then applies the method to the production of DIT waveforms. Arbitrary waveforms can be created by varying the clock frequency input to a programmable read only memory that is then input to a digital-to-analog converter (DAC). The arbitrary waveform is composed of a defined number of points that are triggered to be written after programmed numbers of clock cycles to define the arbitrary waveform. The novelty introduced here is that the direct digital synthesis (DDS) generated clock frequency can be precisely changed as the arbitrary waveform is written because we have developed a method to rapidly switch the DDS frequency exactly at the end of the output clock cycle allowing exact timing of multiple transitions to produce precise and temporally complex waveforms. Changing the frequency only at the end of the output clock cycle is a phase coherent process that permits precise timing between each point in the arbitrary waveform. The waveform generation technique was demonstrated by creating a prototype that was used to operate a digital ion trap mass spectrometer. The jitter in the phase-coherent DDS TTL output that was used as the frequency variable clock was 20 ps. This jitter represents the realizable limit of precision for waveform generation. The rectangular waveforms used to operate the mass spectrometer were created with counters that increased the jitter to 100 ps. The mass resolution achieved was 5000 at m/z = 414. This resolution corresponds to a jitter of 275 ps assuming DC fluctuations and overshoots in the waveform are insignificant. Resolution should improve with increasing mass because the waveforms have

  18. [Direct analysis of 38 polyphenols in wine by ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry].

    PubMed

    Zhang, Xieguang; Zheng, Yanjie; Zeng, Yongting; Liu, Wenli

    2015-06-01

    Wine has been described previously as a rich source of polyphenols. However, an accurate screening of its complete phenolic profile is still lacking. In the present work, the analysis of 38 polyphenols in wine using ultra high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry (UPLC-LTQ/Orbitrap MS) was explored. Wines were directly detected. The sample was loaded onto a Thermo Hypersil Gold C18 column (100 mmx 2.1 mm, 1.9 µm) using a gradient elution of acetonitrile/water containing 0. 1% (v/v) formic acid for the separation. UPLC-LTQ/Orbitrap mass spectrometer acquired full scan MS date for quantification, and data dependent MS2 product ion spectra for identification and/ or confirmation. The regression coefficients (R2) for the calibration curves (two orders of magnitude up to the lowest calibration level) in the study were ≥ 0.99. The limits of detection for the 38 compounds were 0.002-0.50 mg/kg. The average recoveries at three spiked levels were in the range of 90%-102% with the relative standard deviations (RSDs) of 0.51%-2.56%. Mass errors were always ≤ 5 ppm. This procedure was then successfully applied to the analysis of the polyphenols in wines.

  19. Petroleomic Analysis of Bio- Oils from the Fast Pyrolysis or Biomass: Laser Desorption Ionization-Linear Ion Trap-Orbitrap mass Spectrometry Approach

    SciTech Connect

    Smith, Erica A.; Lee, Young Jin

    2010-08-23

    Fast pyrolysis of biomass produces bio-oils that can be upgraded into biofuels. Despite similar physical properties to petroleum, the chemical properties of bio-oils are quite different and their chemical compositions, particularly those of non-volatile compounds, are not well-known. Here, we report the first time attempt at analyzing bio-oils using high-resolution mass spectrometry (MS), which employed laser desorption ionization-linear ion trap-Orbitrap MS. Besides a few limitations, we could determine chemical compositions for over 100 molecular compounds in a bio-oil sample produced from the pyrolysis of a loblolly pine tree. These compounds consist of 3-6 oxygens and 9-17 double-bond equivalents (DBEs). Among those, O{sub 4} compounds with a DBE of 9-13 were most abundant. Unlike petroleum oils, the lack of nearby molecules within a {+-}2 Da mass window for major components enabled clear isolation of precursor ions for subsequent MS/MS structural investigations. Petroleomic analysis and a comparison to low-mass components in hydrolytic lignin suggest that they are dimers and trimers of depolymerized lignin.

  20. [Determination of free carcinogenic aromatic amines in textiles by ultra-performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry].

    PubMed

    Ye, Xiwen; Peng, Yan; Niu, Zengyuan; Gao, Yonggang; Luo, Xin; Zou, Li

    2015-04-01

    A method of ultra-performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry (UPLC-LTQ/Orbitrap MS) was used to determine 24 free carcinogenic aromatic amines in textiles. The main factors influencing the method, including the extraction solvent, the extraction temperature and the extraction time, were optimized. Under the optimized experimental conditions, the analytes were extracted by dichloromethane for 10 min and loaded into a ZORBAX SB-C18 column (150 mm x 2.1 mm, 5 µm) with a gradient elution of methanol and 0.1% aqueous formic acid solution, and finally detected by LTQ/Orbitrap MS. The screening and quantitative analysis were carried out by the accurate mass of quasi-molecular ion and the peak in extracted chromatogram with accurate mass respectively. The correlation coefficients (R2) were higher than 0.99. The recoveries were 87.8%-105.6% with the RSDs were 1.6%-3.4%. The limits of detection were 0.5-1 µg/kg, and the limits of quantification were 1.5-3 µg/kg. The proposed method was applied to 14 textile samples containing spandex. 4,4'-Diaminodiphenylmethane was determined in five samples and the contents were 0.21-25.6 mg/kg. The results indicate that the developed method is a simple, efficient, precise and reliable technique for the determination of free carcinogenic aromatic amines in textiles.

  1. Cryptography, quantum computation and trapped ions

    SciTech Connect

    Hughes, Richard J.

    1998-03-01

    The significance of quantum computation for cryptography is discussed. Following a brief survey of the requirements for quantum computational hardware, an overview of the ion trap quantum computation project at Los Alamos is presented. The physical limitations to quantum computation with trapped ions are analyzed and an assessment of the computational potential of the technology is made.

  2. Characteristics of Ion Activation and Collision Induced Dissociation Using Digital Ion Trap Technology.

    PubMed

    Xu, Fuxing; Dang, Qiankun; Dai, Xinhua; Fang, Xiang; Wang, Yuanyuan; Ding, Li; Ding, Chuan-Fan

    2016-08-01

    Collision induced dissociation (CID) is one of the most established techniques for tandem mass spectrometry analysis. The CID of mass selected ion could be realized by ion resonance excitation with a digital rectangular waveform. The method is simple, and highly efficient CID result could be obtained by optimizing the experimental parameters, such as digital waveform voltage, frequency, and q value. In this work, the relationship between ion trapping waveform voltage and frequency at preselected q value, the relationship between waveform frequency and the q value at certain ion trapping voltage for optimum CID efficiency were investigated. Experiment results showed that the max CID efficiency of precursor reserpine ions can be obtained at different trapping waveform voltage and frequency when q and β are different. Based on systematic experimental analysis, the optimum experimental conditions for high CID efficiency can be calculated at any selected β or q. By using digital ion trap technology, the CID process and efficient fragmentation of parent ions can be realized by simply changing the trapping waveform amplitude, frequency, and the β values in the digital ion trap mass spectrometry. The technology and method are simple. It has potential use in ion trap mass spectrometry. Graphical Abstract ᅟ. PMID:27150507

  3. Characteristics of Ion Activation and Collision Induced Dissociation Using Digital Ion Trap Technology

    NASA Astrophysics Data System (ADS)

    Xu, Fuxing; Dang, Qiankun; Dai, Xinhua; Fang, Xiang; Wang, Yuanyuan; Ding, Li; Ding, Chuan-Fan

    2016-08-01

    Collision induced dissociation (CID) is one of the most established techniques for tandem mass spectrometry analysis. The CID of mass selected ion could be realized by ion resonance excitation with a digital rectangular waveform. The method is simple, and highly efficient CID result could be obtained by optimizing the experimental parameters, such as digital waveform voltage, frequency, and q value. In this work, the relationship between ion trapping waveform voltage and frequency at preselected q value, the relationship between waveform frequency and the q value at certain ion trapping voltage for optimum CID efficiency were investigated. Experiment results showed that the max CID efficiency of precursor reserpine ions can be obtained at different trapping waveform voltage and frequency when q and β are different. Based on systematic experimental analysis, the optimum experimental conditions for high CID efficiency can be calculated at any selected β or q. By using digital ion trap technology, the CID process and efficient fragmentation of parent ions can be realized by simply changing the trapping waveform amplitude, frequency, and the β values in the digital ion trap mass spectrometry. The technology and method are simple. It has potential use in ion trap mass spectrometry.

  4. Modeling and Optimizing RF Multipole Ion Traps

    NASA Astrophysics Data System (ADS)

    Fanghaenel, Sven; Asvany, Oskar; Schlemmer, Stephan

    2016-06-01

    Radio frequency (rf) ion traps are very well suited for spectroscopy experiments thanks to the long time storage of the species of interest in a well defined volume. The electrical potential of the ion trap is determined by the geometry of its electrodes and the applied voltages. In order to understand the behavior of trapped ions in realistic multipole traps it is necessary to characterize these trapping potentials. Commercial programs like SIMION or COMSOL, employing the finite difference and/or finite element method, are often used to model the electrical fields of the trap in order to design traps for various purposes, e.g. introducing light from a laser into the trap volume. For a controlled trapping of ions, e.g. for low temperature trapping, the time dependent electrical fields need to be known to high accuracy especially at the minimum of the effective (mechanical) potential. The commercial programs are not optimized for these applications and suffer from a number of limitations. Therefore, in our approach the boundary element method (BEM) has been employed in home-built programs to generate numerical solutions of real trap geometries, e.g. from CAD drawings. In addition the resulting fields are described by appropriate multipole expansions. As a consequence, the quality of a trap can be characterized by a small set of multipole parameters which are used to optimize the trap design. In this presentation a few example calculations will be discussed. In particular the accuracy of the method and the benefits of describing the trapping potentials via multipole expansions will be illustrated. As one important application heating effects of cold ions arising from non-ideal multipole fields can now be understood as a consequence of imperfect field configurations.

  5. Development and validation of automatic HS-SPME with a gas chromatography-ion trap/mass spectrometry method for analysis of volatiles in wines.

    PubMed

    Paula Barros, Elisabete; Moreira, Nathalie; Elias Pereira, Giuliano; Leite, Selma Gomes Ferreira; Moraes Rezende, Claudia; Guedes de Pinho, Paula

    2012-11-15

    An automated headspace solid-phase microextraction (HS-SPME) combined with gas chromatography-ion trap/mass spectrometry (GC-IT/MS) was developed in order to quantify a large number of volatile compounds in wines such as alcohols, ester, norisoprenoids and terpenes. The procedures were optimized for SPME fiber selection, pre-incubation temperature and time, extraction temperature and time, and salt addition. A central composite experimental design was used in the optimization of the extraction conditions. The volatile compounds showed optimal extraction using a DVB/CAR/PDMS fiber, incubation of 5 ml of wine with 2g NaCl at 45 °C during 5 min, and subsequent extraction of 30 min at the same temperature. The method allowed the identification of 64 volatile compounds. Afterwards, the method was validated successfully for the most significant compounds and was applied to study the volatile composition of different white wines. PMID:23158309

  6. Structural elucidation of biologically active neomycin N-octyl derivatives in a regioisomeric mixture by means of liquid chromatography/ion trap time-of-flight mass spectrometry.

    PubMed

    Giera, Martin; de Vlieger, Jon S B; Lingeman, Henk; Irth, Hubertus; Niessen, Wilfried M A

    2010-05-30

    Structural elucidation of six regioisomers of mono-N-octyl derivatized neomycin is achieved using MS(n) (up to n = 4) on an ion trap time-of-flight (IT-TOF) instrument equipped with electrospray ionization. The mixture of six derivatized neomycin analogues was generated by reductive amination in a shotgun synthetic approach. In parallel to the liquid chromatography/mass spectrometry (LC/MS) detection, the antibacterial activity of the neomycin regioisomers was tested by post-column addition of buffer and bacterial inocula, subsequent microfractionation of the resulting mixture, incubation, and finally a chemiluminescence-based bioactivity measurement based on the production of bacterial ATP. The MS-based high-resolution screening approach described can be applied in medicinal chemistry to help in designing and producing new antibiotic substances, which is particularly challenging due to the high functionality of most antibiotic substances, therefore requiring advanced (hyphenated) separation and detection techniques for compound mixtures.

  7. Determination of specific neuropeptides modulation time course in a rat model of osteoarthritis pain by liquid chromatography ion trap mass spectrometry.

    PubMed

    Ferland, Catherine E; Pailleux, Floriane; Vachon, Pascal; Beaudry, Francis

    2011-12-01

    Animal models are useful to evaluate pharmacological therapies to alleviate joint pain. The present study characterized central neuropeptides modulation in the monoiodoacetate (MIA) rat model. Animals receiving a single 3mg MIA injection were euthanized at 3, 7, 14, 21 and 28 days post injection. Spinal cords were analyzed by liquid chromatography ion trap mass spectrometry. Up-regulations of the calcitonin gene-related peptide and substance P were observed starting on days 7 and 28 respectively, whereas big dynorphin(₁₋₃₂) content decreased significantly on day 14 in comparison to control animals (P<0.05). Preclinical drug evaluations using this model should be conducted between 7 and 21 days post injection when the lesions resemble most to human osteoarthritis.

  8. Combined Fourier-transform infrared imaging and desorption electrospray-ionization linear ion-trap mass spectrometry for analysis of counterfeit antimalarial tablets.

    PubMed

    Ricci, Camilla; Nyadong, Leonard; Fernandez, Facundo M; Newton, Paul N; Kazarian, Sergei G

    2007-01-01

    This paper reports use of a combination of Fourier-transform infrared (FTIR) spectroscopic imaging and desorption electrospray ionization linear ion-trap mass spectrometry (DESI MS) for characterization of counterfeit pharmaceutical tablets. The counterfeit artesunate antimalarial tablets were analyzed by both techniques. The results obtained revealed the ability of FTIR imaging in non-destructive micro-attenuated total reflection (ATR) mode to detect the distribution of all components in the tablet, the identities of which were confirmed by DESI MS. Chemical images of the tablets were obtained with high spatial resolution. The FTIR spectroscopic imaging method affords inherent chemical specificity with rapid acquisition of data. DESI MS enables high-sensitivity detection of trace organic compounds. Combination of these two orthogonal surface-characterization methods has great potential for detection and analysis of counterfeit tablets in the open air and without sample preparation.

  9. Rapid screening and identification of multi-class substances of very high concern in textiles using liquid chromatography-hybrid linear ion trap orbitrap mass spectrometry.

    PubMed

    Zhang, Li; Luo, Xin; Niu, Zengyuan; Ye, Xiwen; Tang, Zhixu; Yao, Peng

    2015-03-20

    A new analytical method was established and validated for the analysis of 19 substances of very high concern (SVHCs) in textiles, including phthalic acid esters (PAEs), organotins (OTs), perfluorochemicals (PFCs) and flame retardants (FRs). After ultrasonic extraction in methanol, the textile samples were analyzed by high performance liquid chromatography-hybrid linear ion trap Orbitrap high resolution mass spectrometry (HPLC-LTQ/Orbitrap). The values of LOQ were in the range of 2-200mg/kg. Recoveries at two levels (at the LOQ and at half the limit of regulation) ranged from 68% to 120%, and the repeatability was lower than 13%. This method was successfully applied to the screening of SVHCs in commercial textile samples and is useful for the fast screening of various SVHCs.

  10. [Simultaneous identification and detection of 16 anabolic steroid hormones in muscle using liquid chromatography oupled to quadrupole/linear ion trap mass spectrometry].

    PubMed

    Zhang, Hongwei'; Cai, Xue; Lin, Liming; Chen, Liangzhen; Liang, Chengzhu; Bao, Lei; Tang, Zhixu; Niu, Zengyuan; Wang, Fengmei

    2012-10-01

    A comprehensive method for simultaneous identification and detection of 16 anabolic steroid hormones (ASs, including andorgens, gestagens and their esters) in muscle samples was developed with liquid chromatography coupled to quadrupole/linear ion trap mass spectrometry (LC-Q/Trap-MS). The ASs in muscle samples were extracted with acetonitrile under ultrasonic assistance. The extract was defatted by n-hexane with liquid-liquid partitioning and followed by clean-up with NH2 solid phase extraction (SPE) cartridge. The separation of analytes was carried out on a CAPCELL PAK C18 MG II column (150 mm x 2.0 mm, 5.0 microm) using mobile phases of 0.1% (v/v) formic acid in acetonitrile and 0.1% (v/v) formic acid-5 mmol/L ammonium formate aqueous solution with gradient elution. A scheduled multiple reaction monitoring (sMRM) in positive mode as survey scan and an enhanced product ion (EPI) scan as dependent scan in an information-dependent acquisition (IDA) experiment was adopted in mass spectrometry acquisition. On-line lab-built MS/MS library and internal standards were employed for the identification and quantification. As a result, the 16 ASs showed good linearity with all correlation coefficients (r) no less than 0. 999 0 within the linear ranges. The limits of quantification (LOQs, S/N > or = 10) for the 16 ASs were in the range of 0.029-0.36 microg/kg. At the three spiked levels (0.5, 2.0 and 20 microg/kg), the overall recoveries ranged from 89.9% to 118% with the relative standard deviations (RSDs) no more than 16.2% under within--laboratory reproducibility conditions. The proposed method can be used to identify and detect the 16 ASs in a single run, which makes it effective in residue surveillance of anabolic hormones in muscle samples.

  11. Spectroscopy with trapped highly charged ions

    SciTech Connect

    Beiersdorfer, P

    2008-01-23

    We give an overview of atomic spectroscopy performed on electron beam ion traps at various locations throughout the world. Spectroscopy at these facilities contributes to various areas of science and engineering, including but not limited to basic atomic physics, astrophysics, extreme ultraviolet lithography, and the development of density and temperature diagnostics of fusion plasmas. These contributions are accomplished by generating, for example, spectral surveys, making precise radiative lifetime measurements, accounting for radiative power emitted in a given wavelength band, illucidating isotopic effects, and testing collisional-radiative models. While spectroscopy with electron beam ion traps had originally focused on the x-ray emission from highly charged ions interacting with the electron beam, the operating modes of such devices have expanded to study radiation in almost all wavelength bands from the visible to the hard x-ray region; and at several facilities the ions can be studied even in the absence of an electron beam. Photon emission after charge exchange or laser excitation has been observed, and the work is no longer restricted to highly charged ions. Much of the experimental capabilities are unique to electron beam ion traps, and the work performed with these devices cannot be undertaken elsewhere. However, in other areas the work on electron beam ion traps rivals the spectroscopy performed with conventional ion traps or heavy-ion storage rings. The examples we present highlight many of the capabilities of the existing electron beam ion traps and their contributions to physics.

  12. Determination of organic acids in urine by solid-phase microextraction and gas chromatography-ion trap tandem mass spectrometry previous 'in sample' derivatization with trimethyloxonium tetrafluoroborate.

    PubMed

    Pacenti, Marco; Dugheri, Stefano; Villanelli, Fabio; Bartolucci, Gianluca; Calamai, Luca; Boccalon, Pierpaolo; Arcangeli, Giulio; Vecchione, Febe; Alessi, Paolo; Kikic, Ireneo; Cupelli, Vincenzo

    2008-10-01

    A method for the determination of the organic acids directly in the urine employing derivatization with trimethyloxonium tetrafluoroborate as a methylating agent and sequential extraction by head space and direct immersion/solid phase microextraction is reported. Furoic acid, hippuric acid, methylhippuric acid, mandelic acid, phenylglyoxylic acid and trans, trans muconic acid contained in urine and proposed by the American Conference of Governmental Industrial Hygienists as biological exposure indices were determined after a fast and economically convenient preparation step and sensitive gas chromatography-ion trap-mass spectrometry/tandem mass spectrometry analysis. Urine is rather a complex sample and hence the acquisition method required specific GC-MS instrumentation capable of supporting the changeover, fully automated during a single chromatographic separation, from mass to tandem mass spectrometry and both chemical and electron ionization modes. The automation of the analytical method provides a number of advantages, including reduced analysis time for both routine analysis and method development, and greater reproducibility. The equilibrium and kinetics of this substances vs head space/direct immersion-solid phase microextraction were investigated and evaluated theoretically.

  13. Single Ion Trapping for the Enriched Xenon Observatory

    SciTech Connect

    Waldman, Samuel J.; /Stanford U., Phys. Dept. /SLAC

    2006-03-28

    In the last decade, a variety of neutrino oscillation experiments have established that there is a mass difference between neutrino flavors, without determining the absolute neutrino mass scale. The Enriched Xenon Observatory for neutrinoless double beta decay (EXO) will search for the rare decays of xenon to determine the absolute value of the neutrino mass. The experiment uses a novel technique to minimize backgrounds, identifying the decay daughter product in real time using single ion spectroscopy. Here, we describe single ion trapping and spectroscopy compatible with the EXO detector. We extend the technique of single ion trapping in ultrahigh vacuum to trapping in xenon gas. With this technique, EXO will achieve a neutrino mass sensitivity of {approx_equal} .010 eV.

  14. Validation of a new liquid chromatography- tandem mass spectrometry ion-trap technique for the simultaneous determination of thirteen anticoagulant rodenticides, drugs, or natural products.

    PubMed

    Fourel, Isabelle; Hugnet, Christophe; Goy-Thollot, Isabelle; Berny, Philippe

    2010-03-01

    The purpose of this study was to develop and validate a liquid chromatography-tandem mass spectrometry method for the identification and quantification of anticoagulant (anti-vitamin K or AVK) compounds, including rodenticides, drugs, and natural products because no published method could be found. The proposed method is based on ion-trap technology with electrospray ionization (ESI) and multiple reaction monitoring (MRM) technique. Each AVK is identified by means of its retention time, precursor ion, and two product ions. Plasma samples are extracted by liquid-liquid partition on Toxi-tube B((R)). The method was validated on dog plasma and gave good results in terms of specificity, linearity, and percent recovery for the 14 AVK tested (warfarin, acenocoumarol, bromadiolone, brodifacoum, chlorophacinone, coumatetralyl, dicoumarol, difenacoum, difethialone, flocoumafen, fluindione, phenindione, and tioclomarol). The limits of detection ranged from 5 to 25 ng/mL. Intraday repeatability was good, but interday repeatability was more variable though still sufficient for our diagnostic purposes. The technique was successfully applied in a series of clinical investigations to demonstrate its applicability in various animal species and gave very high sensitivity and specificity results. PMID:20223102

  15. Validation of a new liquid chromatography- tandem mass spectrometry ion-trap technique for the simultaneous determination of thirteen anticoagulant rodenticides, drugs, or natural products.

    PubMed

    Fourel, Isabelle; Hugnet, Christophe; Goy-Thollot, Isabelle; Berny, Philippe

    2010-03-01

    The purpose of this study was to develop and validate a liquid chromatography-tandem mass spectrometry method for the identification and quantification of anticoagulant (anti-vitamin K or AVK) compounds, including rodenticides, drugs, and natural products because no published method could be found. The proposed method is based on ion-trap technology with electrospray ionization (ESI) and multiple reaction monitoring (MRM) technique. Each AVK is identified by means of its retention time, precursor ion, and two product ions. Plasma samples are extracted by liquid-liquid partition on Toxi-tube B((R)). The method was validated on dog plasma and gave good results in terms of specificity, linearity, and percent recovery for the 14 AVK tested (warfarin, acenocoumarol, bromadiolone, brodifacoum, chlorophacinone, coumatetralyl, dicoumarol, difenacoum, difethialone, flocoumafen, fluindione, phenindione, and tioclomarol). The limits of detection ranged from 5 to 25 ng/mL. Intraday repeatability was good, but interday repeatability was more variable though still sufficient for our diagnostic purposes. The technique was successfully applied in a series of clinical investigations to demonstrate its applicability in various animal species and gave very high sensitivity and specificity results.

  16. Determination of trace levels of herbicides and their degradation products in surface and ground waters by gas chromatography/ion-trap mass spectrometry

    USGS Publications Warehouse

    Pereira, W.E.; Rostad, C.E.; Leiker, T.J.

    1990-01-01

    A rapid, specific and highly sensitive method is described for the determination of several commonly used herbicides and their degradation products in surface and ground waters by using gas chromatography/ion-trap mass spectrometry. The compounds included atrazine, and its degradation products desethylatrazine and desisopropylatrazine; Simazine; Cyanazine; Metolachlor; and alachlor and its degradation products, 2-chloro-2', 6'-diethylacetanilide, 2-hydroxy-2', 6'-diethylacetanilide and 2,6-diethylaniline. The method was applied to surface-water samples collected from 16 different stations along the lower Mississippi River and its major tributaries, and ground-water samples beneath a cornfield in central Nebraska. Average recovery of a surrogate herbicide, terbuthylazine, was greater than 99%. Recoveries of the compounds of interest from river water spiked at environmental levels are also presented. Full-scan mass spectra of these compounds were obtained on 1 ng or less of analyte. Data were collected in the full-scan acquisition mode. Quantitation was based on a single characteristic ion for each compound. The detection limit was 60 pg with a signal-to-noise ratio of greater than 10:1.

  17. Global detection and identification of components from crude and processed traditional Chinese medicine by liquid chromatography connected with hybrid ion trap and time-of-flight-mass spectrometry.

    PubMed

    Cao, Gang; Zhang, Chengrong; Zhang, Yun; Cong, Xiaodong; Cai, Hao; Cai, Baochang; Li, Xiaomeng; Yao, Jinting

    2011-08-01

    We herein present a chemical profiling method to efficiently process the information acquired by ultra fast liquid chromatography (UFLC)-electrospray ionization source in combination with hybrid ion trap and high-resolution time-of-flight mass spectrometry (UFLC-(ESI)-IT-TOF/MS), facilitating the structural determination of serial components contained in crude or processed traditional Chinese medicine (TCM). Under the optimized UFLC and IT-TOF-MS(n) conditions, over 39 compounds were separated and detected in crude or processed Fructus corni within 25 min. The components were identified by comparing the mass spectra and retention time with reference compounds, or tentatively assigned by elucidating low-energy collision-induced dissociation (CID) fragment ions and matching empirical molecular formula with that of the published compounds. Several factors in the processing procedure were examined. The experimental results demonstrate that the chemical reactions that occurred in the processing procedure can be used to elucidate the processed mechanism of F. corni, which is regularly affected by the processing conditions. This study provides a novel approach and methodology to identify the complicated components from various complex mixtures such as crude TCM, processed TCM, and biological samples. It can be used as a valid analytical method for further understanding the processing mechanism of TCM, along with the intrinsic quality control of TCM and its processed product.

  18. Development of online sampling and matrix reduction technique coupled liquid chromatography/ion trap mass spectrometry for determination maduramicin in chicken meat.

    PubMed

    Chang, Kai Chun; Su, Jung Jeng; Cheng, Cheanyeh

    2013-11-15

    An online sampling and matrix reduction technique coupled liquid chromatography electrospray-ion-trap mass spectrometry was developed for rapid analysis of maduramicin (MAD) residue in chicken meat. Multiple-reaction monitoring of mass spectrometry in positive ion mode was used to detect maduramicin. A post-column continuous infusion of internal standard (nigericin) with matrix-matched calibration method was utilised for quantification. The linear concentration range of the calibration curve was 0-10.0 ng mL(-1) (r(2)=0.999). The limit of detection (quantification) was 0.08 ng g(-1) (0.28 ng g(-1)). The analytical accuracy of chicken meat samples for four spiked MAD concentrations (0.5, 1.0, 5.0, and 10.0 ng g(-1)) was 84-97% and their corresponding intra-day and inter-day precisions were 3.7-5.0% and 5.8-7.9%, respectively. The analysis time for one sample was 10 min. The application of the method for incurred chicken samples elucidates that MAD residue in chicken meat decreases during the withdrawal period.

  19. In-trap spectroscopy of charge-bred radioactive ions.

    PubMed

    Lennarz, A; Grossheim, A; Leach, K G; Alanssari, M; Brunner, T; Chaudhuri, A; Chowdhury, U; Crespo López-Urrutia, J R; Gallant, A T; Holl, M; Kwiatkowski, A A; Lassen, J; Macdonald, T D; Schultz, B E; Seeraji, S; Simon, M C; Andreoiu, C; Dilling, J; Frekers, D

    2014-08-22

    In this Letter, we introduce the concept of in-trap nuclear decay spectroscopy of highly charged radioactive ions and describe its successful application as a novel spectroscopic tool. This is demonstrated by a measurement of the decay properties of radioactive mass A=124 ions (here, ^{124}In and ^{124}Cs) in the electron-beam ion trap of the TITAN facility at TRIUMF. By subjecting the trapped ions to an intense electron beam, the ions are charge bred to high charge states (i.e., equivalent to the removal of N-shell electrons), and an increase of storage times to the level of minutes without significant ion losses is achieved. The present technique opens the venue for precision spectroscopy of low branching ratios and is being developed in the context of measuring electron-capture branching ratios needed for determining the nuclear ground-state properties of the intermediate odd-odd nuclei in double-beta (ββ) decay.

  20. Nonlinear spectroscopy of trapped ions

    NASA Astrophysics Data System (ADS)

    Schlawin, Frank; Gessner, Manuel; Mukamel, Shaul; Buchleitner, Andreas

    2014-08-01

    Nonlinear spectroscopy employs a series of laser pulses to interrogate dynamics in large interacting many-body systems, and it has become a highly successful method for experiments in chemical physics. Current quantum optical experiments approach system sizes and levels of complexity that require the development of efficient techniques to assess spectral and dynamical features with scalable experimental overhead. However, established methods from optical spectroscopy of macroscopic ensembles cannot be applied straightforwardly to few-atom systems. Based on the ideas proposed in M. Gessner et al., (arXiv:1312.3365), we develop a diagrammatic approach to construct nonlinear measurement protocols for controlled quantum systems, and we discuss experimental implementations with trapped ion technology in detail. These methods, in combination with distinct features of ultracold-matter systems, allow us to monitor and analyze excitation dynamics in both the electronic and vibrational degrees of freedom. They are independent of system size, and they can therefore reliably probe systems in which, e.g., quantum state tomography becomes prohibitively expensive. We propose signals that can probe steady-state currents, detect the influence of anharmonicities on phonon transport, and identify signatures of chaotic dynamics near a quantum phase transition in an Ising-type spin chain.

  1. Entanglement of Multiple Trapped Ions

    NASA Astrophysics Data System (ADS)

    Sackett, C. A.

    2000-06-01

    Quantum mechanics allows for many-particle wave functions which cannot be factorized into a product of single-particle wave functions, even when the constituent particles are entirely distinct. Such entangled states explicitly demonstrate the nonclassical correlations of quantum theory,(See for instance J. Bell, Speakable and Unspeakable in Quantum Mechanics). (Cambridge Univ. Press, Cambridge, 1987); J.-W. Pan, D. Bouwmeester, M. Daniell, H. Weinfurter, and A. Zeilinger, Nature 403, 515 (2000). have been suggested for use in high-precision spectroscopy,( J. Bollinger, W.M. Itano, D. Wineland, and D. Heinzen, Phys. Rev. A) 54, R4649 (1996). and are a fundamental element of schemes for quantum communication, cryptography, and computation.(See for instance H.-K Lo, S. Popescu, and T. Spiller, editors, Introduction to Quantum Computation and Information). (World Scientific, Singapore, 1997). In general, the more particles which can be entangled, the more useful the states are for quantum applications. In pursuit of these goals, we have demonstrated an entanglement technique which is applicable to any number of trapped ions.(K. Mølmer and A. Sørensen, Phys. Rev. Lett.) 82, 1835 (1999). We have used this technique to generate entangled states of two, and for the first time, four atoms.

  2. Simple analytic potentials for linear ion traps

    NASA Technical Reports Server (NTRS)

    Janik, G. R.; Prestage, J. D.; Maleki, L.

    1990-01-01

    A simple analytical model was developed for the electric and ponderomotive (trapping) potentials in linear ion traps. This model was used to calculate the required voltage drive to a mercury trap, and the result compares well with experiments. The model gives a detailed picture of the geometric shape of the trapping potential and allows an accurate calculation of the well depth. The simplicity of the model allowed an investigation of related, more exotic trap designs which may have advantages in light-collection efficiency.

  3. Simple analytic potentials for linear ion traps

    NASA Technical Reports Server (NTRS)

    Janik, G. R.; Prestage, J. D.; Maleki, L.

    1989-01-01

    A simple analytical model was developed for the electric and ponderomotive (trapping) potentials in linear ion traps. This model was used to calculate the required voltage drive to a mercury trap, and the result compares well with experiments. The model gives a detailed picture of the geometric shape of the trapping potenital and allows an accurate calculation of the well depth. The simplicity of the model allowed an investigation of related, more exotic trap designs which may have advantages in light-collection efficiency.

  4. [Screening and confirmation of carcinogenic dyes in textiles by high performance liquid chromatography-linear ion trap/orbitrap high resolution mass spectrometry].

    PubMed

    Xiu, Xiaoli; Luo, Xin; Niu, Zengyuan; Ye, Xiwen; Zhixu, Tang; Li, Jingying; Wang, Yongwei; Du, Wei

    2013-10-01

    A method of high performance liquid chromatography-linear ion trap/Orbitrap high resolution mass spectrometry (HPLC-LTQ/Orbitrap MS) was used to screen and confirm carcinogenic dyes in textiles. The analytes were extracted from textile samples with pyridine/water (1/1, v/v) in a water bath under controlled conditions (95 degrees C, 150 r/min), and then filtered with a 0.22 microm polytetrafluoroetylene (PTFE) membrane. The eluates were separated on a CAPCELL PAK C18 column (100 mm x 2.0 mm, 5 microm) using gradient elution with acetonitrile/ 5 mmol/L ammonium acetate aqueous solution containing 0.01% formic acid (in positive mode) and acetonitrile/5 mmol/L ammonium acetate aqueous solution (in negative mode), and finally detected by HPLC-LTQ/Orbitrap MS in ESI modes. Full scan experiments were performed over the range of m/z 200-800. The screening and quantitative analysis were carried out by the accurate mass of quasi-molecular ion and the peak area in extracted chromatogram with accurate mass, respectively. The confirmatory analysis for target compounds was performed with the retention time and qualitative fragments obtained by data-dependent scan mode. Under the optimal conditions, nine carcinogenic dyes were routinely detected with mass accuracy below 5 x 10(-6) (5 ppm), and good linearities were provided in their respective linear ranges with correlation coefficients higher than 0.99. The limits of detection were in the range of 0.125-25 mg/kg. The average recoveries at three spiked levels were in the range of 62.13%116.28% with the relative standard deviations (RSDs) lower than 15%. The proposed method was applied to screen and confirm the nine carcinogenic dyes in textile samples. It is convenient and reliable.

  5. Interchange mode excited by trapped energetic ions

    SciTech Connect

    Nishimura, Seiya

    2015-07-15

    The kinetic energy principle describing the interaction between ideal magnetohydrodynamic (MHD) modes with trapped energetic ions is revised. A model is proposed on the basis of the reduced ideal MHD equations for background plasmas and the bounce-averaged drift-kinetic equation for trapped energetic ions. The model is applicable to large-aspect-ratio toroidal devices. Specifically, the effect of trapped energetic ions on the interchange mode in helical systems is analyzed. Results show that the interchange mode is excited by trapped energetic ions, even if the equilibrium states are stable to the ideal interchange mode. The energetic-ion-induced branch of the interchange mode might be associated with the fishbone mode in helical systems.

  6. Ion Trap Array-Based Systems And Methods For Chemical Analysis

    DOEpatents

    Whitten, William B [Oak Ridge, TN; Ramsey, J Michael [Knoxville, TN

    2005-08-23

    An ion trap-based system for chemical analysis includes an ion trap array. The ion trap array includes a plurality of ion traps arranged in a 2-dimensional array for initially confining ions. Each of the ion traps comprise a central electrode having an aperture, a first and second insulator each having an aperture sandwiching the central electrode, and first and second end cap electrodes each having an aperture sandwiching the first and second insulator. A structure for simultaneously directing a plurality of different species of ions out from the ion traps is provided. A spectrometer including a detector receives and identifies the ions. The trap array can be used with spectrometers including time-of-flight mass spectrometers and ion mobility spectrometers.

  7. Structural analysis of poly[(R,S)-3-hydroxybutyrate-co-L-lactide] copolyesters by electrospray ionization ion trap mass spectrometry.

    PubMed

    Adamus, Grazyna

    2007-01-01

    Two random copolyesters of poly[(R,S)-3-hydroxybutyrate-co-L-lactide] (P[(R,S)-3HB-co-LA]), prepared by equimolar reaction of (R,S)-beta-butyrolactone with L-lactic acid and (R,S)-3-hydroxybutyric acid with L-lactide, respectively, were characterized by electrospray ionization ion trap mass spectrometry (ESI-ITMS). Detailed studies of these copolyesters were performed by means of collision-induced dissociation (CID). The molecular architecture of individual copolyester macromolecules, including chemical structures of their end groups (hydroxyl and carboxylate), were established on the basis of their ESI mass spectra. The influence of an intermolecular transesterification reaction on the microstructure of the copolyester synthesized by equimolar reaction of (R,S)-3-hydroxybutyric acid with L-lactide was observed. The mass spectra provided information on sequence distribution and indicated that, despite the synthetic pathway applied, random P[(R,S)-3HB-co-LA] copolyesters were formed predominantly. The arrangements of comonomer structural units along the copolyester chains were evaluated by the respective ESI-MS/MS fragmentation pathways. PMID:17610241

  8. Dipole Field Effects on Ion Ejections from a Paul Ion Trap

    NASA Technical Reports Server (NTRS)

    MacAskill, J. A.; Chutjian, A.

    2011-01-01

    Attempts at improving the quality of mass spectra obtained from a Paul trap mass spectrometer prompted an investigation of the effects of additional fields to supplement the primary rf quadrupole trapping field. Reported here are the results of the first in a series of tests that focuses on the application of a single dipole field to augment the trapping and subsequent ejections of ions stored within a Paul trap. Measurements are presented for a fixed quadrupole frequency with varying dipole frequencies. The presence of the dipole field during the quadrupole trapping phase causes ion ejections of single m/z species at discrete dipole frequencies. During the mass analysis phase, the varying dipole frequency produces a complex set of resonant structures that impact ejection time (mass range), as well as mass spectral peak intensity and width

  9. Comparison of indirect and direct approaches using ion-trap and Fourier transform ion cyclotron resonance mass spectrometry for exploring viperid venom proteomes.

    PubMed

    Fox, Jay W; Ma, Li; Nelson, Kristina; Sherman, Nicholas E; Serrano, Solange M T

    2006-05-01

    In a sense, the field of snake venom proteomics has been under investigation since the very earliest biochemical studies where it was soon recognized that venoms are comprised of complex mixtures of bioactive molecules, most of which are proteins. Only with the re-emergence of 2D polyacrylamide gel electrophoresis (2D PAGE) and the recent developments in mass spectrometry for the identification/characterization of proteins coupled with venom gland transcriptomes has the field of snake venom proteomics began to flourish and provide exciting insights into the protein composition of venoms and subsequently their pathological activities. In this manuscript we will briefly discuss the state of snake venom proteomics followed by the presentation of several straightforward experiments designed to explore approaches to investigating venom proteomics. The first set of experiments used 1D gel electrophoresis (1D PAGE) of Crotalus atrox venom followed by slice-by-slice analysis of the proteins using liquid chromatography/mass spectrometry/mass spectrometry (LC/MS/MS). In the second set of experiments, C. atrox and Bothrops jararaca venoms were subjected to in-solution digestion followed by Fourier transform ion cyclotron resonance (FTICR) LC/MS/MS. The peptide ion-maps of these venoms were compared along with the proteins identified. In addition, the results were compared to the results observed from the 1D PAGE approach. From these studies it is clear that sample de-complexation/fractionation before mass spectrometry is still the best approach for maximum proteome coverage. Furthermore, comparison of venom proteomes based on tryptic peptide identities between the proteomes is not particularly effective since there does not appear to be a sufficient number of such identical peptides, derived from related proteins, present in venoms. Finally, as has previously been recognized without either better databases of venom protein sequences or facile and rapid de novo sequencing

  10. Liquid chromatography/negative electrospray ionization ion trap MS(2) mass spectrometry application for the determination of microcystins occurrence in Southern Portugal water reservoirs.

    PubMed

    Rodrigues, M A; Reis, M P; Mateus, M C

    2013-11-01

    Microcystins (MCs) are toxins produced by cyanobacteria which are common organisms in the phytoplankton of eutrophic lakes, rivers and freshwater reservoirs. In the present work, a novel method of liquid chromatography-electrospray ion trap tandem mass spectrometry (LC/ESI/Ion trap-MS/MS), operated in the negative ionization mode, was developed for the analysis of these cyanotoxins. The method was applied to determine the amounts of total microcystins-LR, -YR and -RR in two water reservoirs in Southern Portugal, namely Alqueva and Beliche. A total of 30 water samples were analysed along 2011. Solid phase extraction (SPE) was used for sample cleaning-up and analyte enrichment. The extracted toxins were separated on a C18 column with a gradient of acetonitrile/water with 0.1% formic acid. Detection of microcystins was carried out using multiple reaction monitoring (MRM) in the negative polarity mode, as this method gave a higher selectivity. The MC-RR, YR and LR quantification limits were 17.9, 31.7 and 15.8 ng/L, respectively; quite below the limits recommended by WHO guidelines for drinking water (1 μg/L). Total MC highest concentrations were found in the warm months of June, July and September in Alqueva sampling sites, with concentrations of MC LR and RR ranging 17-344 and 25-212 ng/L, respectively, showing comparable results for MC-RR and LR and slightly lower concentration of MC-YR. Detected values for Beliche reservoir were below quantification limits.

  11. MEMS-based arrays of micro ion traps for quantum simulation scaling.

    SciTech Connect

    Berkeland, Dana J.; Blain, Matthew Glenn; Jokiel, Bernhard, Jr.

    2006-11-01

    In this late-start Tier I Seniors Council sponsored LDRD, we have designed, simulated, microfabricated, packaged, and tested ion traps to extend the current quantum simulation capabilities of macro-ion traps to tens of ions in one and two dimensions in monolithically microfabricated micrometer-scaled MEMS-based ion traps. Such traps are being microfabricated and packaged at Sandia's MESA facility in a unique tungsten MEMS process that has already made arrays of millions of micron-sized cylindrical ion traps for mass spectroscopy applications. We define and discuss the motivation for quantum simulation using the trapping of ions, show the results of efforts in designing, simulating, and microfabricating W based MEMS ion traps at Sandia's MESA facility, and describe is some detail our development of a custom based ion trap chip packaging technology that enables the implementation of these devices in quantum physics experiments.

  12. Simultaneous identification and quantification of tetrodotoxin in fresh pufferfish and pufferfish-based products using immunoaffinity columns and liquid chromatography/quadrupole-linear ion trap mass spectrometry

    NASA Astrophysics Data System (ADS)

    Guo, Mengmeng; Wu, Haiyan; Jiang, Tao; Tan, Zhijun; Zhao, Chunxia; Zheng, Guanchao; Li, Zhaoxin; Zhai, Yuxiu

    2016-08-01

    In this study, we established a comprehensive method for simultaneous identification and quantification of tetrodotoxin (TTX) in fresh pufferfish tissues and pufferfish-based products using liquid chromatography/quadrupole-linear ion trap mass spectrometry (LC-QqLIT-MS). TTX was extracted by 1% acetic acid-methanol, and most of the lipids were then removed by freezing lipid precipitation, followed by purification and concentration using immunoaffinity columns (IACs). Matrix effects were substantially reduced due to the high specificity of the IACs, and thus, background interference was avoided. Quantitation analysis was therefore performed using an external calibration curve with standards prepared in mobile phase. The method was evaluated by fortifying samples at 1, 10, and 100 ng/g, respectively, and the recoveries ranged from 75.8%-107%, with a relative standard deviation of less than 15%. The TTX calibration curves were linear over the range of 1-1 000 μg/L, with a detection limit of 0.3 ng/g and a quantification limit of 1 ng/g. Using this method, samples can be further analyzed using an information-dependent acquisition (IDA) experiment, in the positive mode, from a single liquid chromatography-tandem mass spectrometry injection, which can provide an extra level of confirmation by matching the full product ion spectra acquired for a standard sample with those from an enhanced product ion (EPI) library. The scheduled multiple reaction monitoring method enabled TTX to be screened for, and TTX was positively identified using the IDA and EPI spectra. This method was successfully applied to analyze a total of 206 samples of fresh pufferfish tissues and pufferfish-based products. The results from this study show that the proposed method can be used to quantify and identify TTX in a single run with excellent sensitivity and reproducibility, and is suitable for the analysis of complex matrix pufferfish samples.

  13. [Rapid screening and identification of 22 allergenic disperse dyes in ecological textiles by high performance liquid chromatography-linear ion trap/orbitrap mass spectrometry].

    PubMed

    Niu, Zengyuan; Luo, Xin; Ye, Xiwen; Xiu, Xiaoli; Zhang, Li; Wang, Xin; Chen, Jing

    2015-10-01

    A rapid screening method based on high performance liquid chromatography-linear ion trap/orbitrap high-resolution mass spectrometry (HPLC-LTQ/Orbitrap MS) for 22 disperse dyes in ecological textiles has been established. The target compounds were extracted by pyridine/water (1:1, v/v) by shaking extraction in 90 degrees C water bath. The extracts were then separated by a CAPCELL PAK C18 column (100 mm x 2.0 mm, 5 μm) using gradient elution with acetonitrile-5 mmol/L ammonium acetate containing 0.01% (v/v) formic acid as mobile phases, and finally analyzed by HPLC-LTQ/Orbitrap in positive and negative ESI modes. The retention time and accurate mass of parent ion were used for fast screening of 22 disperse dyes, while the confirmatory analysis was obtained by fragments generated by collision-induced dissociation (CID) MS/MS. Target analysis exhibited high mass accuracy (< 5 x 10(-6)). Each target showed a good linearity in its own concentration range and the correlation coefficient was higher than 0.99. The LOQs were 0.125-2.5 mg/kg. Except for Disperse Yellow 49, the average recoveries of most disperse dyes at three spiked levels were 65%-120%, and the relative standard deviations (n = 6) were less than 15%. The method was applied for screening 40 different kinds of textiles, and Disperse Orange 37/76 was detected in one of them. With high selectivity and strong anti-jamming ability, this method is simple, rapid, accurate, and it can be used for the inspection of disperse dyes in textiles.

  14. [Rapid screening and identification of 22 allergenic disperse dyes in ecological textiles by high performance liquid chromatography-linear ion trap/orbitrap mass spectrometry].

    PubMed

    Niu, Zengyuan; Luo, Xin; Ye, Xiwen; Xiu, Xiaoli; Zhang, Li; Wang, Xin; Chen, Jing

    2015-10-01

    A rapid screening method based on high performance liquid chromatography-linear ion trap/orbitrap high-resolution mass spectrometry (HPLC-LTQ/Orbitrap MS) for 22 disperse dyes in ecological textiles has been established. The target compounds were extracted by pyridine/water (1:1, v/v) by shaking extraction in 90 degrees C water bath. The extracts were then separated by a CAPCELL PAK C18 column (100 mm x 2.0 mm, 5 μm) using gradient elution with acetonitrile-5 mmol/L ammonium acetate containing 0.01% (v/v) formic acid as mobile phases, and finally analyzed by HPLC-LTQ/Orbitrap in positive and negative ESI modes. The retention time and accurate mass of parent ion were used for fast screening of 22 disperse dyes, while the confirmatory analysis was obtained by fragments generated by collision-induced dissociation (CID) MS/MS. Target analysis exhibited high mass accuracy (< 5 x 10(-6)). Each target showed a good linearity in its own concentration range and the correlation coefficient was higher than 0.99. The LOQs were 0.125-2.5 mg/kg. Except for Disperse Yellow 49, the average recoveries of most disperse dyes at three spiked levels were 65%-120%, and the relative standard deviations (n = 6) were less than 15%. The method was applied for screening 40 different kinds of textiles, and Disperse Orange 37/76 was detected in one of them. With high selectivity and strong anti-jamming ability, this method is simple, rapid, accurate, and it can be used for the inspection of disperse dyes in textiles. PMID:26930969

  15. Application and field test of a mobile thermal desorption - single photon ionization - ion trap mass spectrometer (TD-SPI-ITMS) for trace detection of security relevant substances

    NASA Astrophysics Data System (ADS)

    Schramm, Elisabeth; Heindl, Thomas; Hölzer, Jasper; McNeish, Alexander; Puetz, Michael; Ries, Hermann; Schall, Patricia; Schulte-Ladbeck, Rasmus; Schultze, Rainer; Sklorz, Martin; Spieker, Gerd; Trebbe, Roman; Ulrich, Andreas; Wieser, Jochen; Zimmermann, Ralf

    2009-05-01

    The objective of this accomplished project funded by the German BMBF was to develop a single photon ionization ion trap mass spectrometer (SPI-ITMS) for detection of security relevant substances in complex matrices at low concentrations. The advantage of such a soft ionization technique is a reduction of target ion fragmentation allowing identification of signals from complex matrices and enabling MS/MS capability. To obtain low detection limits, the applied photon energy has to be below the ionization potential (IP) of the bulk matrix components. Therefore, photon energies between 8 eV (155 nm) and 12 eV (103 nm) are necessary which was achieved with newly developed electron beam excimer lamps (EBEL). They generate light at different wavelengths depending on the selected rare gas emitting wavelengths adapted to the analyzed substances. So, e.g. with a krypton-EBEL with 8.4 eV photon energy most narcotics can be ionized without notable fragmentation. Due to their higher IPs, EBEL with higher photon energy have to be used for most explosives. Very low false-positive and false-negative rates have been achieved using MS/MS studies. First field tests of a demonstrator provided the proof of principle.

  16. Ultra-high-performance liquid chromatography-ion trap mass spectrometry characterisation of milk polar lipids from dairy cows fed different diets.

    PubMed

    Craige Trenerry, V; Akbaridoust, Ghazal; Plozza, Tim; Rochfort, Simone; Wales, William J; Auldist, Martin; Ajlouni, Said

    2013-11-15

    Milk polar lipids are an important class of biologically active species for human health and for improving the physical functionality of food ingredients. Milk polar lipids from 144 multiparous Holstein-Friesian dairy cows fed different diets were analysed using ultra-high-performance liquid chromatography-ion trap mass spectrometry (UHPLC-MS(n)). A complex profile of polar lipids, consisting of 7 species of phosphatidylinositol (PI), 12 species of phosphatidylethanolamine (PE), 18 species of phosphatidylcholine (PC) and 13 species of sphingomyelin (SM) were identified from the molecular ions and sequential MS(n) fragmentation. Qualitative assessment of the data suggested that different cow diets influenced the relative amounts of a small number of species in the milk samples, e.g. PE 14:0/18:1, PE 18:0/18:1, PC 15:0/18:1, PC 18:0/18:1, SM d18:1/14:0, SM d18:1/15:0, SM d18:1/22:0 and SM d18:1/23:0. PMID:23790938

  17. Subcellular-level resolution MALDI-MS imaging of maize leaf metabolites by MALDI-linear ion trap-Orbitrap mass spectrometer.

    PubMed

    Korte, Andrew R; Yandeau-Nelson, Marna D; Nikolau, Basil J; Lee, Young Jin

    2015-03-01

    A significant limiting factor in achieving high spatial resolution for matrix-assisted laser desorption ionization-mass spectrometry (MALDI-MS) imaging is the size of the laser spot at the sample surface. Here, we present modifications to the beam-delivery optics of a commercial MALDI-linear ion trap-Orbitrap instrument, incorporating an external Nd:YAG laser, beam-shaping optics, and an aspheric focusing lens, to reduce the minimum laser spot size from ~50 μm for the commercial configuration down to ~9 μm for the modified configuration. This improved system was applied for MALDI-MS imaging of cross sections of juvenile maize leaves at 5-μm spatial resolution using an oversampling method. A variety of different metabolites including amino acids, glycerolipids, and defense-related compounds were imaged at a spatial resolution well below the size of a single cell. Such images provide unprecedented insights into the metabolism associated with the different tissue types of the maize leaf, which is known to asymmetrically distribute the reactions of C4 photosynthesis among the mesophyll and bundle sheath cell types. The metabolite ion images correlate with the optical images that reveal the structures of the different tissues, and previously known and newly revealed asymmetric metabolic features are observed.

  18. Subcellular-level resolution MALDI-MS imaging of maize leaf metabolites by MALDI-linear ion trap-Orbitrap mass spectrometer

    DOE PAGES

    Korte, Andrew R.; Yandeau-Nelson, Marna D.; Nikolau, Basil J.; Lee, Young Jin

    2015-01-25

    A significant limiting factor in achieving high spatial resolution for matrix-assisted laser desorption ionization-mass spectrometry (MALDI-MS) imaging is the size of the laser spot at the sample surface. We present modifications to the beam-delivery optics of a commercial MALDI-linear ion trap-Orbitrap instrument, incorporating an external Nd:YAG laser, beam-shaping optics, and an aspheric focusing lens, to reduce the minimum laser spot size from ~50 μm for the commercial configuration down to ~9 μm for the modified configuration. This improved system was applied for MALDI-MS imaging of cross sections of juvenile maize leaves at 5-μm spatial resolution using an oversampling method. Theremore » are a variety of different metabolites including amino acids, glycerolipids, and defense-related compounds were imaged at a spatial resolution well below the size of a single cell. Such images provide unprecedented insights into the metabolism associated with the different tissue types of the maize leaf, which is known to asymmetrically distribute the reactions of C4 photosynthesis among the mesophyll and bundle sheath cell types. The metabolite ion images correlate with the optical images that reveal the structures of the different tissues, and previously known and newly revealed asymmetric metabolic features are observed.« less

  19. Subcellular-level resolution MALDI-MS imaging of maize leaf metabolites by MALDI-linear ion trap-Orbitrap mass spectrometer

    SciTech Connect

    Korte, Andrew R.; Yandeau-Nelson, Marna D.; Nikolau, Basil J.; Lee, Young Jin

    2015-01-25

    A significant limiting factor in achieving high spatial resolution for matrix-assisted laser desorption ionization-mass spectrometry (MALDI-MS) imaging is the size of the laser spot at the sample surface. We present modifications to the beam-delivery optics of a commercial MALDI-linear ion trap-Orbitrap instrument, incorporating an external Nd:YAG laser, beam-shaping optics, and an aspheric focusing lens, to reduce the minimum laser spot size from ~50 μm for the commercial configuration down to ~9 μm for the modified configuration. This improved system was applied for MALDI-MS imaging of cross sections of juvenile maize leaves at 5-μm spatial resolution using an oversampling method. There are a variety of different metabolites including amino acids, glycerolipids, and defense-related compounds were imaged at a spatial resolution well below the size of a single cell. Such images provide unprecedented insights into the metabolism associated with the different tissue types of the maize leaf, which is known to asymmetrically distribute the reactions of C4 photosynthesis among the mesophyll and bundle sheath cell types. The metabolite ion images correlate with the optical images that reveal the structures of the different tissues, and previously known and newly revealed asymmetric metabolic features are observed.

  20. Identification of in vivo nitrosylated phytochelatins in Arabidopsis thaliana cells by liquid chromatography-direct electrospray-linear ion trap-mass spectrometry.

    PubMed

    Elviri, L; Speroni, F; Careri, M; Mangia, A; di Toppi, L Sanità; Zottini, M

    2010-06-18

    Reversed-phase liquid chromatography (RPLC) and electrospray (ESI)-linear ion trap (LIT) mass spectrometry was applied to the direct characterization of in vivo S-nitrosylated (SNO) phytochelatins (PCs) expressed in cadmium-stressed Arabidopsis thaliana cells. Cys-nitrosylation is under discussion as in vivo redox-based post-translational modification of proteins and peptides in plants in which the -NO group is involved as signal molecule in different biological functions. The gas-phase ion chemistry of in vivo and in vitro generated SNO-PC(s) was compared with the aim of evaluating NO binding stability and improving MS knowledge about peptide nitrosation. Using RPLC separation and ESI-LIT-MS, mono-nitrosylated PCs were identified in in vivo cadmium treated A. thaliana cells without derivatization. The in vivo binding of the NO group to PC(2), PC(3) and PC(4) resulted to occur selectively on only one cystein residue. The fragmentation pathway energies of the in vitro GSNO-generated NO-PCs with respect to the in vivo NO-PCs were investigated, suggesting the presence of a different internal stability for these molecules. By carrying out MS(2) experiments on these quasi-symmetric peptides, the different stability degree of the NO group was demonstrated to be correlated with the PC chain length. In addition, the data obtained highlight a putative role of the adjacent Glu/Cys motif in the gas-phase stability of the NO-containing molecule.

  1. Determination of non-ionic polyethoxylated surfactants in sewage sludge by coacervative extraction and ion trap liquid chromatography-mass spectrometry.

    PubMed

    Cantero, Manuel; Rubio, Soledad; Pérez-Bendito, Dolores

    2004-08-13

    Alkylphenol polyethoxylates (APE, nonyl and octyl) and alcohol ethoxylates (AE, C12-C16) were analysed in sewage sludge by extraction with sodium dodecane sulphonate (SDoS), that undergoes coacervation under acid conditions, followed by quantitation with liquid chromatography/atmospheric pressure chemical ionisation ion/trap mass spectrometry, in positive ion mode. Coacervative extraction was optimised using an aged, fortified dehydrated sludge. Recoveries ranged from 78 to nearly 100% irrespective of the sludge matrix analysed. The method provided good agreement between the ethoxamer distribution of surfactants after extraction from sludge and that in the original surfactant. Detection limits for polyethoxylated surfactants in the sludge were 0.09-0.38 mg/kg. The procedure was used to assess the concentrations of APE and AE in activated and dehydrated sludge from two sewage treatment plants. Polyethoxylates were found in all samples in the concentration ranges 11-151, 100-138 and 23-141 mg/kg for octylphenol, nonylphenol and individual AE homologues, respectively. The method did not require clean-up or preconcentration steps. PMID:15387183

  2. Suitability of magnetic particle immunoassay for the analysis of PBDEs in Hawaiian freshwater fish and crabs in comparison with gas chromatography/electron capture detection-ion trap mass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A gas chromatograph/electron capture detector-ion trap mass spectrometer (GC/ECD-ITMS) was used for the determination of polybrominated diphenyl ethers (PBDEs) in freshwater fish and crabs. The samples were also analyzed with an enzyme-linked immunosorbent assay (ELISA). GC/ECD-ITMS results showed...

  3. Online volatile organic compound measurements using a newly developed proton-transfer ion-trap mass spectrometry instrument during New England Air Quality Study--Intercontinental Transport and Chemical Transformation 2004: performance, intercomparison, and compound identification.

    PubMed

    Warneke, Carsten; Kato, Shuji; De Gouw, Joost A; Goldan, Paul D; Kuster, William C; Shao, Min; Lovejoy, Edward R; Fall, Ray; Fehsenfeld, Fred C

    2005-07-15

    We have used a newly developed proton-transfer ion-trap mass spectrometry (PIT-MS) instrument for online trace gas analysis of volatile organic compounds (VOCs) during the 2004 New England Air Quality Study-Intercontinental Transport and Chemical Transformation study. The PIT-MS instrument uses proton-transfer reactions with H3O+ ions to ionize VOCs, similarto a PTR-MS (proton-transfer reaction mass spectrometry) instrument but uses an ion trap mass spectrometer to analyze the product ions. The advantages of an ion trap are the improved identification of VOCs and a near 100% duty cycle. During the experiment, the PIT-MS instrument had a detection limit between 0.05 and 0.3 pbbv (S/N = 3 (signal-to-noise ratio)) for 2-min integration time for most tested VOCs. PIT-MS was used for ambient air measurements onboard a research ship and agreed well with a gas chromatography mass spectrometer). The comparison included oxygenated VOCs, aromatic compounds, and others such as isoprene, monoterpenes, acetonitrile, and dimethyl sulfide. Automated collision-induced dissociation measurements were used to determine the contributions of acetone and propanal to the measured signal at 59 amu; both species are detected at this mass and are thus indistinguishable in conventional PTR-MS.

  4. An introduction to hybrid ion trap/time-of-flight mass spectrometry coupled with liquid chromatography applied to drug metabolism studies.

    PubMed

    Liu, Zhao-Ying

    2012-12-01

    Metabolism studies play an important role at various stages of drug discovery and development. Liquid chromatography combined with mass spectrometry (LC/MS) has become a most powerful and widely used analytical tool for identifying drug metabolites. The suitability of different types of mass spectrometers for metabolite profiling differs widely, and therefore, the data quality and reliability of the results also depend on which instrumentation is used. As one of the latest LC/MS instrumentation designs, hybrid ion trap/time-of-flight MS coupled with LC (LC-IT-TOF-MS) has successfully integrated ease of operation, compatibility with LC flow rates and data-dependent MS(n) with high mass accuracy and mass resolving power. The MS(n) and accurate mass capabilities are routinely utilized to rapidly confirm the identification of expected metabolites or to elucidate the structures of uncommon or unexpected metabolites. These features make the LC-IT-TOF-MS a very powerful analytical tool for metabolite identification. This paper begins with a brief introduction to some basic principles and main properties of a hybrid IT-TOF instrument. Then, a general workflow for metabolite profiling using LC-IT-TOF-MS, starting from sample collection and preparation to final identification of the metabolite structures, is discussed in detail. The data extraction and mining techniques to find and confirm metabolites are discussed and illustrated with some examples. This paper is directed to readers with no prior experience with LC-IT-TOF-MS and will provide a broad understanding of the development and utility of this instrument for drug metabolism studies.

  5. Scaling the ion trap quantum processor.

    PubMed

    Monroe, C; Kim, J

    2013-03-01

    Trapped atomic ions are standards for quantum information processing, serving as quantum memories, hosts of quantum gates in quantum computers and simulators, and nodes of quantum communication networks. Quantum bits based on trapped ions enjoy a rare combination of attributes: They have exquisite coherence properties, they can be prepared and measured with nearly 100% efficiency, and they are readily entangled with each other through the Coulomb interaction or remote photonic interconnects. The outstanding challenge is the scaling of trapped ions to hundreds or thousands of qubits and beyond, at which scale quantum processors can outperform their classical counterparts in certain applications. We review the latest progress and prospects in that effort, with the promise of advanced architectures and new technologies, such as microfabricated ion traps and integrated photonics.

  6. Cavity QED in a molecular ion trap

    SciTech Connect

    Schuster, D. I.; Bishop, Lev S.; Chuang, I. L.; DeMille, D.; Schoelkopf, R. J.

    2011-01-15

    We propose a class of experiments using rotational states of dipolar molecular ions trapped near an on-chip superconducting microwave cavity. Molecular ions have several advantages over neutral molecules for such cavity quantum electrodynamics experiments. In particular, ions can be loaded easily into deep rf traps and are held independent of their internal state. An analysis of the detection efficiency for, and coherence properties of, the molecular ions is presented. We discuss approaches for manipulating quantum information and performing high-resolution rotational spectroscopy using this system.

  7. An integrated strategy to quantitatively differentiate chemome between Cistanche deserticola and C. tubulosa using high performance liquid chromatography-hybrid triple quadrupole-linear ion trap mass spectrometry.

    PubMed

    Song, Yuelin; Song, Qingqing; Li, Jun; Zhang, Na; Zhao, Yunfang; Liu, Xiao; Jiang, Yong; Tu, Pengfei

    2016-01-15

    It is important to conduct large-scale detection, identification, and quantitation of metabolites in a given sample. Herein, a practical strategy was proposed to quantitatively compare the chemome between Cistanche deserticola (CD) and C. tubulosa (CT), which have been widely believed as the ideal edible and medicinal plants for conquering the deserts. The entire workflow was implemented on high performance liquid chromatography-hybrid triple quadrupole-linear ion trap mass spectrometer and consisted of three primary steps: (1) component detection and identification, various mass spectrometric approaches were applied to globally screen the chemical constituents, and structural elucidation was achieved by comparing with authentic compounds, analyzing MS(2) spectra, and referring to the literature along with accessible databases; (2) comprehensive relative quantitation, scheduled multiple reaction monitoring algorithm was introduced for relative quantitation of all detected ingredients; and (3) chemome comparison, the quantitative dataset was subjected for multivariate statistical analysis to carry out comparative study. A total of 513 metabolites were detected and relatively quantitated, and 379 ones were annotated. Betaine, Krebs cycle intermediates, phenylethanoid glycosides, and iridoids were picked out as the chemical markers being responsible for the discrimination of the chemical profiles between CD and CT. Above all, the quantitative chemome of CD and CT were exhaustively characterized and compared, which could advance their values concerning drug development, economics, and desertification control. The proposed strategy is expected as a reliable choice for widely targeted metabolomics of plants.

  8. Simultaneous determination of plant hormones in peach based on dispersive liquid-liquid microextraction coupled with liquid chromatography-ion trap mass spectrometry.

    PubMed

    Lu, Qiaomei; Zhang, Wenmin; Gao, Jia; Lu, Minghua; Zhang, Lan; Li, Jianrong

    2015-06-15

    Fruit development is influenced greatly by endogenous hormones including salicylic acid (SA) and abscisic acid (ABA). Mass spectrometry with high sensitivity has become a routine technology to analyze hormones. However, pretreatment of plant samples remains a difficult problem. Thus, dispersive liquid-liquid microextraction (DLLME) was used to concentrate trace plant hormones before liquid chromatography-ion trap mass spectrometry (LC-ITMS) analysis. Standard curves were linear within the ranges of 0.5-50, 0.2-20ng/mL for SA and ABA, respectively. The correlation coefficients were greater than 0.9995 with recoveries above 87.5%. The limits of detection were 0.2ng/mL for SA and 0.1ng/mL for ABA in spiked water solution, respectively (injection 20μL). The successful analysis of SA and ABA in fruit samples indicated our DLLME-LC-ITMS approach was efficient, allowing reliable quantification of both two compounds from very small amounts of plant material. Moreover, this research revealed the relationship between SA and ABA content and development of peach fruit at different growth stages.

  9. Characterization of oxygenated derivatives of isoprene related to 2-methyltetrols in Amazonian aerosols using trimethylsilylation and gas chromatography/ion trap mass spectrometry.

    PubMed

    Wang, Wu; Kourtchev, Ivan; Graham, Bim; Cafmeyer, Jan; Maenhaut, Willy; Claeys, Magda

    2005-01-01

    In the present study, we have tentatively identified the structures of three oxygenated derivatives of isoprene in Amazonian rain forest aerosols as the C(5) alkene triols, 2-methyl-1,3,4-trihydroxy-1-butene (cis and trans) and 3-methyl-2,3,4-trihydroxy-1-butene. The formation of these oxygenated derivatives of isoprene can be explained by acid-catalyzed ring opening of epoxydiol derivatives of isoprene, namely, 1,2-epoxy-2-methyl-3,4-dihydroxybutane and 1,2-dihydroxy-2-methyl-3,4-epoxybutane. The structural proposals of the C(5) alkene triols were based on chemical derivatization reactions and detailed interpretation of electron and chemical ionization mass spectral data, including data obtained from first-order mass spectra, deuterium labeling of the trimethylsilyl methyl groups, and MS(2) ion trap experiments. The characterization of 2-methyl-1,3,4-trihydroxy-1-butene (cis and trans) and 3-methyl-2,3,4-trihydroxy-1-butene in forest aerosols is important from an atmospheric chemistry viewpoint in that these compounds hint at the formation of intermediate isomeric epoxydiol derivatives of isoprene and as such provide mechanistic insights into the formation of the previously reported 2-methyltetrols through photooxidation of isoprene.

  10. Analysis of veterinary drug residues in shrimp: a multi-class method by liquid chromatography-quadrupole ion trap mass spectrometry.

    PubMed

    Li, Hui; Kijak, Philip James; Turnipseed, Sherri B; Cui, Wei

    2006-05-19

    A liquid chromatography-mass spectrometry (LC-MS) method was developed to screen and confirm veterinary drug residues in raw shrimp meat. This method simultaneously monitors 18 drugs of different classes, including oxytetracycline (OTC), sulfonamides, quinolones, cationic dyes, and toltrazuril sulfone (TOLS). The homogenized shrimp meat is extracted with 5% trichloroacetic acid. The extract is further cleaned using polymer-based SPE. A 50 mm phenyl column separates the analytes, prior to analysis with an ion trap mass spectrometer interfaced with an atmospheric pressure chemical ionization source. This method is able to confirm oxytetracycline residues at 200 ng/g, toltrazuril sulfone at 50 ng/g, sulfaquinoxaline at 20 ng/g, and the other 15 drugs at 10 ng/g or lower levels. An estimate of the level of residues can also be made so that only confirmed samples above action levels will be sent for quantitation. The method is validated with both fortified and incurred samples, using multiple shrimp species as well. This multi-class method can provide a means to simultaneously monitor for a wide range of illegal drug residues in shrimp. PMID:16597519

  11. An integrated strategy to quantitatively differentiate chemome between Cistanche deserticola and C. tubulosa using high performance liquid chromatography-hybrid triple quadrupole-linear ion trap mass spectrometry.

    PubMed

    Song, Yuelin; Song, Qingqing; Li, Jun; Zhang, Na; Zhao, Yunfang; Liu, Xiao; Jiang, Yong; Tu, Pengfei

    2016-01-15

    It is important to conduct large-scale detection, identification, and quantitation of metabolites in a given sample. Herein, a practical strategy was proposed to quantitatively compare the chemome between Cistanche deserticola (CD) and C. tubulosa (CT), which have been widely believed as the ideal edible and medicinal plants for conquering the deserts. The entire workflow was implemented on high performance liquid chromatography-hybrid triple quadrupole-linear ion trap mass spectrometer and consisted of three primary steps: (1) component detection and identification, various mass spectrometric approaches were applied to globally screen the chemical constituents, and structural elucidation was achieved by comparing with authentic compounds, analyzing MS(2) spectra, and referring to the literature along with accessible databases; (2) comprehensive relative quantitation, scheduled multiple reaction monitoring algorithm was introduced for relative quantitation of all detected ingredients; and (3) chemome comparison, the quantitative dataset was subjected for multivariate statistical analysis to carry out comparative study. A total of 513 metabolites were detected and relatively quantitated, and 379 ones were annotated. Betaine, Krebs cycle intermediates, phenylethanoid glycosides, and iridoids were picked out as the chemical markers being responsible for the discrimination of the chemical profiles between CD and CT. Above all, the quantitative chemome of CD and CT were exhaustively characterized and compared, which could advance their values concerning drug development, economics, and desertification control. The proposed strategy is expected as a reliable choice for widely targeted metabolomics of plants. PMID:26742897

  12. Accurate mass determination of short-lived isotopes by a tandem Penning-trap mass spectrometer

    SciTech Connect

    Stolzenberg, H.; Becker, S.; Bollen, G.; Kern, F.; Kluge, H.; Otto, T.; Savard, G.; Schweikhard, L. ); Audi, G. ); Moore, R.B. ); The ISOLDE Collaboration

    1990-12-17

    A mass spectrometer consisting of two Penning traps has been set up for short-lived isotopes at the on-line mass separator ISOLDE at CERN. The ion beam is collected and cooled in the first trap. After delivery to the second trap, high-accuracy direct mass measurements are made by determining the cyclotron frequency of the stored ions. Measurements have been performed for {sup 118}Cs--{sup 137}Cs. A resolving power of over 10{sup 6} and an accuracy of 1.4{times}10{sup {minus}7} have been achieved, corresponding to about 20 keV.

  13. Identification of glucosinolates in capers by LC-ESI-hybrid linear ion trap with Fourier transform ion cyclotron resonance mass spectrometry (LC-ESI-LTQ-FTICR MS) and infrared multiphoton dissociation.

    PubMed

    Bianco, Giuliana; Lelario, Filomena; Battista, Fabio Giuseppe; Bufo, Sabino A; Cataldi, Tommaso R I

    2012-09-01

    An liquid chromatography-mass spectrometry method using electrospray ionization in negative ion mode coupled with a hybrid quadrupole linear ion trap and Fourier transform ion cyclotron resonance (FTICR) mass spectrometer was applied to characterize of intact glucosinolates (GLSs) in crude sample extracts of wild bud flowers of Capparis spinosa (Capparis species, family Capparaceae). Structural information of GLSs was obtained upon precursor ions' isolation within the FTICR trapping cell and subsequent fragmentation induced by infrared multiphoton dissociation (IRMPD). Such a fragmentation was found very useful in terms of chemical identification of all precursor ions [M-H](-) including sulfur-rich GLSs reported here for the first time. Along with most common GLSs already found in capers such as glucocapparin, isopropyl/n-propyl-GLS, mercapto-glucocapparin, and two indolic GLS, i.e., 4-hydroxyglucobrassicin and glucobrassicin, the occurrence of the uncommon glycinyl-glucocapparin as well as two sulfur-rich GLSs is reported. IRMPD showed an increased selectivity towards disulfide bond cleavages with thiol migration, suggesting the side chain structure of non-targeted compounds, i.e., disulfanyl-glucocapparin and trisulfanyl-glucocapparin. Glucocapparin [2.05 ± 0.25 mg/g, dry weight (dw)] was the most abundant GLS, followed by glucobrassicin (232 ± 18 µg/g, dw) and 4-hydroxyglucobrassicin (89 ± 12 µg/g, dw). All other compounds were present at very low content ranging from 0.5 to 1.5 µg/g dw.

  14. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn) for measuring organic acids in concentrated bulk aerosol - a laboratory and field study

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Brüggemann, M.; Ehn, M.; Junninen, H.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Williams, J.; Hoffmann, T.

    2012-08-01

    The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was increased by a factor of 7.5 to 11 (e.g. ~40 ng m-3 for pinonic acid) by using the miniature Versatile Aerosol Concentration Enrichment System (mVACES) upstream of the mass spectrometer. The APCI-IT-MS was calibrated in the negative ion mode with two biogenic organic acid standards - pinic acid and pinonic acid. Pinic acid was used as a surrogate for the quantification of the total amount of organic acids in the ambient aerosol based on the total signal intensities in the negative ion mode. The results were compared with the total organic signal of a C-ToF-AMS during the HUMPPA-COPEC 2010 field campaign. The campaign average contribution of organic acids measured by APCI-IT-MS to the total sub-micron organic aerosol mass was estimated to be about 60%. Very good correlation between APCI-IT-MS and C-ToF-AMS (Pearson's R = 0.94) demonstrates soft ionization mass spectrometry as a complimentary technique to AMS with electron impact ionization. MS2 studies of specific m/z ratios recorded during the HUMPPA-COPEC 2010 field campaign were compared to MS2 studies of selected monoterpene oxidation products formed in simulation chamber experiments. The comparison of the resulting fragments shows that oxidation products of the main VOCs emitted at Hyytiälä (α-pinene and Δ3-carene) cannot account for all of the measured fragments, which illustrates the complexity of ambient aerosol and possibly indicates unidentified or underestimated biogenic SOA precursor in the boreal forest.

  15. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn) for measuring organic acids in concentrated bulk aerosol - a laboratory and field study

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Brüggemann, M.; Ehn, M.; Junninen, H.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Williams, J.; Hoffmann, T.

    2013-02-01

    The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft-ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was improved by a factor of 7.5 to 11 (e.g. ∼40 ng m3 for pinonic acid) by using the miniature versatile aerosol concentration enrichment system (mVACES) upstream of the mass spectrometer. The APCI-IT-MS was calibrated in the negative ion mode with two biogenic organic acid standards - pinic acid and pinonic acid. Pinic acid was used as a surrogate for the quantification of the total amount of organic acids in the ambient aerosol based on the total signal intensities in the negative ion mode. The results were compared with the total organic signal of a C-ToF-AMS during the HUMPPA-COPEC 2010 field campaign. The campaign average contribution of organic acids measured by APCI-IT-MS to the total submicron organic aerosol mass was estimated to be about 60%, based on the response of pinic acid. Very good correlation between APCI-IT-MS and C-ToF-AMS (Pearson's R = 0.94) demonstrates soft-ionization mass spectrometry as a complimentary technique to AMS with electron impact ionization. MS2 studies of specific m/z ratios recorded during the HUMPPA-COPEC 2010 field campaign were compared to MS2 studies of selected monoterpene oxidation products formed in simulation chamber experiments. The comparison of the resulting fragments shows that oxidation products of the main VOCs emitted at Hyytiälä (α-pinene and Δ3-carene) cannot account for all of the measured fragments. Possible explanations for those unaccounted fragments are the presence of unidentified or underestimated biogenic SOA precursors, or that different products are formed by a different oxidant

  16. Vibrational Spectroscopy on Trapped Cold Molecular Ions

    NASA Astrophysics Data System (ADS)

    Khanyile, Ncamiso B.; Brown, Kenneth R.

    2014-06-01

    We perform vibrational spectroscopy on the V0←10 overtone of a trapped and sympathetically cooled CaH+ molecular ion using a resonance enhanced two photon dissociation scheme. Our experiments are motivated by theoretical work that proposes comparing the vibrational overtones of CaH^+ with electronic transitions in atoms to detect possible time variation of in the mass ratio of the proton to electron. Due to the nonexistence of experimental data of the transition, we start the search with a broadband femtosecond Ti:Saph laser guided by theoretical calculations. Once the vibrational transition has been identified, we will move to CW lasers to perform rotationally resolved spectroscopy. M. Kajita and Y. Moriwaki, J. Phys. B. At. Mol. Opt.Phys., 42,154022(2009) Private communication

  17. Measuring Gas-Phase Basicities of Amino Acids Using an Ion Trap Mass Spectrometer: A Physical Chemistry Laboratory Experiment

    ERIC Educational Resources Information Center

    Sunderlin, Lee S.; Ryzhov, Victor; Keller, Lanea M. M.; Gaillard, Elizabeth R.

    2005-01-01

    An experiment is performed to measure the relative gas-phase basicities of a series of five amino acids to compare the results to literature values. The experiments use the kinetic method for deriving ion thermochemistry and allow students to perform accurate measurements of thermodynamics in a relatively short time.

  18. Rydberg Excitation of a Single Trapped Ion.

    PubMed

    Feldker, T; Bachor, P; Stappel, M; Kolbe, D; Gerritsma, R; Walz, J; Schmidt-Kaler, F

    2015-10-23

    We demonstrate excitation of a single trapped cold (40)Ca(+) ion to Rydberg levels by laser radiation in the vacuum ultraviolet at a wavelength of 122 nm. Observed resonances are identified as 3d(2)D(3/2) to 51F, 52F and 3d(2)D(5/2) to 64F. We model the line shape and our results imply a large state-dependent coupling to the trapping potential. Rydberg ions are of great interest for future applications in quantum computing and simulation, in which large dipolar interactions are combined with the superb experimental control offered by Paul traps. PMID:26551109

  19. Identification of N-Oxide and Sulfoxide Functionalities in Protonated Drug Metabolites by Using Ion-Molecule Reactions Followed by Collisionally Activated Dissociation in a Linear Quadrupole Ion Trap Mass Spectrometer.

    PubMed

    Sheng, Huaming; Tang, Weijuan; Yerabolu, Ravikiran; Max, Joann; Kotha, Raghavendhar R; Riedeman, James S; Nash, John J; Zhang, Minli; Kenttämaa, Hilkka I

    2016-01-15

    The in vivo oxidation of sulfur and nitrogen atoms in many drugs into sulfoxide and N-oxide functionalities is a common biotransformation process. Unfortunately, the unambiguous identification of these metabolites can be challenging. In the present study, ion-molecule reactions of tris(dimethylamino)borane followed by collisionally activated dissociation (CAD) in an ion trap mass spectrometer are demonstrated to allow the identification of N-oxide and sulfoxide functionalities in protonated polyfunctional drug metabolites. Only ions with N-oxide or sulfoxide functionality formed diagnostic adducts that had lost dimethyl amine (DMA). This was demonstrated even for an analyte that contains a substantially more basic functionality than the functional group of interest. CAD of the diagnostic product ions (M) resulted mainly in type A (M - DMA) and B fragment ions (M - HO-B(N(CH3)2)2) for N-oxides, but sulfoxides also formed diagnostic C ions (M - O═BN(CH3)2), thus allowing differentiation of the functionalities. Some protonated analytes yielded abundant TDMAB adducts that had lost two DMA molecules instead of just one. This provides information on the environment of the N-oxide and sulfoxide functionalities. Quantum chemical calculations were performed to explore the mechanisms of the above-mentioned reactions. The method can be implemented on HPLC for real drug analysis. PMID:26651970

  20. Identification of cytochrome P450 3A4 modification site with reactive metabolite using linear ion trap-Fourier transform mass spectrometry.

    PubMed

    Yukinaga, Hideo; Takami, Tomonori; Shioyama, Sho-Hei; Tozuka, Zenzaburo; Masumoto, Hiroshi; Okazaki, Osamu; Sudo, Ken-Ichi

    2007-10-01

    Covalent binding of reactive metabolites to cytochrome P450s (P450s) often causes their mechanism-based inactivation (MBI), resulting in drug-drug interactions or toxicity. The detection and identification of the P450 sites to which reactive metabolites bind would elucidate MBI mechanisms. We describe a proteomic approach using nano-LC/linear ion trap-Fourier transform ion cyclotron resonance (FTICR) mass spectrometry to characterize the binding of a reactive metabolite of raloxifene, which is a known P450 3A4 inhibitor, to the P450 3A4 isozyme. LTQ-FT analyses revealed that the metabolic reaction of raloxifene in a reconstituted P450 3A4 system formed a reactive metabolite adduct to P450 3A4 apoprotein, accompanied by a mass shift of 471 Da relative to intact P450 3A4 apoprotein. The reaction mixtures were digested with trypsin, and then the tryptic digests were analyzed by nano-LC-MS/MS. This technique revealed that VWGFYDGQQPVLAITDPDMIK (position 71-91) was a tryptic peptide modified by the reactive metabolite derived from raloxifene. The site of adduction with the reactive metabolite was further postulated to be the nucleophilic OH group of Tyr-75 of P450 3A4. A proteomic approach using LTQ-FT can yield direct information on the P450 3A4 modification site without radiolabeled compounds. In addition, this information can elucidate mechanisms involved in the covalent binding of reactive metabolites and the inactivation of P450 3A4. PMID:17867646

  1. A Quadrupole Ion Trap Mass Spectrometer for Quantitative Analysis of Nitrogen-Purged Compartments within the Space Shuttle

    NASA Technical Reports Server (NTRS)

    Ottens, Andrew K.; Griffin, Timothy P.; Helms, William R.; Yost, Richard A.; Steinrock, T. (Technical Monitor)

    2001-01-01

    To enter orbit the Space Shuttle burns 1.8 million liters of liquid hydrogen combined with 0.8 million liters of liquid oxygen through three rocket engines mounted in the aft. NASA monitors the nitrogen-purged aft compartment for increased levels of hydrogen or oxygen in order to detect and determine the severity of a cryogenic fuel leak. Current monitoring is accomplished with a group of mass spectrometer systems located as much as 400 feet away from the shuttle. It can take up to 45 seconds for gas to reach the mass spectrometer, which precludes monitoring for leaks in the final moments before liftoff (the orbiter engines are started at T-00:06 seconds). To remedy the situation, NASA is developing a small rugged mass spectrometer to be used as point-sources around the Space Shuttle.

  2. A study of the analytical behaviour of selected psycho-active drugs using liquid chromatography, ion trap mass spectrometry, gas chromatography and polarography and the construction of an appropriate database for drug characterisation.

    PubMed

    Doherty, Bernadette; O'Donnell, Fionnuala; Smyth, W Franklin; Leslie, Julian C; Ramachandran, Venkataraman N; Boyd, Neil S; Hack, Catherine J; O'Kane, Edmund; McClean, Stephen

    2007-04-30

    This paper provides analytical chemical information on a range of psycho-active drugs. This analytical chemical information on liquid chromatography-electrospray ionisation-mass spectrometry (HPLC-ESI-MS), ion trap mass spectrometry (ESI-MS(n)), gas chromatography-flame ionisation detection (GLC-FID) and polarographic behaviour is then incorporated into a database which is of use in drug characterisation. Application is found in the determination of selected drug compounds in hair samples.

  3. Quantitation of isobaric phosphatidylcholine species in human plasma using a hybrid quadrupole linear ion trap mass spectrometer

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Phosphatidylcholine (PC) species in human plasma are used as biomarkers of disease. PC biomarkers are often limited by the inability to separate isobaric PC. In this work, we developed a targeted shotgun approach for analysis of isobaric and isomeric PC. This approach is comprised of two mass spectr...

  4. A trapped mercury 199 ion frequency standard

    NASA Technical Reports Server (NTRS)

    Cutler, L. S.; Giffard, R. P.; Mcguire, M. D.

    1982-01-01

    Mercury 199 ions confined in an RF quadrupole trap and optically pumped by mercury 202 ion resonance light are investigated as the basis for a high performance frequency standard with commercial possibilities. Results achieved and estimates of the potential performance of such a standard are given.

  5. Recent developments in Penning-trap mass spectrometry

    NASA Astrophysics Data System (ADS)

    Block, M.

    2016-06-01

    Penning-trap mass spectrometry provides atomic masses with the highest precision. At accelerator-based on-line facilities it is applied to investigate exotic radionuclides in the context of tests of fundamental symmetries, nuclear structure studies, and nuclear astrophysics research. Recent progress in slowing down radioactive ion-beams in buffer-gas cells in combination with advanced ion-manipulation techniques has paved the way to reach nuclides ever-more far from stability. In this endeavor many efforts are underway to increase the sensitivity, the efficiency, and the precision of Penning-trap mass spectrometry. In this article some recent experimental developments are addressed with the focus on the phase-imaging ion-cyclotron-resonance technique and the Fourier transform ion-cyclotron-resonance technique.

  6. Analysis of active alkaloids in the Menispermaceae family by nonaqueous capillary electrophoresis-ion trap mass spectrometry.

    PubMed

    Chen, Qinhua; Zhang, Juan; Zhang, Wenpeng; Chen, Zilin

    2013-01-01

    A nonaqueous CE-IT MS with a nanospray ionization interface method was developed for the identification and quantification of tetrandrine (TET), fangchinoline (FAN), and sinomenine (SIN) using berberine as internal standard. The TET, FAN, and SIN standard solutions were directly infused into IT-MS for collecting MS(1-3) spectra. The major fragment ions of analytes were confirmed and possible main cleavage pathways of fragment ions were studied. A bare fused-silica capillary was used for separation of the analytes. A sheath liquid (50% aqueous methanol containing 0.2% acetic acid) to the capillary effluent with a nanoelectrospray ionization interface was added. Separation buffer comprised 80 mM solution of ammonium acetate, in a mixture of 70% methanol, 20% ACN, and 10% water, which also contained 1% acetic acid. The CE-MS method was validated for linearity, sensitivity, accuracy, and precision, and then used to determine the content of the above components. The detection limits of TET, FAN, and SIN are 0.05, 0.08, and 0.15 μg/mL, respectively. The precision was no more than 4.67% and the mean recovery of the analytes were 95.36-99.24%. This method was successfully applied to determine TET, FAN, and SIN in real samples radix Stephaniae tetrandrae and rhizomes of Menispermum dauricum. PMID:23255368

  7. Design, microfabrication, and analysis of micrometer-sized cylindrical ion trap arrays.

    PubMed

    Cruz, D; Chang, J P; Fico, M; Guymon, A J; Austin, D E; Blain, M G

    2007-01-01

    A description of the design and microfabrication of arrays of micrometer-scale cylindrical ion traps is offered. Electrical characterization and initial ion trapping experiments with a massively parallel array of 5 microm internal radius (r(0)) sized cylindrical ion traps (CITs) are also described. The ion trap, materials, and design are presented and shown to be critical in achieving minimal trapping potential while maintaining minimal power consumption. The ion traps, fabricated with metal electrodes, have inner radii of 1, 2, 5, and 10 microm and range from 5 to 24 microm in height. The electrical characteristics of packaged ion trap arrays were measured with a vector network analyzer. The testing focused on trapping toluene (C(7)H(8)), mass 91, 92, or 93 amu, in the 5 microm sized CITs. Ions were formed via electron impact ionization and were ejected by turning off the rf voltage applied to the ring electrode; a current signal was collected at this time. Optimum ionization and trapping conditions, such as a sufficient pseudopotential well and high ionization to ion loss rate ratio (as determined by simulation), proved to be difficult to establish due to the high device capacitance and the presence of exposed dielectric material in the trapping region. However, evidence was obtained suggesting the trapping of ions in 1%-15% of the traps in the array. These first tests on micrometer-scale CITs indicated the necessary materials and device design modifications for realizing ultrasmall and low power ion traps.

  8. Trapped ion scaling with pulsed fast gates

    NASA Astrophysics Data System (ADS)

    Bentley, C. D. B.; Carvalho, A. R. R.; Hope, J. J.

    2015-10-01

    Fast entangling gates for trapped ion pairs offer vastly improved gate operation times relative to implemented gates, as well as approaches to trap scaling. Gates on a neighbouring ion pair only involve local ions when performed sufficiently fast, and we find that even a fast gate between a pair of distant ions with few degrees of freedom restores all the motional modes given more stringent gate speed conditions. We compare pulsed fast gate schemes, defined by a timescale faster than the trap period, and find that our proposed scheme has less stringent requirements on laser repetition rate for achieving arbitrary gate time targets and infidelities well below 10-4. By extending gate schemes to ion crystals, we explore the effect of ion number on gate fidelity for coupling two neighbouring ions in large crystals. Inter-ion distance determines the gate time, and a factor of five increase in repetition rate, or correspondingly the laser power, reduces the infidelity by almost two orders of magnitude. We also apply our fast gate scheme to entangle the first and last ions in a crystal. As the number of ions in the crystal increases, significant increases in the laser power are required to provide the short gate times corresponding to fidelity above 0.99.

  9. Studies on the metabolism of mitragynine, the main alkaloid of the herbal drug Kratom, in rat and human urine using liquid chromatography-linear ion trap mass spectrometry.

    PubMed

    Philipp, Anika A; Wissenbach, Dirk K; Zoerntlein, Siegfried W; Klein, Oliver N; Kanogsunthornrat, Jidapha; Maurer, Hans H

    2009-08-01

    Mitragynine (MG) is an indole alkaloid of the Thai medicinal plant Mitragyna speciosa (Kratom in Thai) and reported to have opioid agonistic properties. Because of its stimulant and euphoric effects, Kratom is used as a herbal drug of abuse. The aim of the presented study is to identify the phase I and II metabolites of MG in rat and human urine after solid-phase extraction (SPE) using liquid chromatography-linear ion trap mass spectrometry providing detailed structure information in the MSn mode particularly with high resolution. The seven identified phase I metabolites indicated that MG was metabolized by hydrolysis of the methylester in position 16, O-demethylation of the 9-methoxy group and of the 17-methoxy group, followed, via the intermediate aldehydes, by oxidation to carboxylic acids or reduction to alcohols and combinations of some steps. In rats, four metabolites were additionally conjugated to glucuronides and one to sulfate, but in humans, three metabolites to glucuronides and three to sulfates. PMID:19536806

  10. Fused-core silica column ultra-performance liquid chromatography-ion trap tandem mass spectrometry for determination of global DNA methylation status.

    PubMed

    Yang, Ill; Fortin, Marie C; Richardson, Jason R; Buckley, Brian

    2011-02-01

    Epigenetic modifications, such as DNA methylation, play key roles in transcriptional regulation of gene expression. More recently, global DNA methylation levels have been documented to be altered in several diseases, including cancer, and as the result of exposure to environmental toxicants. Based on the potential use of global DNA methylation status as a biomarker of disease status and exposure to environmental toxicants, we sought to develop a rapid, sensitive, and precise analytical method for the quantitative measurement of global DNA methylation status using ultra-performance liquid chromatography with detection by ion trap tandem mass spectrometry. Using a fused-core silica column, 2'-deoxyguanosine (2dG) and 5-methyl-2'-deoxycytidine (5mdC) were resolved in less than 1 min with detection limits of 0.54 and 1.47 fmol for 5mdC and 2dG, respectively. The accuracy of detection was 95% or higher, and the day-to-day coefficient of variation was found to be 3.8%. The method was validated by quantification of global DNA methylation status following treatment of cells with the DNA methyltransferase inhibitor 5-aza-2'-deoxycytidine, which reduced DNA methylation from 3.1% in control cells to 1.1% in treated cells. The sensitivity and high throughput of this method rend it suitable for large-scale analysis of epidemiological and clinical DNA samples.

  11. Method for detection of trace metal and metalloid contaminants in coal-generated fuel gas using gas chromatography/ion trap mass spectrometry.

    PubMed

    Rupp, Erik C; Granite, Evan J; Stanko, Dennis C

    2010-07-15

    There exists an increasing need to develop a reliable method to detect trace contaminants in fuel gas derived from coal gasification. While Hg is subject to current and future regulations, As, Se, and P emissions may eventually be regulated. Sorbents are the most promising technology for the removal of contaminants from coal-derived fuel gas, and it will be important to develop a rapid analytical detection method to ensure complete removal and determine the ideal time for sorbent replacement/regeneration in order to reduce costs. This technical note explores the use of a commercial gas chromatography/ion trap mass spectrometry system for the detection of four gaseous trace contaminants in a simulated fuel gas. Quantitative, repeatable detection with limits at ppbv to ppmv levels were obtained for arsine (AsH(3)), phosphine (PH(3)), and hydrogen selenide (H(2)Se), while qualitative detection was observed for mercury. Decreased accuracy and response caused by the primary components of fuel gas were observed.

  12. Trace analysis of pesticides in paddy field water by direct injection using liquid chromatography-quadrupole-linear ion trap-mass spectrometry.

    PubMed

    Pareja, Lucía; Martínez-Bueno, M J; Cesio, Verónica; Heinzen, Horacio; Fernández-Alba, A R

    2011-07-29

    A multiresidue method was developed for the quantification and confirmation of 70 pesticides in paddy field water. After its filtration, water was injected directly in a liquid chromatograph coupled to a hybrid triple quadrupole-linear ion trap-mass spectrometer (QqLIT). The list of target analytes included organophosphates, phenylureas, sulfonylureas, carbamates, conazoles, imidazolinones and others compounds widely used in different countries where rice is cropped. Detection and quantification limits achieved were in the range from 0.4 to 80 ng L(-1) and from 2 to 150 ng L(-1), respectively. Correlation coefficients for the calibration curves in the range 0.1-50 μg L(-1) were higher than 0.99 except for diazinon (0.1-25 μg L(-1)). Only 9 pesticides presented more than 20% of signal suppression/enhancement, no matrix effect was observed in the studied conditions for the rest of the target pesticides. The method developed was used to investigate the occurrence of pesticides in 59 water samples collected in paddy fields located in Spain and Uruguay. The study shows the presence of bensulfuron methyl, tricyclazole, carbendazim, imidacloprid, tebuconazole and quinclorac in a concentration range from 0.08 to 7.20 μg L(-1).

  13. Identification of sulfoglycolipids from the alga Porphyridium purpureum by matrix-assisted laser desorption/ionisation quadrupole ion trap time-of-flight mass spectrometry.

    PubMed

    Naumann, Ivonne; Darsow, Kai H; Walter, Christian; Lange, Harald A; Buchholz, Rainer

    2007-01-01

    Sulfoglycolipids, isolated from different phototrophic organisms, particularly plants and algae, have already been identified as bioactive compounds. In addition to their antiviral activity their influence on the immune response in mammalian cells is the focus of many studies. For the first time it has been possible to investigate purified sulfoquinovosyldiacylglycerols (SQDGs) from the microalga Porphyridium purpureum by matrix-assisted laser desorption/ionisation (MALDI) in the negative ion reflectron mode. Thereby, different solid and ionic liquid matrices have been tested to improve signal intensity during the laser ionisation. By using the MALDI Trap time-of-flight (ToF) multiple-stage (MS(n)) hybrid mass spectrometer the fatty acid compositions of the SQDGs were analysed by MS, and confirmed by MS(2) and MS(3) experiments. Thereby, hexadecanoic acid (C16:0), octadecadienoic acid (C18:2), eicosatetraenoic acid (C20:4), and eicosapentaenoic acid (C20:5) were detected in the purified fraction of SQDGs. The localisation of hexadecanoic acid (C16:0) at the sn-2 position, and unsaturated fatty acids at the sn-1 position of the SQDGs, determined by specific enzymatic hydrolysis, marks a procaryotic biosynthesis of SQDGs in the eucaryotic alga cells.

  14. Polar organic chemical integrative sampling and liquid chromatography- electrospray/ion-trap mass spectrometry for assessing selected prescription and illicit drugs in treated sewage effluents

    USGS Publications Warehouse

    Jones-Lepp, T. L.; Alvarez, D.A.; Petty, J.D.; Huckins, J.N.

    2004-01-01

    The purpose of the research presented in this paper was twofold: (1) to demonstrate the coupling of two state-of-the-art techniques: a time-weighted polar organic chemical integrative sampler (POCIS) and microliquid chromatography-electrospray/ion-trap mass spectrometry and (2) to assess the ability of these methodologies to detect six drugs (azithromycin, fluoxetine, omeprazole, levothyroxine, methamphetamine, methylenedioxymethamphetamine [MDMA]) in a real-world environment, e.g., waste water effluent. In the effluent from three wastewater treatment plants (WWTPs), azithromycin was detected at concentrations ranging from 15 to 66 ng/L, which is equivalent to a total annual release of 1 to 4 kg into receiving waters. Detected and confirmed in the effluent from two WWTPs were two illicit drugs, methamphetamine and MDMA, at 2 and 0.5 ng/L, respectively. Although the ecotoxicologic significance of drugs in environmental matrices, particularly water, has not been closely examined, it can only be surmised that these substances have the potential to adversely affect biota that are continuously exposed to them even at very low levels. The potential for chronic effects on human health is also unknown but of increasing concern because of the multi-use character of water, particularly in densely populated, arid areas.

  15. HPLC/ESI-quadrupole ion trap mass spectrometry for characterization and direct quantification of amphoteric and nonionic surfactants in aqueous samples

    NASA Technical Reports Server (NTRS)

    Levine, Lanfang H.; Garland, Jay L.; Johnson, Jodie V.

    2002-01-01

    An amphoteric (cocamidopropylbetaine, CAPB) and a nonionic (alcohol polyethoxylate, AE) surfactant were characterized by electrospray ionization quadrupole ion trap mass spectrometry (ESI-MS) as to their homologue distribution and ionization/fragmentation chemistry. Quantitative methods involving reversed-phase gradient HPLC and (+)ESI-MSn were developed to directly determine these surfactants in hydroponic plant growth medium that received simulated graywater. The predominant homologues, 12 C alkyl CAPB and 9 EO AE, were monitored to represent the total amount of the respective surfactants. The methods demonstrated dynamic linear ranges of 0.5-250 ng (r2 > 0.996) for CAPB and 8-560 ng (r2 > 0.998) for AE homologue mixture, corresponding to minimum quantification limits of 25 ppb CAPB and 0.4 ppm AE with 20-microL injections. This translated into an even lower limit for individual components due to the polydispersive nature of the surfactants. The procedure was successfully employed for the assessment of CAPB and AE biodegradation in a hydroponic plant growth system used as a graywater bioreactor.

  16. Liquid chromatography-electrospray linear ion trap mass spectrometry analysis of targeted neuropeptides in Tac1(-/-) mouse spinal cords reveals significant lower concentration of opioid peptides.

    PubMed

    Saidi, Mouna; Beaudry, Francis

    2015-08-01

    Tachykinin and opioid peptides play a central role in pain transmission, modulation and inhibition. The treatment of pain is very important in medicine and many studies using NK1 receptor antagonists failed to show significant analgesic effects in humans. Recent investigations suggest that both pronociceptive tachykinins and the analgesic opioid systems are important for normal pain sensation. The analysis of opioid peptides in Tac1(-/-) spinal cord tissues offers a great opportunity to verify the influence of the tachykinin system on specific opioid peptides. The objectives of this study were to develop an HPLC-MS/MRM assay to quantify targeted peptides in spinal cord tissues. Secondly, we wanted to verify if the Tac1(-/-) mouse endogenous opioid system is hampered and therefore affects significantly the pain modulatory pathways. Targeted neuropeptides were analyzed by high performance liquid chromatography linear ion trap mass spectrometry. Our results reveal that EM-2, Leu-Enk and Dyn A were down-regulated in Tac1(-/-) spinal cord tissues. Interestingly, Dyn A was almost 3 fold down-regulated (p<0.0001). No significant concentration differences were observed in mouse Tac1(-/-) spinal cords for Met-Enk and CGRP. The analysis of Tac1(-/-) mouse spinal cords revealed noteworthy decreases of EM-2, Leu-Enk and Dyn A concentrations which strongly suggest a significant impact on the endogenous pain-relieving mechanisms. These observations may have insightful impact on future analgesic drug developments and therapeutic strategies.

  17. Determination of pesticides associated with suspended sediments in the San Joaquin River, California, USA, using gas chromatography-ion trap mass spectrometry

    USGS Publications Warehouse

    Bergamaschi, B.A.; Baston, D.S.; Crepeau, K.L.; Kuivila, K.M.

    1999-01-01

    An analytical method useful for the quantification of a range of pesticides and pesticide degradation products associated with suspended sediments was developed by testing a variety of extraction and cleanup schemes. The final extraction and cleanup methods chosen for use are suitable for the quantification of the listed pesticides using gas chromatography-ion trap mass spectrometry and the removal of interfering coextractable organic material found in suspended sediments. Methylene chloride extraction followed by Florisil cleanup proved most effective for separation of coextractives from the pesticide analytes. Removal of elemental sulfur was accomplished with tetrabutylammonium hydrogen sulfite. The suitability of the method for the analysis of a variety of pesticides was evaluated, and the method detection limits (MDLs) were determined (0.1-6.0 ng/g dry weight of sediment) for 21 compounds. Recovery of pesticides dried onto natural sediments averaged 63%. Analysis of duplicate San Joaquin River suspended-sediment samples demonstrated the utility of the method for environmental samples with variability between replicate analyses lower than between environmental samples. Eight of 21 pesticides measured were observed at concentrations ranging from the MDL to more than 80 ng/g dry weight of sediment and exhibited significant temporal variability. Sediment-associated pesticides, therefore, may contribute to the transport of pesticides through aquatic systems and should be studied separately from dissolved pesticides.

  18. Analysis of polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in vegetable oil samples by gas chromatography-ion trap tandem mass spectrometry.

    PubMed

    Malavia, J; Abalos, M; Santos, F J; Abad, E; Rivera, J; Galceran, M T

    2007-05-18

    Gas chromatography coupled to ion trap tandem mass spectrometry (CG-MS-MS) has been evaluated for the analysis of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in vegetable oil samples containing different concentration levels (0.2-6 pg WHO-TEQ g(-1) for both PCDD/Fs and dl-PCBs) of the 29 toxic congeners of PCDD/F and dioxin-like PCBs. The effect of potential interfering compounds such as polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs) and polychlorinated diphenylethers (PCDEs) on the quantification of mono-ortho PCBs has been investigated. In addition, the influence of the clean-up procedure on the final determination by CG-MS-MS was studied, showing that the quality of the results depends to a great extent on this analytical step. Quality parameters have been established and good precisions (CV: 3-19%) and low limits of detection for PCDD/Fs (0.04-0.20 pg g(-1) oil) and dl-PCBs (0.08-0.64 pg g(-1) oil) were obtained. The method was validated by a comparison of the CG-MS-MS results with those obtained by GC-HRMS.

  19. Liquid chromatography coupled to ion trap-tandem mass spectrometry to evaluate juvenile hormone III levels in bee hemolymph from Nosema spp. infected colonies.

    PubMed

    Ares, A M; Nozal, M J; Bernal, J L; Martín-Hernández, R; M Higes; Bernal, J

    2012-06-15

    It has been described a fast, simple and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method to measure juvenile hormone III (JH III), which was used to study of the effects of Nosema spp. infection on JH III levels in bee hemolymph. Honey bee hemolymph was extracted by centrifugation and mixed with a solution of phenylthiourea in methanol. This mixture was then centrifuged and the supernatant removed and evaporated to dryness. The residue was reconstituted in methanol containing the internal standard (methoprene) and injected onto an LC-MS/MS (ion-trap) system coupled to electrospray ionization (ESI) in positive mode. Chromatography was performed on a Synergi Hydro-RP column (4 μm, 30 mm × 4.60 mm i.d.) using a mobile phase of 20 mM ammonium formate and methanol in binary gradient elution mode. The method was fully validated and it was found to be selective, linear from 15 to 14,562 pg/μL, precise and accurate, with %RSD values below 5%. The limits of detection and quantification were: LOD, 6 pg/μL; LOQ, 15 pg/μL. Finally, the proposed LC-MS/MS method was used to analyze JH III levels in the hemolymph of worker honey bees (Apis mellifera iberiensis) experimentally infected with different Nosema spp. (Nosema apis, Spanish and Dutch Nosema ceranae strains). The highest concentrations of JH III were detected in hemolymph from bees infected with Spanish N. ceranae.

  20. Quantitative determination of isoquinoline alkaloids and chlorogenic acid in Berberis species using ultra high performance liquid chromatography with hybrid triple quadrupole linear ion trap mass spectrometry.

    PubMed

    Singh, Awantika; Bajpai, Vikas; Kumar, Sunil; Arya, Kamal Ram; Sharma, Kulwant Rai; Kumar, Brijesh

    2015-06-01

    Berberis species are well known and used extensively as medicinal plants in traditional medicine. They have many medicinal values attributable to the presence of alkaloids having different pharmacological activities. In this study, a method was developed and validated as per international conference on harmonization guidelines using ultra high performance liquid chromatography with hybrid triple quadrupole-linear ion trap mass spectrometry operated in the multiple reaction monitoring mode for nine bioactive compounds, including protoberberine alkaloids, aporphine alkaloids and chlorogenic acid. This method was applied in different plant parts of eight Berberis species to determine variations in content of nine bioactive compounds. The separation was achieved on an ACQUITY UPLC CSH™ C18 column using a gradient mobile phase at flow rate 0.3 mL/min. Calibration curves for all the nine analytes provided optimum linear detector response (with R(2) ≥0.9989) over the concentration range of 0.5-1000 ng/mL. The precision and accuracy were within RSDs ≤2.4 and ≤2.3%, respectively. The results indicated significant variation in the total contents of the nine compounds in Berberis species.

  1. Application of low-pressure gas chromatography-ion-trap mass spectrometry to the analysis of the essential oil of Turnera diffusa (Ward.) Urb.

    PubMed

    Godoi, Ana F L; Vilegas, Wagner; Godoi, Ricardo H M; Van Vaeck, Luc; Van Grieken, René

    2004-02-20

    Turnera diffusa Willd. var. afrodisiaca (Ward) Urb. (syn. T. aphrodisiaca) belongs to the family of Turneraceae and is an aromatic plant growing wild in the subtropical regions of America and Africa. It is widely used in the traditional medicine as e.g. anti-cough, diuretic, and aphrodisiac agent. This work presents a 3 min chromatographic analysis using low-pressure (LP) gas chromatography (GC)-ion-trap (IT) mass spectrometry (MS). The combination of a deactivated 0.6 m x 0.10 mm i.d., restrictor with a wide-bore CP-Wax 52 capillary column (10 m x 0.53 mm i.d., 1 microm) reduces the analysis time by a factor of 3-7 in comparison to the use of a conventional narrow bore column. Chromatographic conditions have been optimized to achieve the fastest separation with the highest signal/noise ratio in MS detection. These results allow fast and reliable quality control of the essential oil to be achieved. PMID:14971493

  2. [Determination of aldicarb and its metabolites in peanuts by high performance liquid chromatography-linear ion trap triple stage mass spectrometry].

    PubMed

    Yang, Xin; Li, Peng; Zhao, Yunfeng; Wu, Yongning

    2012-03-01

    A high performance liquid chromatography-linear ion trap triple stage mass spectrometry (HPLC-IT/MS3) method was established to detect aldicarb, aldicarb sulfoxide, and aldicarb sulfone in peanuts. The samples were extracted by acetonitrile saturated with cyclohexane, followed by clean-up with gel permeation chromatography (GPC). The determination was performed using HPLC-IT/MS3 for the identification and quantification of the compounds. The separation was carried on a Capcell PAK CR column with gradient elution using 5 mmol/L acetic acid/ammonium acetate/acetonitrile as mobile phase. The ionization of molecules was performed by electrospray mode. Selective reaction monitoring (SRM) was the acquisition mode used for the monitoring of MS3 transitions for each compound using aldicarb-d3 as internal standard for three analytes. Matrix effects were evaluated by comparing the recovery of matrix-matched and solvent-based calibration curves. The calibration graphs were linear in the ranges of 10 - 500 microg/L and the detection limits ranged from 4 to 5 microg/kg. The average recoveries ranged between 81.5% and 115% at three different spiked levels (10, 20 and 40 microg/kg). Satisfactory results were obtained in the determination of real peanut samples by this method.

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

    PubMed

    Zrnčić, Mirta; Gros, Meritxell; Babić, Sandra; Kaštelan-Macan, Marija; Barcelo, Damia; Petrović, Mira

    2014-03-01

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

  4. Metabolism, distribution, and excretion of deoxynivalenol with combined techniques of radiotracing, high-performance liquid chromatography ion trap time-of-flight mass spectrometry, and online radiometric detection.

    PubMed

    Wan, Dan; Huang, Lingli; Pan, Yuanhu; Wu, Qinghua; Chen, Dongmei; Tao, Yanfei; Wang, Xu; Liu, Zhenli; Li, Juan; Wang, Liye; Yuan, Zonghui

    2014-01-01

    Dispositions of deoxynivalenol (DON) in rats and chickens were investigated, using a radiotracer method coupled with a novel γ-accurate radioisotope counting (γ-ARC) radio-high-performance liquid chromatography ion trap time-of-flight tandem mass spectrometry (radio-HPLC-IT-TOF-MS/MS) system. 3β-(3)H-DON was chemically synthesized and orally administrated to both sexes of rats and chickens as single or multiple doses. The results showed that DON was widely distributed and quickly eliminated in all tissues. The highest concentration was found in the gastrointestinal tract at 6 h post-administration. Substantially lower levels were detected in the kidney, liver, heart, lung, spleen, and brain. Three new metabolites were identified tentatively as 10-deoxynivalenol-sulfonate, 10-deepoxy-deoxynivalenol (DOM-1)-sulfonate, and deoxynivalenol-3α-sulfate. Deoxynivalenol-3α-sulfate was a major metabolite in chickens, while the major forms in rats were DOM-1 and DON. Additionally, a higher excretion rate in urine was observed in female rats than in male rats. The differences in metabolite profiles and excretion rates, which suggested diverse ways to detoxify, may relate to the different tolerances in different genders or species.

  5. Solid-phase microextraction coupled with gas chromatography-ion trap mass spectrometry for the analysis of haloacetic acids in water.

    PubMed

    Sarrión, M N; Santos, F J; Galceran, M T

    1999-10-29

    Headspace solid-phase microextraction (SPME) was studied as a possible alternative to liquid-liquid extraction for the analysis of haloacetic acids (HAAs) in water. The method involves derivatization of the acids to their ethyl esters using sulphuric acid and ethanol after evaporation, followed by headspace SPME with a polydimethylsiloxane fibre and gas chromatography-ion trap mass spectrometry (GC-IT-MS). The derivatization procedure was optimized: maximum sensitivity was obtained with esterification for 10 min at 50 degrees C in 30 microl of sulphuric acid and 40 microl of ethanol. The headspace SPME conditions were also optimized and good sensitivity was obtained at a sampling temperature of 25 degrees C, an absorption time of 10 min, the addition of 0.1 g of anhydrous sodium sulfate and a desorption time of 2 min. Good precision (RSD lower than 10%) and detection limits in the ng l(-1) range (from 10 to 200 ng l(-1)) were obtained for all the compounds. The optimized procedure was applied to the analysis of HAAs in tap water and the results obtained by standard addition agreed with those of EPA method 552.2, whereas discrepancies due to matrix interferences were observed using external calibration. Consequently, headspace SPME-GC-IT-MS with standard addition is recommended for the analysis of these compounds in drinking water. PMID:10574209

  6. Low-pressure gas chromatography-ion trap mass spectrometry for the fast determination of polycyclic aromatic hydrocarbons in air samples.

    PubMed

    Ravindra, Khaiwal; Godoi, Ana F L; Bencs, László; Van Grieken, René

    2006-05-12

    A low-pressure gas chromatography-ion trap mass spectrometry (LPGC-ITMS) method was investigated to shorten the analysis time for 18 US Environmental Protection Agency priority listed polycyclic aromatic hydrocarbons (PAHs). Their elution was optimised with a short, wide-bore column coupled to a deactivated capillary at the inlet end and with a long, conventional column to compare their analytical performance. The analytical figures of merit under optimal LPGC-ITMS conditions were determined with respect to chromatographic separation, S/N ratio, limit of detection and precision. The peak width at half height of 1.5s matched the ITMS duty cycle. Up to 16 PAHs in the molecular weight (MW) range of 128-278 Da could be separated in a very short time, i.e. less than 13 min using LPGC-ITMS, whereas with conventional GC-MS, it took approximately 40 min. However, LPGC-ITMS has a limited loss of separation power compared to that of conventional GC-MS due to the occurrence of three critical pairs for high-MW PAHs. For a practical evaluation, the LPGC-ITMS approach was applied to the determination of PAHs in gas and aerosol phase samples collected in the ambient air of Hasselt, Belgium.

  7. Determination of alkylphenols and alkylphenol carboxylates in wastewater and river samples by hemimicelle-based extraction and liquid chromatography-ion trap mass spectrometry.

    PubMed

    Cantero, Manuel; Rubio, Soledad; Pérez-Bendito, Dolores

    2006-07-01

    Sodium dodecyl sulfate (SDS)-coated alumina and cetylpyridinium chloride (CPC)-coated silica were investigated as new sorbents for the concentration of alkylphenol polyethoxylate (APE) biodegradation products from wastewater and river water samples. Octylphenol (OP), nonylphenol (NP), octylphenol carboxylic acid (OPC) and nonylphenol carboxylic acid (NPC) were quantitatively retained on both supramolecular sorbents on the basis of the formation of mixed hemimicelles and admicelles. SDS hemimicelles-based SPE was proposed for the extraction/concentration of the target compounds prior to their separation and quantitation by liquid chromatography/electrospray ionization in negative mode, ion trap mass spectrometry. No clean-up steps or evaporation of the eluent were required. The recovery of APE metabolites from sewage and river water ranged between 87 and 100%. Concentration factors of about 500, using sample volumes of 1 l, were achieved. Detection limits were between 75 and 193 ng/l. The approach developed was applied to the determination of alklylphenols and alkylphenol carboxylic acids in raw and treated sewage and river samples. The concentrations of APE metabolites found ranged between 0.8 and 78 microg/l. PMID:16412449

  8. Liquid chromatography quadrupole linear ion trap mass spectrometry for quantitative steroid hormone analysis in plasma, urine, saliva and hair.

    PubMed

    Gaudl, Alexander; Kratzsch, Juergen; Bae, Yoon Ju; Kiess, Wieland; Thiery, Joachim; Ceglarek, Uta

    2016-09-16

    Steroid analysis is being conquered by liquid chromatography tandem mass spectrometry (LC-MS/MS) benefiting from higher standardization, selectivity and diversity. Regarding high throughput in routine diagnostics rapid chromatography is mandatory. Introducing MS(3) (MS/MS/MS), specificity of mass spectrometric detection can be enhanced without sacrificing analysis time. 100mL of human plasma/serum, saliva, urine and 10-20mg of hair are used for the simultaneous quantification of 17α-hydroxyprogesterone, aldosterone, androstenedione, cortisol, cortisone, dehydroepiandrosterone sulfate (DHEAS), estradiol, progesterone, and testosterone using online solid phase extraction (SPE) LC-MS/MS or LC-MS(3). Steroids can be analyzed in 4min after a single manual dilution and protein precipitation step. In complex sample matrices like hair MS(3) detection was found to be appropriate for quantitation. Lower limits of quantitation ranged from 37pmol/L (estradiol) up to 3.1nmol/L (DHEAS). General accuracy was 89-107% with between-run imprecision ≤10%. Comparison to immunoassays revealed significant differences in quantitation for urinary cortisol (-71% mean), aldosterone (-40% mean) and plasma aldosterone (-45% mean). The comparison of MS(2) and MS(3) quantitation of hair cortisol also revealed significant differences. In general, quantitation via MS(3) was not applicable for a long time. But with the current generation of mass spectrometers quantitation via MS(3) can be superior to MS(2) regarding specificity and accuracy when dealing with matrix issues. However, drawbacks regarding flexibility and precision have to be taken into account. Concludingly, simple protein precipitation combined with rapid online SPE LC-MS/MS/MS allows us to quantify over broad, essential concentration ranges in human serum, saliva, urine and hair. PMID:27554022

  9. Extended linear ion trap frequency standard apparatus

    NASA Technical Reports Server (NTRS)

    Prestage, John D. (Inventor)

    1995-01-01

    A linear ion trap for frequency standard applications is provided with a plurality of trapping rods equally spaced and applied quadruple rf voltages for radial confinement of atomic ions and biased level pins at each end for axial confinement of the ions. The trapping rods are divided into two linear ion trap regions by a gap in each rod in a common radial plane to provide dc discontinuity, thus dc isolating one region from the other. A first region for ion-loading and preparation fluorescence is biased with a dc voltage to transport ions into a second region for resonance frequency comparison with a local oscillator derived frequency while the second region is held at zero voltage. The dc bias voltage of the regions is reversed for transporting the ions back into the first region for fluorescence measurement. The dual mode cycle is repeated continuously for comparison and feedback control of the local oscillator derived frequency. Only the second region requires magnetic shielding for the resonance function which is sensitive to any ambient magnetic fields.

  10. Rapid and sensitive gas chromatography ion-trap mass spectrometry method for the determination of tobacco specific N-nitrosamines in secondhand smoke

    SciTech Connect

    SLEIMAN, Mohamad; MADDALENA, Randy L.; GUNDEL, Lara A.; DESTAILLATS, Hugo

    2009-07-01

    Tobacco-specific nitrosamines (TSNAs) are some of the most potent carcinogens in tobacco and cigarette smoke. Accurate quantification of these chemicals is needed to help assess public health risks. We developed and validated a specific and sensitive method to measure four TSNAs in both the gas- and particle-phase of secondhand smoke (SHS) using gas chromatography and ion-trap tandem mass spectrometry,. A smoking machine in an 18-m3 room-sized chamber generated relevant concentrations of SHS that were actively sampled on Teflon coated fiber glass (TCFG) filters, and passively sampled on cellulose substrates. A simple solid-liquid extraction protocol using methanol as solvent was successfully applied to both filters with high recoveries ranging from 85 to 115percent. Tandem MS parameters were optimized to obtain the best sensitivity in terms of signal to-noise ratio (S/N) for the target compounds. For each TSNA, the major fragmentation pathways as well as ion structures were elucidated and compared with previously published data. The method showed excellent performances with a linear dynamic range between 2 and 1000 ng mL-1, low detection limits (S/N> 3) of 30-300 pg.ml-1 and precision with experimental errors below 10percent for all compounds. Moreover, no interfering peaks were observed indicating a high selectivity of MS/MS without the need for a sample clean up step. The sampling and analysis method provides a sensitive and accurate tool to detect and quantify traces of TSNA in SHS polluted indoor environments.

  11. Simultaneous determination of diclofenac, its human metabolites and microbial nitration/nitrosation transformation products in wastewaters by liquid chromatography/quadrupole-linear ion trap mass spectrometry.

    PubMed

    Osorio, Victoria; Imbert-Bouchard, Marta; Zonja, Bozo; Abad, José-Luis; Pérez, Sandra; Barceló, Damià

    2014-06-20

    An analytical method was developed and validated for the first determination of five major human metabolites of the non-steroidal anti-inflammatory drug diclofenac as well as two microbial transformation products in wastewater. The method was based on the extraction of diclofenac and the chemically synthetized compounds by solid-phase extraction (SPE), using a hydrophilic-lipophilic balanced polymer followed by liquid chromatography (LC) coupled to hybrid quadrupole-linear ion trap mass spectrometry (QqLIT-MS). Quantitation was performed by the internal standard approach, to correct for matrix effects. The accuracy of the method was generally higher than 40% for raw and treated wastewater with a precision below 12%. In wastewater influent and effluent samples the detection limits for the majority of target compounds were 0.3-2.5ngL(-1) and 0.1-3.1ngL(-1), respectively. The method was applied to the analysis of influent and effluent wastewater samples from urban wastewater treatment plants. Moreover, to obtain an extra tool for confirmation and identification of the studied diclofenac-derived compounds, Information-Dependent Acquisition (IDA) experiments were performed, with selected reaction monitoring (SRM) as the survey scan and an enhanced product ion (EPI) scan as the dependent scan. Diclofenac and its major human metabolite, 4'-hydroxydiclofenac were detected in all samples at concentrations of 331-1150ngL(-1) and 585-6000ngL(-1), respectively. Neither microbial transformation product of diclofenac was detected in any of the influent samples analyzed, but in effluents, their concentrations ranged from 4 to 105ngL(-1).

  12. Direct and Sensitive Detection of CWA Simulants by Active Capillary Plasma Ionization Coupled to a Handheld Ion Trap Mass Spectrometer.

    PubMed

    Wolf, Jan-Christoph; Etter, Raphael; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

    2016-07-01

    An active capillary plasma ionization (ACI) source was coupled to a handheld mass spectrometer (Mini 10.5; Aston Labs, West Lafayette, IN, USA) and applied to the direct gas-phase detection and quantification of chemical warfare agent (CWA) related chemicals. Complementing the discontinuous atmospheric pressure interface (DAPI) of the Mini 10.5 mass spectrometer with an additional membrane pump, a quasi-continuous sample introduction through the ACI source was achieved. Nerve agent simulants (three dialkyl alkylphosphonates, a dialkyl phosporamidate, and the pesticide dichlorvos) were detected at low gas-phase concentrations with limits of detection ranging from 1.0 μg/m(3) to 6.3 μg/m(3). Our results demonstrate a sensitivity enhancement for portable MS-instrumentation by using an ACI source, enabling direct, quantitative measurements of volatile organic compounds. Due to its high sensitivity, selectivity, low power consumption (<80 W) and weight (<13 kg), this instrumentation has the potential for direct on-site CWA detection as required by military or civil protection. Graphical Abstract ᅟ.

  13. Direct and Sensitive Detection of CWA Simulants by Active Capillary Plasma Ionization Coupled to a Handheld Ion Trap Mass Spectrometer.

    PubMed

    Wolf, Jan-Christoph; Etter, Raphael; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

    2016-07-01

    An active capillary plasma ionization (ACI) source was coupled to a handheld mass spectrometer (Mini 10.5; Aston Labs, West Lafayette, IN, USA) and applied to the direct gas-phase detection and quantification of chemical warfare agent (CWA) related chemicals. Complementing the discontinuous atmospheric pressure interface (DAPI) of the Mini 10.5 mass spectrometer with an additional membrane pump, a quasi-continuous sample introduction through the ACI source was achieved. Nerve agent simulants (three dialkyl alkylphosphonates, a dialkyl phosporamidate, and the pesticide dichlorvos) were detected at low gas-phase concentrations with limits of detection ranging from 1.0 μg/m(3) to 6.3 μg/m(3). Our results demonstrate a sensitivity enhancement for portable MS-instrumentation by using an ACI source, enabling direct, quantitative measurements of volatile organic compounds. Due to its high sensitivity, selectivity, low power consumption (<80 W) and weight (<13 kg), this instrumentation has the potential for direct on-site CWA detection as required by military or civil protection. Graphical Abstract ᅟ. PMID:27020924

  14. Direct and Sensitive Detection of CWA Simulants by Active Capillary Plasma Ionization Coupled to a Handheld Ion Trap Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Wolf, Jan-Christoph; Etter, Raphael; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

    2016-07-01

    An active capillary plasma ionization (ACI) source was coupled to a handheld mass spectrometer (Mini 10.5; Aston Labs, West Lafayette, IN, USA) and applied to the direct gas-phase detection and quantification of chemical warfare agent (CWA) related chemicals. Complementing the discontinuous atmospheric pressure interface (DAPI) of the Mini 10.5 mass spectrometer with an additional membrane pump, a quasi-continuous sample introduction through the ACI source was achieved. Nerve agent simulants (three dialkyl alkylphosphonates, a dialkyl phosporamidate, and the pesticide dichlorvos) were detected at low gas-phase concentrations with limits of detection ranging from 1.0 μg/m3 to 6.3 μg/m3. Our results demonstrate a sensitivity enhancement for portable MS-instrumentation by using an ACI source, enabling direct, quantitative measurements of volatile organic compounds. Due to its high sensitivity, selectivity, low power consumption (<80 W) and weight (<13 kg), this instrumentation has the potential for direct on-site CWA detection as required by military or civil protection.

  15. Ion trapping and separation using potential wells

    SciTech Connect

    Butler, M.A.

    2000-01-04

    A new mode of operation for an ion mobility spectrometer (IMS) has been demonstrated that uses potential wells to trap and separate ions by their mobility. This mode of operation has been made feasible by the improvements in personal computers that now allow real-time control of the potentials on ring electrodes in the IMS drift tube. This mode of operation does not require a shutter grid and allows the accumulation of ions in the potential well to enhance the ion signal. Loss of ions from the potential well is controlled by the radial electric fields required by Gauss's law.

  16. Cryogenically cooled octupole ion trap for spectroscopy of biomolecular ions.

    PubMed

    Boyarkin, Oleg V; Kopysov, Vladimir

    2014-03-01

    We present here the design of a linear octupole ion trap, suitable for collisional cryogenic cooling and spectroscopy of large ions. The performance of this trap has been assessed using ultraviolet (UV) photofragmentation spectroscopy of protonated dipeptides. At the trap temperature of 6.1 K, the vibrational temperature of the ions reaches 9.1 K, although their estimated translational temperature is ~150 K. This observation suggests that, despite the significant translational heating by radio-frequency electrical field, vibrational cooling of heavy ions in the octupole is at least as efficient as in the 22-pole ion traps previously used in our laboratory. In contrast to the 22-pole traps, excellent radial confinement of ions in the octupole makes it convenient for laser spectroscopy and boosts the dissociation yield of the stored ions to 30%. Overlap of the entire ion cloud by the laser beam in the octupole also allows for efficient UV depletion spectroscopy of ion-He clusters. The measured electronic spectra of the dipeptides and the clusters differ drastically, complicating a use of UV tagging spectroscopy for structural determination of large species.

  17. Cryogenically cooled octupole ion trap for spectroscopy of biomolecular ions

    NASA Astrophysics Data System (ADS)

    Boyarkin, Oleg V.; Kopysov, Vladimir

    2014-03-01

    We present here the design of a linear octupole ion trap, suitable for collisional cryogenic cooling and spectroscopy of large ions. The performance of this trap has been assessed using ultraviolet (UV) photofragmentation spectroscopy of protonated dipeptides. At the trap temperature of 6.1 K, the vibrational temperature of the ions reaches 9.1 K, although their estimated translational temperature is ˜150 K. This observation suggests that, despite the significant translational heating by radio-frequency electrical field, vibrational cooling of heavy ions in the octupole is at least as efficient as in the 22-pole ion traps previously used in our laboratory. In contrast to the 22-pole traps, excellent radial confinement of ions in the octupole makes it convenient for laser spectroscopy and boosts the dissociation yield of the stored ions to 30%. Overlap of the entire ion cloud by the laser beam in the octupole also allows for efficient UV depletion spectroscopy of ion-He clusters. The measured electronic spectra of the dipeptides and the clusters differ drastically, complicating a use of UV tagging spectroscopy for structural determination of large species.

  18. Mobility-Selected Ion Trapping and Enrichment Using Structures for Lossless Ion Manipulations

    DOE PAGES

    Chen, Tsung-Chi; Ibrahim, Yehia M.; Webb, Ian K.; Garimella, Sandilya V. B.; Zhang, Xing; Hamid, Ahmed M.; Deng, Liulin; Karnesky, William E.; Prost, Spencer A.; Sandoval, Jeremy A.; et al

    2016-01-11

    The integration of ion mobility spectrometry (IMS) with mass spectrometry (MS) and the ability to trap ions in IMS-MS measurements is of great importance for performing reactions, accumulating ions, and increasing analytical measurement sensitivity. The development of Structures for Lossless Ion Manipulations (SLIM) offers the potential for ion manipulations in a more reliable and cost-effective manner, while opening opportunities for much more complex sequences of manipulations. Here, we demonstrate an ion separation and trapping module and a method based upon SLIM that consists of a linear mobility ion drift region, a switch/tee and a trapping region that allows the isolationmore » and accumulation of mobility-separated species. The operation and optimization of the SLIM switch/tee and trap are described and demonstrated for the enrichment of the low abundance ions. Lastly, we observed a linear increase in ion intensity with the number of trapping/accumulation events using the SLIM trap, illustrating its potential for enhancing the sensitivity of low abundance or targeted species.« less

  19. Quantification of Biogenic and Anthropogenic Hydrocarbons using a Commercial Gas Chromatograph - Ion Trap Mass Spectrometer at a Ground Site near Fort McKay, AB

    NASA Astrophysics Data System (ADS)

    Tokarek, T. W.; Osthoff, H. D.

    2014-12-01

    The extraction of fossil fuels from the Alberta oil sands has been the focus of considerable attention due to its association with sizeable emissions of a variety of atmospheric pollutants, the magnitude and impacts of which are currently poorly constrained by observations. In order to more reliably estimate the magnitude and impact of these emissions, an intensive air quality measurement campaign, called "Fort McMurray Oil Sands Strategic Investigation of Local Sources" (FOSSILS), was conducted in the summer of 2013 as part of the Alberta-Canada joint oil sands monitoring program (JOSM) to identify and quantify emissions and their transformations from the Alberta oil sands. The challenge is that the region is surrounded by boreal forest, which provides a substantial background of biogenic hydrocarbons during summer. In this presentation, measurements of volatile organic compounds (VOCs) at the AMS13 ground site near Fort McKay, Alberta, from Aug 17 to Sept 6, 2013 using a commercial Griffin 450 gas chromatograph equipped with ion trap mass spectrometric detection and Tenax preconcentration are described. The combination of retention information and electron impact mass spectral data allowed unambiguous identification and quantification of the major biogenic monoterpenes, e.g., α and β-pinene, limonene, camphene, and 3Δ-carene, and of many anthropogenically derived hydrocarbons. Mixing ratios of biogenic hydrocarbons varied with time of day, temperature, and solar radiation, with maxima typically occurring at night, rationalized by nocturnal mixing heights and low mixing ratios of the nocturnal oxidants ozone (O3) and the nitrate radical (NO3). In contrast, mixing ratios of anthropogenic VOCs, e.g., benzene, toluene, ethyl benzene, and o-, p-, and m-xylene (BTEX), strongly depended on meteorological conditions, i.e., local wind direction. During episodes with high BTEX abundance, many additional high molecular weight hydrocarbons were observed which were not

  20. Motional-mode analysis of trapped ions

    NASA Astrophysics Data System (ADS)

    Kalis, Henning; Hakelberg, Frederick; Wittemer, Matthias; Mielenz, Manuel; Warring, Ulrich; Schaetz, Tobias

    2016-08-01

    We present two methods for characterization of motional-mode configurations that are generally applicable to the weak- and strong-binding limit of single or multiple trapped atomic ions. Our methods are essential to realize control of the individual as well as the common motional degrees of freedom. In particular, when implementing scalable radio-frequency trap architectures with decreasing ion-electrode distances, local curvatures of electric potentials need to be measured and adjusted precisely, e.g., to tune phonon tunneling and control effective spin-spin interaction. We demonstrate both methods using single 25Mg+ ions that are individually confined 40 μ m above a surface-electrode trap array and prepared close to the ground state of motion in three dimensions.

  1. Mass Trapping for Anastrepha suspensa

    Technology Transfer Automated Retrieval System (TEKTRAN)

    ABSTRACT In field tests conducted in south Florida to test grape juice as an alternative inexpensive bait for Anastrepha suspensa Loew, high numbers of Zaprionus indianus Gupta were captured in traps baited with aqueous grape juice. These experiments included comparisons of grape juice with standard...

  2. Lifetime measurements in an electrostatic ion beam trap using image charge monitoring

    SciTech Connect

    Rahinov, Igor; Toker, Yoni; Heber, Oded; Rappaport, Michael; Zajfman, Daniel; Strasser, Daniel; Schwalm, Dirk

    2012-03-15

    A technique for mass-selective lifetime measurements of keV ions in a linear electrostatic ion beam trap is presented. The technique is based on bunching the ions using a weak RF potential and non-destructive ion detection by a pick-up electrode. This method has no mass-limitation, possesses the advantage of inherent mass-selectivity, and offers a possibility of measuring simultaneously the lifetimes of different ion species with no need for prior mass-selection.

  3. A hybrid liquid chromatography-mass spectrometry strategy in a forensic laboratory for opioid, cocaine and amphetamine classes in human urine using a hybrid linear ion trap-triple quadrupole mass spectrometer.

    PubMed

    Dowling, Geraldine; Regan, Liam; Tierney, Julie; Nangle, Michael

    2010-10-29

    A rapid method has been developed to analyse morphine, codeine, morphine-3-glucuronide, 6-monoacetylmorphine, cocaine, benzoylegonine, buprenorphine, dihydrocodeine, cocaethylene, 3,4-methylenedioxyamphetamine, ketamine, 3,4-methylenedioxymethamphetamine, pseudoephedrine, lignocaine, benzylpiperazine, methamphetamine, amphetamine, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine and methadone in human urine. Urine samples were diluted with methanol:water (1:1, v/v) and sample aliquots were analysed by hybrid linear ion trap-triple quadrupole mass spectrometry with a runtime of 12.5 min. Multiple reaction monitoring (MRM) as survey scan and an enhanced product ion (EPI) scan as dependent scan were performed in an information-dependent acquisition (IDA) experiment. Finally, drug identification and confirmation was carried out by library search with a developed in-house MS/MS library based on EPI spectra at a collision energy spread of 35±15 in positive mode and MRM ratios. The method was validated in urine, according to the criteria defined in Commission Decision 2002/657/EC. At least two MRM transitions for each substance were monitored in addition to EPI spectra and deuterated analytes were used as internal standards for quantitation. The reporting level was 0.05 μg mL(-1) for the range of analytes tested. The regression coefficients (r(2)) for the calibration curves (0-4 μg mL(-1)) in the study were ≥0.98. The method proved to be simple and time efficient and was implemented as an analytical strategy for the illicit drug monitoring of opioids, cocaines and amphetamines in criminal samples from crime offenders, abusers or victims in the Republic of Ireland. To the best of our knowledge there are no hybrid LC-MS applications using MRM mode and product ion spectra in the linear ion trap mode for opioids, cocaines or amphetamines with validation data in urine. PMID:20855077

  4. Electron beam ion source and electron beam ion trap (invited)

    SciTech Connect

    Becker, Reinard; Kester, Oliver

    2010-02-15

    The electron beam ion source (EBIS) and its trap variant [electron beam ion trap (EBIT)] celebrated their 40th and 20th anniversary, respectively, at the EBIS/T Symposium 2007 in Heidelberg. These technologically challenging sources of highly charged ions have seen a broad development in many countries over the last decades. In contrast to most other ion sources the recipe of improvement was not ''sorcery'' but a clear understanding of the physical laws and obeying the technological constraints. This review will report important achievements of the past as well as promising developments in the future.

  5. Quantum computation with ions in microscopic traps

    NASA Astrophysics Data System (ADS)

    Šašura, Marek; Steane, Andrew M.

    2002-12-01

    We discuss a possible experimental realization of fast quantum gates with high fidelity with ions confined in microscopic traps. The original proposal of this physical system for quantum computation comes from Cirac and Zoller (Nature 404, 579 (2000)). In this paper we analyse a sensitivity of the ion-trap quantum gate on various experimental parameters which was omitted in the original proposal. We address imprecision of laser pulses, impact of photon scattering, nonzero temperature effects and influence of laser intensity fluctuations on the total fidelity of the two-qubit phase gate.

  6. Wide-scope screening and quantification of 50 pesticides in wine by liquid chromatography/quadrupole time-of-flight mass spectrometry combined with liquid chromatography/quadrupole linear ion trap mass spectrometry.

    PubMed

    He, Zeying; Xu, Yaping; Wang, Lu; Peng, Yi; Luo, Ming; Cheng, Haiyan; Liu, Xiaowei

    2016-04-01

    In this paper, a wide scope screening method of pesticides in wine was established using liquid chromatography/quadrupole time-of-flight mass spectrometry (LC-QTOF MS) and liquid chromatography/quadrupole linear ion trap mass spectrometry (LC-QqLIT MS). Information dependent acquisition (IDA) experiments are used to obtain both MS and MS/MS information for LC-QTOF MS analysis. For LC-QqLIT MS analysis, MS/MS spectra of target pesticides were simultaneously acquired using Enhanced Product Ion (EPI) mode at very low concentrations to increase the confidence in analytical results of multiple reaction monitoring (MRM) by library searching. Method validation was carried out using 50 pesticides commonly used in vineyards. The LOQs, linearity, repeatability were determined and good enough for quantification. The screening and quantification results obtained using LC-QTOF MS and LC-QqLIT MS were compared. Contaminants were screened against libraries containing over 2800 compounds based on accurate mass, isotopic patterns, and MS/MS spectra searching to extend the scope of this methodology to non-target screening. PMID:26593613

  7. Wide-scope screening and quantification of 50 pesticides in wine by liquid chromatography/quadrupole time-of-flight mass spectrometry combined with liquid chromatography/quadrupole linear ion trap mass spectrometry.

    PubMed

    He, Zeying; Xu, Yaping; Wang, Lu; Peng, Yi; Luo, Ming; Cheng, Haiyan; Liu, Xiaowei

    2016-04-01

    In this paper, a wide scope screening method of pesticides in wine was established using liquid chromatography/quadrupole time-of-flight mass spectrometry (LC-QTOF MS) and liquid chromatography/quadrupole linear ion trap mass spectrometry (LC-QqLIT MS). Information dependent acquisition (IDA) experiments are used to obtain both MS and MS/MS information for LC-QTOF MS analysis. For LC-QqLIT MS analysis, MS/MS spectra of target pesticides were simultaneously acquired using Enhanced Product Ion (EPI) mode at very low concentrations to increase the confidence in analytical results of multiple reaction monitoring (MRM) by library searching. Method validation was carried out using 50 pesticides commonly used in vineyards. The LOQs, linearity, repeatability were determined and good enough for quantification. The screening and quantification results obtained using LC-QTOF MS and LC-QqLIT MS were compared. Contaminants were screened against libraries containing over 2800 compounds based on accurate mass, isotopic patterns, and MS/MS spectra searching to extend the scope of this methodology to non-target screening.

  8. Accuracy studies with carbon clusters at the Penning trap mass spectrometer TRIGA-TRAP

    NASA Astrophysics Data System (ADS)

    Ketelaer, J.; Beyer, T.; Blaum, K.; Block, M.; Eberhardt, K.; Eibach, M.; Herfurth, F.; Smorra, C.; Nagy, Sz.

    2010-05-01

    Extensive cross-reference measurements of well-known frequency ratios using various sizes of carbon cluster ions 12Cn + (10≤n≤23) were performed to determine the effects limiting the accuracy of mass measurements at the Penning-trap facility TRIGA-TRAP. Two major contributions to the uncertainty of a mass measurement have been identified. Fluctuations of the magnetic field cause an uncertainty in the frequency ratio due to the required calibration by a reference ion of uf(νref)/νref = 6(2) × 10-11/min × Δt. A mass-dependent systematic shift of the frequency ratio of epsilonm(r)/r = -2.2(2) × 10-9 × (m-mref)/u has been found as well. Finally, the nuclide 197Au was used as a cross-check since its mass is already known with an uncertainty of 0.6 keV.

  9. Ion trap collision-induced dissociation of locked nucleic acids.

    PubMed

    Huang, Teng-yi; Kharlamova, Anastasia; McLuckey, Scott A

    2010-01-01

    Gas-phase dissociation of model locked nucleic acid (LNA) oligonucleotides and functional LNA-DNA chimeras have been investigated as a function of precursor ion charge state using ion trap collision-induced dissociation (CID). For the model LNA 5 and 8 mer, containing all four LNA monomers in the sequence, cleavage of all backbone bonds, generating a/w-, b/x-, c/y-, and d/z-ions, was observed with no significant preference at lower charge states. Base loss ions, except loss of thymine, from the cleavage of N-glycosidic bonds were also present. In general, complete sequence coverage was achieved in all charge states. For the two LNA-DNA chimeras, however, dramatic differences in the relative contributions of the competing dissociation channels were observed among different precursor ion charge states. At lower charge states, sequence information limited to the a-Base/w-fragment ions from cleavage of the 3'C-O bond of DNA nucleotides, except thymidine (dT), was acquired from CID of both the LNA gapmer and mixmer ions. On the other hand, extensive fragmentation from various dissociation channels was observed from post-ion/ion ion trap CID of the higher charge state ions of both LNA-DNA chimeras. This report demonstrates that tandem mass spectrometry is effective in the sequence characterization of LNA oligonucleotides and LNA-DNA chimeric therapeutics.

  10. Resolution of nuclear ground and isomeric states by a Penning trap mass spectrometer

    SciTech Connect

    Bollen, G.; Kluge, H.; Koenig, M.; Otto, T.; Savard, G.; Stolzenberg, H. ); Moore, R.B.; Rouleau, G. ); Audi, G. )

    1992-12-01

    Ground and isomeric states of a nucleus have been resolved for the first time by mass spectrometry. Measurements on [sup 78]Rb[sup [ital m],][ital g] and [sup 84]Rb[sup [ital m],][ital g] were performed using a tandem Penning trap mass spectrometer on-line with the isotope separator ISOLDE/CERN. The effects of ion-ion interaction were investigated for two ion species differing in mass and stored simultaneously in the trap.

  11. Determination of N,N-dimethyltryptamine in beverages consumed in religious practices by headspace solid-phase microextraction followed by gas chromatography ion trap mass spectrometry.

    PubMed

    Gaujac, Alain; Dempster, Nicola; Navickiene, Sandro; Brandt, Simon D; de Andrade, Jailson Bittencourt

    2013-03-15

    A novel analytical approach combining solid-phase microextraction (SPME)/gas chromatography ion trap mass spectrometry (GC-IT-MS) was developed for the detection and quantification N,N-dimethyltryptamine (DMT), a powerful psychoactive indole alkaloid present in a variety of South American indigenous beverages, such as ayahuasca and vinho da jurema. These particular plant products, often used within a religious context, are increasingly consumed throughout the world following an expansion of religious groups and the availability of plant material over the Internet and high street shops. The method described in the present study included the use of SPME in headspace mode combined GC-IT-MS and included the optimization of the SPME procedure using multivariate techniques. The method was performed with a polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber in headspace mode (70 min at 60 °C) which resulted in good precision (RSD<8.6%) and accuracy values (71-109%). Detection and quantification limits obtained for DMT were 0.78 and 9.5 mg L(-1), respectively and good linearity (1.56-300 mg L(-1), r(2)=0.9975) was also observed. In addition, the proposed method showed good robustness and allowed for the minimization of sample manipulation. Five jurema beverage samples were prepared in the laboratory in order to study the impact of temperature, pH and ethanol on the ability to extract DMT into solution. The developed method was then applied to the analysis of twelve real ayahuasca and vinho da jurema samples, obtained from Brazilian religious groups, which revealed DMT concentration levels between 0.10 and 1.81 g L(-1). PMID:23598143

  12. Trapped Atomic Ions and Quantum Information Processing

    SciTech Connect

    Wineland, D. J.; Leibfried, D.; Bergquist, J. C.; Blakestad, R. B.; Bollinger, J. J.; Britton, J.; Chiaverini, J.; Epstein, R. J.; Hume, D. B.; Itano, W. M.; Jost, J. D.; Koelemeij, J. C. J.; Langer, C.; Ozeri, R.; Reichle, R.; Rosenband, T.; Schaetz, T.; Schmidt, P. O.; Seidelin, S.; Shiga, N.

    2006-11-07

    The basic requirements for quantum computing and quantum simulation (single- and multi-qubit gates, long memory times, etc.) have been demonstrated in separate experiments on trapped ions. Construction of a large-scale information processor will require synthesis of these elements and implementation of high-fidelity operations on a very large number of qubits. This is still well in the future. NIST and other groups are addressing part of the scaling issue by trying to fabricate multi-zone arrays of traps that would allow highly-parallel and scalable processing. In the near term, some simple quantum processing protocols are being used to aid in quantum metrology, such as in atomic clocks. As the number of qubits increases, Schroedinger's cat paradox and the measurement problem in quantum mechanics become more apparent; with luck, trapped ion systems might be able to shed light on these fundamental issues.

  13. [An ultra-high-pressure liquid chromatography/linear ion trap-Orbitrap mass spectrometry method coupled with a diagnostic fragment ions-searching-based strategy for rapid identification and characterization of chemical components in Polygonum cuspidatum].

    PubMed

    Pan, Zhiran; Liang, Hailong; Liang, Chabhufi; Xu, Wen

    2015-01-01

    A method for qualitative analysis of constituents in Polygonum cuspidatum by ultra-high-pressure liquid chromatography coupled with linear ion trap-Orbitrap mass spectrometry (UHPLC-LTQ-Orbitrap MS) has been established. The methanol extract of Polygonum cuspidatumrn was separated on a Waters UPLC C18 column using acetonitrile-water (containing formic acid) eluting system and detected by LTQ-Orbitrap hybrid mass spectrometer in negative mode. The targeted components were further fragmented in LTQ and high accuracy data were acquired by Orbitrap MS. The summarized fragmentation pathways of typical reference components and a diagnostic fragment ions-searching-based strategy were used for detection and identification of the main phenolic components in Polygonum cuspidatum. Other clues such as nitrogen rule, even electron rule, degree of unsaturation rule and isotopic peak data were included for the structural elucidation as well. The whole analytical procedure was within 10 min and more than 30 components were identified or tentatively identified. This method is helpful for further phytochemical research and quality control on Polygonum cuspidatum and related preparations.

  14. [An ultra-high-pressure liquid chromatography/linear ion trap-Orbitrap mass spectrometry method coupled with a diagnostic fragment ions-searching-based strategy for rapid identification and characterization of chemical components in Polygonum cuspidatum].

    PubMed

    Pan, Zhiran; Liang, Hailong; Liang, Chabhufi; Xu, Wen

    2015-01-01

    A method for qualitative analysis of constituents in Polygonum cuspidatum by ultra-high-pressure liquid chromatography coupled with linear ion trap-Orbitrap mass spectrometry (UHPLC-LTQ-Orbitrap MS) has been established. The methanol extract of Polygonum cuspidatumrn was separated on a Waters UPLC C18 column using acetonitrile-water (containing formic acid) eluting system and detected by LTQ-Orbitrap hybrid mass spectrometer in negative mode. The targeted components were further fragmented in LTQ and high accuracy data were acquired by Orbitrap MS. The summarized fragmentation pathways of typical reference components and a diagnostic fragment ions-searching-based strategy were used for detection and identification of the main phenolic components in Polygonum cuspidatum. Other clues such as nitrogen rule, even electron rule, degree of unsaturation rule and isotopic peak data were included for the structural elucidation as well. The whole analytical procedure was within 10 min and more than 30 components were identified or tentatively identified. This method is helpful for further phytochemical research and quality control on Polygonum cuspidatum and related preparations. PMID:25958663

  15. Accelerated simulation study of space charge effects in quadrupole ion traps using GPU techniques.

    PubMed

    Xiong, Xingchuang; Xu, Wei; Fang, Xiang; Deng, Yulin; Ouyang, Zheng

    2012-10-01

    Space charge effects play important roles in the performance of various types of mass analyzers. Simulation of space charge effects is often limited by the computation capability. In this study, we evaluate the method of using graphics processing unit (GPU) to accelerate ion trajectory simulation. Simulation using GPU has been compared with multi-core central processing unit (CPU), and an acceleration of about 390 times have been obtained using a single computer for simulation of up to 10(5) ions in quadrupole ion traps. Characteristics of trapped ions can be investigated at detailed levels within a reasonable simulation time. Space charge effects on the trapping capacities of linear and 3D ion traps, ion cloud shapes, ion motion frequency shift, mass spectrum peak coalescence effects between two ion clouds of close m/z are studied with the ion trajectory simulation using GPU.

  16. Quantum simulations with cold trapped ions

    NASA Astrophysics Data System (ADS)

    Blatt, Rainer

    2016-05-01

    The quantum toolbox of the Innsbruck ion-trap quantum computer is applied to simulate the dynamics and to investigate the propagation of entanglement in a quantum many-body system represented by long chains of trapped-ion qubits. Quantum dynamics can be described by particle-like carriers of information that emerge in the collective behavior of the underlying system, the so-called quasiparticles. These elementary excitations are predicted to distribute quantum information in a fashion determined by the system's interactions. First, we observe the entanglement distributed by quasiparticles as they trace out light-cone-like wavefronts. Second, using the ability to tune the interaction range in our system, we observe information propagation in an experimental regime where the effective-lightcone picture does not apply. Moreover, a spectroscopic technique is presented to study artificial quantum matter and use it for characterizing quasiparticles in a many-body system of trapped atomic ions. Our approach is to excite combinations of the system's fundamental quasiparticle eigenmodes, given by delocalized spin waves. By observing the dynamical response to superpositions of such eigenmodes, we extract the system dispersion relation, magnetic order, and even detect signatures of quasiparticle interactions. In the second part of the talk, it will be shown how strings of trapped ions can be used for quantum simulations of a lattice gauge field theory. As an example, we map the real-time evolution of the Schwinger mechanism to a string of trapped ions in a few-qubit quantum computer, simulating the spontaneous creation of electron-positron pairs.

  17. Trapped Ion Magnetic Resonance: Concepts and Designs

    NASA Astrophysics Data System (ADS)

    Pizarro, Pedro Jose

    A novel spectroscopy of trapped ions is proposed which will bring single-ion detection sensitivity to the observation of magnetic resonance spectra and resolve the apparent incompatibility in existing techniques between high information content and high sensitivity. Methods for studying both electron spin resonance (ESR) and nuclear magnetic resonance (NMR) are designed. They assume established techniques for trapping ions in high magnetic field and observing electrically the trapping frequencies with high resolution (<1 Hz) and sensitivity (single -ion). A magnetic bottle field gradient couples the spin and spatial motions together and leads to the small spin -dependent force on the ion exploited by Dehmelt to observe directly the perturbation of the ground-state electron's axial frequency by its spin magnetic moment. A series of fundamental innovations is described to extend magnetic resonance to molecular ions ( cong 100 amu) and nuclear magnetic moments. It is demonstrated how time-domain trapping frequency observations before and after magnetic resonance can be used to make cooling of the particle to its ground state unnecessary. Adiabatic cycling of the magnetic bottle off between detection periods is shown to be practical and to allow high-resolution magnetic resonance to be encoded pointwise as the presence or absence of trapping frequency shifts. Methods of inducing spin -dependent work on the ion orbits with magnetic field gradients and Larmor frequency irradiation are proposed which greatly amplify the attainable shifts in trapping frequency. The first proposal presented builds on Dehmelt's experiment to reveal ESR spectra. A more powerful technique for ESR is then designed where axially synchronized spin transitions perform spin-dependent work in the presence of a magnetic bottle, which also converts axial amplitude changes into cyclotron frequency shifts. The most general approach presented is a continuous Stern-Gerlach effect in which a magnetic field

  18. Limiting temperature of sympathetically cooled ions in a radio-frequency trap

    SciTech Connect

    Hasegawa, Taro; Shimizu, Tadao

    2003-01-01

    The limiting temperature achieved by sympathetic cooling in an rf trap is calculated with a theoretical model in which no fitting parameters are used. The calculated result agrees well with observation. The dependence of the temperature on trapping parameters and ion mass is also analyzed. The results can be used for designing an rf trap system.

  19. Linear ion trap based atomic frequency standard

    NASA Technical Reports Server (NTRS)

    Prestage, John D.; Dick, G. J.; Maleki, Lute

    1991-01-01

    In order to develop a trapped ion-based fieldable frequency standard with stability 1 x 10 to the -13th/sq rt tau for averaging times tau greater than 10,000 s, a hybrid RF/DC linear ion trap was developed which permits storage of large numbers of ions with reduced susceptibility to the second-order Doppler effect caused by the RF confining fields. The authors have confined Hg-199(+) ions in this trap and have measured very high Q transitions with good SNRs. In preliminary measurements they obtained stabilities of 1.6 x 10 to the -13th/sq rt tau (tau between 50 and 800 s) with a 160-mHz wide atomic resonance linewidth and a signal-to-noise ratio of 40 for each measurement cycle. Atomic resonance lines as narrow as 30 mHz on the 40.5-GHz clock transition have been measured with no appreciable reduction in the ion signal. A stability of 7 x 10 to the -14th/sq rt tau is made possible by the signal-to-noise and line Q of this measured transition. Analysis of fundamental sources of frequency instability indicates that a long-term stability of 2 x 10 to the -16th is feasible for this device with existing technology for tau = 10 to the 6th s or more.

  20. A Dual Pressure Linear Ion Trap Orbitrap Instrument with Very High Sequencing Speed*

    PubMed Central

    Olsen, Jesper V.; Schwartz, Jae C.; Griep-Raming, Jens; Nielsen, Michael L.; Damoc, Eugen; Denisov, Eduard; Lange, Oliver; Remes, Philip; Taylor, Dennis; Splendore, Maurizio; Wouters, Eloy R.; Senko, Michael; Makarov, Alexander; Mann, Matthias; Horning, Stevan

    2009-01-01

    Since its introduction a few years ago, the linear ion trap Orbitrap (LTQ Orbitrap) instrument has become a powerful tool in proteomics research. For high resolution mass spectrometry measurements ions are accumulated in the linear ion trap and passed on to the Orbitrap analyzer. Simultaneously with acquisition of this signal, the major peaks are isolated in turn, fragmented and recorded at high sensitivity in the linear ion trap, combining the strengths of both mass analyzer technologies. Here we describe a next generation LTQ Orbitrap system termed Velos, with significantly increased sensitivity and scan speed. This is achieved by a vacuum interface using a stacked ring radio frequency ion guide with 10-fold higher transfer efficiency in MS/MS mode and 3–5-fold in full scan spectra, by a dual pressure ion trap configuration, and by reduction of overhead times between scans. The first ion trap efficiently captures and fragments ions at relatively high pressure whereas the second ion trap realizes extremely fast scan speeds at reduced pressure. Ion injection times for MS/MS are predicted from full scans instead of performing automatic gain control scans. Together these improvements routinely enable acquisition of up to ten fragmentation spectra per second. Furthermore, an improved higher-energy collisional dissociation cell with increased ion extraction capabilities was implemented. Higher-collision energy dissociation with high mass accuracy Orbitrap readout is as sensitive as ion trap MS/MS scans in the previous generation of the instrument. PMID:19828875

  1. Trapping of Intact, Singly-Charged, Bovine Serum Albumin Ions Injected from the Atmosphere with a 10-cm Diameter, Frequency-Adjusted Linear Quadrupole Ion Trap

    SciTech Connect

    Koizumi, Hideya; Whitten, William B; Reilly, Pete

    2008-12-01

    High-resolution real-time particle mass measurements have not been achievable because the enormous amount of kinetic energy imparted to the particles upon expansion into vacuum competes with and overwhelms the forces applied to the charged particles within the mass spectrometer. It is possible to reduce the kinetic energy of a collimated particulate ion beam through collisions with a buffer gas while radially constraining their motion using a quadrupole guide or trap over a limited mass range. Controlling the pressure drop of the final expansion into a quadrupole trap permits a much broader mass range at the cost of sacrificing collimation. To achieve high-resolution mass analysis of massive particulate ions, an efficient trap with a large tolerance for radial divergence of the injected ions was developed that permits trapping a large range of ions for on-demand injection into an awaiting mass analyzer. The design specifications required that frequency of the trapping potential be adjustable to cover a large mass range and the trap radius be increased to increase the tolerance to divergent ion injection. The large-radius linear quadrupole ion trap was demonstrated by trapping singly-charged bovine serum albumin ions for on-demand injection into a mass analyzer. Additionally, this work demonstrates the ability to measure an electrophoretic mobility cross section (or ion mobility) of singly-charged intact proteins in the low-pressure regime. This work represents a large step toward the goal of high-resolution analysis of intact proteins, RNA, DNA, and viruses.

  2. IDENTIFICATION OF MICROCYSTIN TOXINS FROM A STRAIN OF MICROCYSTIS AERUGINOSA BY LIQUID CHROMATOGRAPHY INTRODUCTION INTO A HYBRID LINEAR ION TRAP-FOURIER TRANSFORM ION CYCLOTRON RESONANCE MASS SPECTROMETER

    EPA Science Inventory

    The cyclic heptapeptide microcystin toxins produced by a strain of Microcystis aeruginosa that has not been investigated previously were separated by liquid chromatography and identified by high-accuracy m/z measurements of their [M + H]+ ions and the fragment i...

  3. Mass measurements on radioactive isotopes with a Penning trap mass spectrometer

    SciTech Connect

    Bollen, G.; Ames, F.; Schark, E.; Audi, G.; Lunney, D.; Saint Simon, M. de; Beck, D.; Herfurth, F.; Kluge, H.-J.; Kohl, A.; Schwarz, S.; Moore, R. B.; Szerypo, J.

    1999-01-15

    Penning trap mass measurements on short-lived isotopes are performed with the ISOLTRAP mass spectrometer at the radioactive beam facility ISOLDE/CERN. In the last years the applicability of the spectrometer has been considerably extended by the installation of an RFQ trap ion beam buncher and a new cooler Penning trap, which is operated as an isobar separator. These improvements allowed for the first time measurements on isotopes of rare earth elements and on isotopes with Z=80-85. In all cases an accuracy of {delta}m/m{approx_equal}1{center_dot}10{sup -7} was achieved.

  4. Extending the Dynamic Range of the Ion Trap by Differential Mobility Filtration

    NASA Astrophysics Data System (ADS)

    Hall, Adam B.; Coy, Stephen L.; Kafle, Amol; Glick, James; Nazarov, Erkinjon; Vouros, Paul

    2013-09-01

    A miniature, planar, differential ion mobility spectrometer (DMS) was interfaced to an LCQ classic ion trap to conduct selective ion filtration prior to mass analysis in order to extend the dynamic range of the trap. Space charge effects are known to limit the functional ion storage capacity of ion trap mass analyzers and this, in turn, can affect the quality of the mass spectral data generated. This problem is further exacerbated in the analysis of mixtures where the indiscriminate introduction of matrix ions results in premature trap saturation with non-targeted species, thereby reducing the number of parent ions that may be used to conduct MS/MS experiments for quantitation or other diagnostic studies. We show that conducting differential mobility-based separations prior to mass analysis allows the isolation of targeted analytes from electrosprayed mixtures preventing the indiscriminate introduction of matrix ions and premature trap saturation with analytically unrelated species. Coupling these two analytical techniques is shown to enhance the detection of a targeted drug metabolite from a biological matrix. In its capacity as a selective ion filter, the DMS can improve the analytical performance of analyzers such as quadrupole (3D or linear) and ion cyclotron resonance (FT-ICR) ion traps that depend on ion accumulation.

  5. Extending the Dynamic Range of the Ion Trap by Differential Mobility Filtration

    PubMed Central

    Hall, Adam B.; Coy, Stephen L.; Kafle, Amol; Glick, James; Nazarov, Erkinjon

    2013-01-01

    A miniature, planar, differential ion mobility spectrometer (DMS) was interfaced to an LCQ classic ion trap to conduct selective ion filtration prior to mass analysis in order to extend the dynamic range of the trap. Space charge effects are known to limit the functional ion storage capacity of ion trap mass analyzers and this, in turn, can affect the quality of the mass spectral data generated. This problem is further exacerbated in the analysis of mixtures where the indiscriminate introduction of matrix ions results in premature trap saturation with non-targeted species, thereby reducing the number of parent ions that may be used to conduct MS/MS experiments for quantitation or other diagnostic studies. We show that conducting differential mobility-based separations prior to mass analysis allows the isolation of targeted analytes from electrosprayed mixtures preventing the indiscriminate introduction of matrix ions and premature trap saturation with analytically unrelated species. Coupling these two analytical techniques is shown to enhance the detection of a targeted drug metabolite from a biological matrix. In its capacity as a selective ion filter, the DMS can improve the analytical performance of analyzers such as quadrupole (3-D or linear) and ion cyclotron resonance (FT-ICR) ion traps that depend on ion accumulation. PMID:23797861

  6. Experiments with Single Trapped Ytterbium Ions at JPL

    NASA Technical Reports Server (NTRS)

    Yu, Nan; Maleki, Lute

    2000-01-01

    This paper presents viewgraphs of experiments performed with single trapped Ytterbium ions. The topics include: 1) Ytterbium ion level scheme; 2) Paul-Straubel rf trap and single ion image; 3) D5/2 state lifetime measurement; 4) D3/2 state lifetime measurement; 5) Trapped individual ions in an optical cavity; 6) Initial exploratory system: experimental goals; and 7) Future systems: trap-cavity integration II.

  7. The JPL trapped mercury ion frequency standard

    NASA Technical Reports Server (NTRS)

    Prestage, J. D.; Dick, G. J.; Maleki, L.

    1988-01-01

    In order to provide frequency standards for the Deep Space Network (DSN) which are more stable than present-day hydrogen masers, a research task was established under the Advanced Systems Program of the TDA to develop a Hg-199(+) trapped ion frequency standard. The first closed-loop operation of this kind is described. Mercury-199 ions are confined in an RF trap and are state-selected through the use of optical pumping with 194 nm UV light from a Hg-202 discharge lamp. Absorption of microwave radiation at the hyperfine frequency (40.5 GHz) is signaled by atomic fluorescence of the UV light. The frequency of a 40.5 GHz oscillator is locked to a 1.6 Hz wide atomic absorption line of the trapped ions. The measured Allan variance of this locked oscillator is currently gamma sub y (pi) = 4.4 x 10 to the minus 12th/square root of pi for 20 is less than pi is less than 320 seconds, which is better stability than the best commercial cesium standards by almost a factor of 2. This initial result was achieved without magnetic shielding and without regulation of ion number.

  8. Multi-mycotoxin Analysis of Finished Grain and Nut Products Using Ultrahigh-Performance Liquid Chromatography and Positive Electrospray Ionization-Quadrupole Orbital Ion Trap High-Resolution Mass Spectrometry.

    PubMed

    Liao, Chia-Ding; Wong, Jon W; Zhang, Kai; Yang, Paul; Wittenberg, James B; Trucksess, Mary W; Hayward, Douglas G; Lee, Nathaniel S; Chang, James S

    2015-09-23

    Ultrahigh-performance liquid chromatography using positive electrospray ionization and quadrupole orbital ion trap high-resolution mass spectrometry was evaluated for analyzing mycotoxins in finished cereal and nut products. Optimizing the orbital ion trap mass analyzer in full-scan mode using mycotoxin-fortified matrix extracts gave mass accuracies, δM, of < ± 2.0 ppm at 70,000 full width at half maximum (FWHM) mass resolution (RFWHM). The limits of quantitation were matrix- and mycotoxin-dependent, ranging from 0.02 to 11.6 μg/kg. Mean recoveries and standard deviations for mycotoxins from acetonitrile/water extraction at their relevant fortification levels were 91 ± 10, 94 ± 10, 98 ± 12, 91 ± 13, 99 ± 15, and 93 ± 17% for corn, rice, wheat, almond, peanut, and pistachio, respectively. Nineteen mycotoxins with concentrations ranging from 0.3 (aflatoxin B1 in peanut and almond) to 1175 μg/kg (fumonisin B1 in corn flour) were found in 35 of the 70 commercial grain and nut samples surveyed. Mycotoxins could be identified at δM < ± 5 ppm by identifying the precursor and product ions in full-scan MS and data-dependent MS/MS modes. This method demonstrates a new analytical approach for monitoring mycotoxins in finished grain and nut products. PMID:25531669

  9. Multi-mycotoxin Analysis of Finished Grain and Nut Products Using Ultrahigh-Performance Liquid Chromatography and Positive Electrospray Ionization-Quadrupole Orbital Ion Trap High-Resolution Mass Spectrometry.

    PubMed

    Liao, Chia-Ding; Wong, Jon W; Zhang, Kai; Yang, Paul; Wittenberg, James B; Trucksess, Mary W; Hayward, Douglas G; Lee, Nathaniel S; Chang, James S

    2015-09-23

    Ultrahigh-performance liquid chromatography using positive electrospray ionization and quadrupole orbital ion trap high-resolution mass spectrometry was evaluated for analyzing mycotoxins in finished cereal and nut products. Optimizing the orbital ion trap mass analyzer in full-scan mode using mycotoxin-fortified matrix extracts gave mass accuracies, δM, of < ± 2.0 ppm at 70,000 full width at half maximum (FWHM) mass resolution (RFWHM). The limits of quantitation were matrix- and mycotoxin-dependent, ranging from 0.02 to 11.6 μg/kg. Mean recoveries and standard deviations for mycotoxins from acetonitrile/water extraction at their relevant fortification levels were 91 ± 10, 94 ± 10, 98 ± 12, 91 ± 13, 99 ± 15, and 93 ± 17% for corn, rice, wheat, almond, peanut, and pistachio, respectively. Nineteen mycotoxins with concentrations ranging from 0.3 (aflatoxin B1 in peanut and almond) to 1175 μg/kg (fumonisin B1 in corn flour) were found in 35 of the 70 commercial grain and nut samples surveyed. Mycotoxins could be identified at δM < ± 5 ppm by identifying the precursor and product ions in full-scan MS and data-dependent MS/MS modes. This method demonstrates a new analytical approach for monitoring mycotoxins in finished grain and nut products.

  10. Peptide profiling of Internet-obtained Cerebrolysin using high performance liquid chromatography - electrospray ionization ion trap and ultra high performance liquid chromatography - ion mobility - quadrupole time of flight mass spectrometry.

    PubMed

    Gevaert, Bert; D'Hondt, Matthias; Bracke, Nathalie; Yao, Han; Wynendaele, Evelien; Vissers, Johannes Petrus Cornelis; De Cecco, Martin; Claereboudt, Jan; De Spiegeleer, Bart

    2015-09-01

    Cerebrolysin, a parenteral peptide preparation produced by controlled digestion of porcine brain proteins, is an approved nootropic medicine in some countries. However, it is also easily and globally available on the Internet. Nevertheless, until now, its exact chemical composition was unknown. Using high performance liquid chromatography (HPLC) coupled to ion trap and ultra high performance liquid chromatography (UHPLC) coupled to quadrupole-ion mobility-time-of-flight mass spectrometry (Q-IM-TOF MS), combined with UniProt pig protein database search and PEAKS de novo sequencing, we identified 638 unique peptides in an Internet-obtained Cerebrolysin sample. The main components in this sample originate from tubulin alpha- and beta-chain, actin, and myelin basic protein. No fragments of known neurotrophic factors like glial cell-derived neurotrophic factor (GDNF), neurotrophin nerve growth factor (NGF), brain-derived neurotrophic factor (BDNF), and ciliary neurotrophic factor (CNTF) were found, suggesting that the activities reported in the literature are likely the result of new, hitherto unknown cryptic peptides with nootropic properties. PMID:26017115

  11. Peptide profiling of Internet-obtained Cerebrolysin using high performance liquid chromatography - electrospray ionization ion trap and ultra high performance liquid chromatography - ion mobility - quadrupole time of flight mass spectrometry.

    PubMed

    Gevaert, Bert; D'Hondt, Matthias; Bracke, Nathalie; Yao, Han; Wynendaele, Evelien; Vissers, Johannes Petrus Cornelis; De Cecco, Martin; Claereboudt, Jan; De Spiegeleer, Bart

    2015-09-01

    Cerebrolysin, a parenteral peptide preparation produced by controlled digestion of porcine brain proteins, is an approved nootropic medicine in some countries. However, it is also easily and globally available on the Internet. Nevertheless, until now, its exact chemical composition was unknown. Using high performance liquid chromatography (HPLC) coupled to ion trap and ultra high performance liquid chromatography (UHPLC) coupled to quadrupole-ion mobility-time-of-flight mass spectrometry (Q-IM-TOF MS), combined with UniProt pig protein database search and PEAKS de novo sequencing, we identified 638 unique peptides in an Internet-obtained Cerebrolysin sample. The main components in this sample originate from tubulin alpha- and beta-chain, actin, and myelin basic protein. No fragments of known neurotrophic factors like glial cell-derived neurotrophic factor (GDNF), neurotrophin nerve growth factor (NGF), brain-derived neurotrophic factor (BDNF), and ciliary neurotrophic factor (CNTF) were found, suggesting that the activities reported in the literature are likely the result of new, hitherto unknown cryptic peptides with nootropic properties.

  12. High-Precision Mass Measurements At TRIGA-TRAP

    NASA Astrophysics Data System (ADS)

    Smorra, C.; Beyer, T.; Blaum, K.; Block, M.; Eberhardt, K.; Eibach, M.; Herfurth, F.; Ketelaer, J.; Knuth, K.; Nörtershäuser, W.; Nagy, Sz.

    2010-04-01

    In order to study neutron-rich nuclides far from the valley of stability as well as long-lived actinoids the double Penning-trap mass spectrometer TRIGA-TRAP has been recently installed at the research reactor TRIGA Mainz. Short-lived neutron-rich fission products are produced by thermal neutron-induced fission of an actinoid target installed close to the reactor core. A helium gas-jet system with carbon aerosol particles is used to extract the fission products to the experiment. The Penning trap system has already been commissioned. Off-line mass measurements are routinely performed using a recently developed laser ablation ion source, and the gas-jet system has been tested. An overview of the experiment and current status will be given.

  13. Quantum error correction with trapped ions

    NASA Astrophysics Data System (ADS)

    Schindler, Philipp

    Quantum computers promise exponential speed-up compared to their classical counterparts for certain problems. Unfortunately, the states required for quantum computation are fragile and lose their quantum properties with growing system size. In a milestone work, it has been shown that quantum error correction can overcome this problem and enable arbitrary long and arbitrary high quality quantum algorithms. However, current experiments are not able to fulfill the requirements to employ useful quantum error correction procedures. In this talk, I will first review past proof-of-principle experiments in trapped ion quantum information processors. Building on that, I will sketch a way towards a medium-sized trapped ion system that will be capable of running an error correction procedure that outperforms it constituents.

  14. Quantum Rabi Model with Trapped Ions.

    PubMed

    Pedernales, J S; Lizuain, I; Felicetti, S; Romero, G; Lamata, L; Solano, E

    2015-01-01

    We propose the quantum simulation of the quantum Rabi model in all parameter regimes by means of detuned bichromatic sideband excitations of a single trapped ion. We show that current setups can reproduce, in particular, the ultrastrong and deep strong coupling regimes of such a paradigmatic light-matter interaction. Furthermore, associated with these extreme dipolar regimes, we study the controlled generation and detection of their entangled ground states by means of adiabatic methods. Ion traps have arguably performed the first quantum simulation of the Jaynes-Cummings model, a restricted regime of the quantum Rabi model where the rotating-wave approximation holds. We show that one can go beyond and experimentally investigate the quantum simulation of coupling regimes of the quantum Rabi model that are difficult to achieve with natural dipolar interactions. PMID:26482660

  15. Ultrafast Interferometry and Gates with Trapped Ions

    NASA Astrophysics Data System (ADS)

    Johnson, Kale; Wong-Campos, David; Neyenhuis, Brian; Mizrahi, Jonathan; Monroe, Christopher

    2016-05-01

    We sense the motion of a trapped atomic ion using a sequence of state-dependent ultrafast momentum kicks. We use this atom interferometer to characterize a nearly-pure quantum state with n = 1 phonon and accurately measure thermal states ranging from near the zero-point energy to n ~104 , with the possibility of extending at least 100 times higher in energy. The complete energy range of this method spans from the ground state to far outside of the Lamb-Dicke regime, where atomic motion is greater than the optical wavelength. Apart from thermometry, these interferometric techniques are useful for quantum information purposes, and we discuss the outlook for ultrafast entangling gates between multiple trapped ions. This work is supported by the NSF Physics Frontier Center at JQI.

  16. Trapped Ion Quantum Computation by Adiabatic Passage

    SciTech Connect

    Feng Xuni; Wu Chunfeng; Lai, C. H.; Oh, C. H.

    2008-11-07

    We propose a new universal quantum computation scheme for trapped ions in thermal motion via the technique of adiabatic passage, which incorporates the advantages of both the adiabatic passage and the model of trapped ions in thermal motion. Our scheme is immune from the decoherence due to spontaneous emission from excited states as the system in our scheme evolves along a dark state. In our scheme the vibrational degrees of freedom are not required to be cooled to their ground states because they are only virtually excited. It is shown that the fidelity of the resultant gate operation is still high even when the magnitude of the effective Rabi frequency moderately deviates from the desired value.

  17. Quantum Rabi Model with Trapped Ions

    PubMed Central

    Pedernales, J. S.; Lizuain, I.; Felicetti, S.; Romero, G.; Lamata, L.; Solano, E.

    2015-01-01

    We propose the quantum simulation of the quantum Rabi model in all parameter regimes by means of detuned bichromatic sideband excitations of a single trapped ion. We show that current setups can reproduce, in particular, the ultrastrong and deep strong coupling regimes of such a paradigmatic light-matter interaction. Furthermore, associated with these extreme dipolar regimes, we study the controlled generation and detection of their entangled ground states by means of adiabatic methods. Ion traps have arguably performed the first quantum simulation of the Jaynes-Cummings model, a restricted regime of the quantum Rabi model where the rotating-wave approximation holds. We show that one can go beyond and experimentally investigate the quantum simulation of coupling regimes of the quantum Rabi model that are difficult to achieve with natural dipolar interactions. PMID:26482660

  18. Direct mass measurements of the heaviest elements with Penning traps

    NASA Astrophysics Data System (ADS)

    Block, M.

    2015-12-01

    Penning-trap mass spectrometry (PTMS) is a mature technique to provide atomic masses with highest precision. Applied to radionuclides it enables us to investigate their nuclear structure via binding energies and derived quantities such as nucleon separation energies. Recent progress in slowing down radioactive ion beams in buffer gas cells in combination with advanced ion-manipulation techniques has opened the door to access even the elements above fermium by PTMS. Such elements are produced in complete fusion-evaporation reactions of heavy ions with lead, bismuth, and actinide targets at very low rates. Pioneering high-precision mass measurements of nobelium and lawrencium isotopes have been performed with SHIPTRAP at the GSI Darmstadt, Germany. These have illustrated that direct mass measurements provide reliable anchor points to pin down decay chains and that they allow mapping nuclear shell effects, the reason for the very existence of the heaviest elements. Thus, accurate masses contribute to our understanding of these exotic nuclei with extreme proton numbers. In this article experimental challenges in mass measurements of the heaviest elements with Penning traps are discussed. Some illustrative examples of the nuclear structure features displayed based on the presently known masses are given.

  19. Note: Ion source design for ion trap systems

    NASA Astrophysics Data System (ADS)

    Noriega, J. R.; Quevedo, M.; Gnade, B.; Vasselli, J.

    2013-06-01

    A small plasma (glow discharge) based ion source and circuit are described in this work. The ion source works by producing a high voltage pulsed discharge between two electrodes in a pressure range of 50-100 mTorr. A third mesh electrode is used for ion extraction. The electrodes are small stainless steel screws mounted in a MACOR ionization chamber in a linear arrangement. The electrode arrangement is driven by a circuit, design for low power operation. This design is a proof of concept intended for applications on small cylindrical ion traps.

  20. Gas phase reaction of substituted isoquinolines to carboxylic acids in ion trap and triple quadrupole mass spectrometers after electrospray ionization and collision-induced dissociation.

    PubMed

    Thevis, Mario; Kohler, Maxie; Schlörer, Nils; Schänzer, Wilhelm

    2008-01-01

    Within the mass spectrometric study of bisubstituted isoquinolines that possess great potential as prolylhydroxylase inhibitor drug candidates (e.g., FG-2216), unusually favored gas-phase formations of carboxylic acids after collisional activation were observed. The protonated molecule of [(1-chloro-4-hydroxy-isoquinoline-3-carbonyl)-amino]-acetic acid was dissociated, yielding the 1-chloro-4-hydroxy-isoquinoline-3-carboxylic acid methyleneamide cation. Subsequent dissociation caused the nominal elimination of 11 u that resulted from the loss of HCN and concomitant addition of oxygen to the product ion, which formed the protonated 1-chloro-4-hydroxy-isoquinoline-3-carboxylic acid. The preference of this structure under mass spectrometric conditions was substantiated by tandem mass spectrometry analyses using the corresponding methyl ester (1-chloro-4-hydroxy-isoquinoline-3-carboxylic acid methyl ester) that eliminated methylene (-14 u) upon collisional activation. Moreover, the major product ion of 1-chloro-4-hydroxy-isoquinoline-3-carboxylic acid, which resulted from the loss of water in MS3 experiments, restored the precursor ion structure by re-addition of H2O. Evidences for these phenomena were obtained by chemical synthesis of proposed gas-phase intermediates, H/D exchange experiments, high-resolution/high accuracy mass spectrometry at MSn level, and "ping-pong" analyses (MS7, in which the precursor ion was dissociated and the respective product ion isolated to regenerate the precursor ion for repeated dissociation. Based on these results, dissociation pathways for [(1-chloro-4-hydroxy-isoquinoline-3-carbonyl)-amino]-acetic acid were suggested that can be further utilized for the characterization of structurally related compounds or metabolic products in clinical, forensic, or doping control analysis.

  1. Spectroscopy of ions using fast beams and ion traps

    SciTech Connect

    Pinnington, E H; Trabert, E

    2004-10-01

    A knowledge of the spectra of ionized atoms is of importance in many fields. They can be studied in a wide variety of light sources. In recent years techniques coming under the broad heatings of fast beams and ion traps have been used extensively for such investigations. This article considers the advantages that various techniques have for particular applications.

  2. Different target surfaces for the analysis of peptides, peptide mixtures and peptide mass fingerprints by AP-MALDI ion trap-mass spectrometry.

    PubMed

    Pittenauer, Ernst; Kassler, Alexander; Haubner, Roland; Allmaier, Günter

    2011-06-10

    The desorption/ionization behavior of individual peptides, an equimolare peptide mixture and a tryptic digest was investigated by AP-MALDI-IT-MS using four different target materials (gold-covered stainless steel (SS), titanium nitride-covered SS, hand-polished SS, and microdiamond-covered hardmetal) under identical conditions. Gold-covered as well as polished SS targets yielded comparable mass spectra for peptides and peptide mixture in the low pMol-range. The first target exhibited superior data down to the 10fMol-range. In contrast, titanium nitride-covered SS and microdiamond-covered hardmetal AP-MALDI-targets yielded poor sensitivity. These observations could be correlated with the surface roughness of the targets determined by 3D-confocal-white-light-microscopy. The roughest surfaces were found for titanium nitride-covered SS and microdiamond-covered hardmetal material showing both poor MS sensitivity. A less rough surface could be determined for the hand-polished SS target and the smoothest surface was found for the gold-covered target yielding the best sensitivity of all surfaces. These differences in the roughness having a strong impact on the ultimate sensitivity obtainable for peptide samples could be corroborated by electron microscopy. A peptide mixture covering a wide range of molecular weights and a tryptic protein digest (from 2-DE) exhibit the same behavior. This clearly indicates that the smooth gold-covered SS target is the surface of choice in AP-MALDI MS proteomics.

  3. Resonance of the Macromotion of Ions Trapped in a RF Trap by the Subharmonic Oscillation

    NASA Astrophysics Data System (ADS)

    Yoda, Jun; Sugiyama, Kazuhiko

    1992-11-01

    Yb+ ions were trapped in an uncompensated rf trap with light buffer gas and then the storage time, as well as the total number of the trapped ions, was determined by the rf resonance method. When the ratio of the frequency of the trapping field to that of the macromotion of the trapped ions was an integer, the total number and the storage time were smaller and shorter, respectively, than those obtained when the ratio was a half-integer. A theoretical calculation shows that this effect, called the subharmonic oscillation, is caused by excitation of the macromotion of the trapped ions by the leaked trapping rf field, in the case in which the ion trap has an octupole besides a quadrupole potential.

  4. A study of the analytical behaviour of selected synthetic and naturally occurring quinolines using electrospray ionisation ion trap mass spectrometry, liquid chromatography and gas chromatography and the construction of an appropriate database for quinoline characterisation.

    PubMed

    O'Donnell, F; Ramachandran, V N; Smyth, W F; Hack, C J; Patton, E

    2006-07-14

    Mass spectral fragmentation of quinoline alkaloids of significance in plants has been investigated using electrospray ionisation ion trap mass spectrometry (ESI-MS(n)) with a view to characterisation of molecules of unknown structure isolated from these natural sources. This investigation has led to the generation of an appropriate database incorporating data from ESI-MS(n) and also from gas liquid chromatography (GLC) and liquid chromatography (HPLC) for these low molecular mass quinolines. This has been put to practical application in the identification of quinoline alkaloids in a plant extract. Thus, an acid extraction of the leaves of Choisya ternata containing such tertiary alkaloids was analysed by liquid chromatography-electrospray ionisation mass spectrometry (HPLC-ESI-MS) and the resulting behaviour of the quinolines was compared with that of the quinoline alkaloids in the database.

  5. Design, microfabrication, and analysis of micrometer-sized cylindrical ion trap arrays

    NASA Astrophysics Data System (ADS)

    Cruz, D.; Chang, J. P.; Fico, M.; Guymon, A. J.; Austin, D. E.; Blain, M. G.

    2007-01-01

    A description of the design and microfabrication of arrays of micrometer-scale cylindrical ion traps is offered. Electrical characterization and initial ion trapping experiments with a massively parallel array of 5μm internal radius (r0) sized cylindrical ion traps (CITs) are also described. The ion trap, materials, and design are presented and shown to be critical in achieving minimal trapping potential while maintaining minimal power consumption. The ion traps, fabricated with metal electrodes, have inner radii of 1, 2, 5, and 10μm and range from 5to24μm in height. The electrical characteristics of packaged ion trap arrays were measured with a vector network analyzer. The testing focused on trapping toluene (C7H8), mass 91, 92, or 93amu, in the 5μm sized CITs. Ions were formed via electron impact ionization and were ejected by turning off the rf voltage applied to the ring electrode; a current signal was collected at this time. Optimum ionization and trapping conditions, such as a sufficient pseudopotential well and high ionization to ion loss rate ratio (as determined by simulation), proved to be difficult to establish due to the high device capacitance and the presence of exposed dielectric material in the trapping region. However, evidence was obtained suggesting the trapping of ions in 1%-15% of the traps in the array. These first tests on micrometer-scale CITs indicated the necessary materials and device design modifications for realizing ultrasmall and low power ion traps.

  6. Design, microfabrication, and analysis of micrometer-sized cylindrical ion trap arrays

    SciTech Connect

    Cruz, D.; Chang, J. P.; Fico, M.; Guymon, A. J.; Austin, D. E.; Blain, M. G.

    2007-01-15

    A description of the design and microfabrication of arrays of micrometer-scale cylindrical ion traps is offered. Electrical characterization and initial ion trapping experiments with a massively parallel array of 5 {mu}m internal radius (r{sub 0}) sized cylindrical ion traps (CITs) are also described. The ion trap, materials, and design are presented and shown to be critical in achieving minimal trapping potential while maintaining minimal power consumption. The ion traps, fabricated with metal electrodes, have inner radii of 1, 2, 5, and 10 {mu}m and range from 5 to 24 {mu}m in height. The electrical characteristics of packaged ion trap arrays were measured with a vector network analyzer. The testing focused on trapping toluene (C{sub 7}H{sub 8}), mass 91, 92, or 93 amu, in the 5 {mu}m sized CITs. Ions were formed via electron impact ionization and were ejected by turning off the rf voltage applied to the ring electrode; a current signal was collected at this time. Optimum ionization and trapping conditions, such as a sufficient pseudopotential well and high ionization to ion loss rate ratio (as determined by simulation), proved to be difficult to establish due to the high device capacitance and the presence of exposed dielectric material in the trapping region. However, evidence was obtained suggesting the trapping of ions in 1%-15% of the traps in the array. These first tests on micrometer-scale CITs indicated the necessary materials and device design modifications for realizing ultrasmall and low power ion traps.

  7. A carbon-cluster laser ion source for TRIGA-TRAP

    NASA Astrophysics Data System (ADS)

    Smorra, C.; Blaum, K.; Eberhardt, K.; Eibach, M.; Ketelaer, J.; Ketter, J.; Knuth, K.; Nagy, Sz

    2009-08-01

    A new laser ablation ion source was developed and tested for the Penning trap mass spectrometer TRIGA-TRAP in order to provide carbon-cluster ions for absolute mass calibration. Ions of different cluster sizes up to C+24 were successfully produced, covering the mass range up to the heavy actinide elements. The ions were captured in a Penning trap, and their time-of-flight cyclotron resonances recorded in order to determine their cyclotron frequency. Furthermore, the same ion source was used to produce GdO+ ions from a gadolinium target in sufficient amount for mass spectrometry purposes. The design of the source and its characteristics are presented. This paper comprises partly the PhD theses of J Ketelaer and C Smorra.

  8. Precision Penning Trap Mass Measurements for Nuclear Structure at Triumf

    NASA Astrophysics Data System (ADS)

    Kwiatkowski, A. A.; Dilling, J.; Andreoiu, C.; Brunner, T.; Chaudhuri, A.; Chowdhury, U.; Delheij, P.; Ettenauer, S.; Frekers, D.; Gallant, A. T.; Grossheim, A.; Gwinner, G.; Lennarz, A.; Mané, E.; Pearson, M. R.; Schultz, B. E.; Simon, M. C.; Simon, V. V.

    2013-03-01

    Precision determinations of ground state or even isomeric state masses reveal fingerprints of nuclear structure. In particular at the limits at existence for very neutron-rich or deficient isotopes, this allows one to find detailed information about nuclear structure from separation energies or binding energies. This is important to test theoretical predictions or to refine model approaches, for example for new "magic numbers," as predicted around N = 34, where strong indications exist that the inclusion of NNN forces in theoretical calculations for Ca isotopes leads to significantly better predictions for ground state binding energies. Similarly, halo nuclei present an excellent application for ab-initio theory, where ground state properties, like masses and radii, present prime parameters for testing our understanding of nuclear structure. Precision mass determinations at TRIUMF are carried out with the TITAN (TRIUMF's Ion Trap for Atomic and Nuclear science) system. It is an ion trap setup coupled to the on-line facility ISAC. TITAN has measured masses of isotopes as short-lived as 9 ms (almost an order of magnitude shorter-lived than any other Penning trap system) and the only one with charge breeding capabilities, a feature that allows us to boost the precision by almost 2 orders of magnitude. We recently were able to make use of this feature by measuring short-lived Rb-isotopes, up to 74Rb, and reaching the 12+ charge state, which together with other improvements lead to an increase in precision by a factor 36.

  9. Simultaneous determination of 18 preservative residues in vegetables by ultra high performance liquid chromatography coupled with triple quadrupole/linear ion trap mass spectrometry using a dispersive-SPE procedure.

    PubMed

    Zhou, Xue; Cao, Shurui; Li, Xianliang; Tang, Bobin; Ding, Xiaowen; Xi, Cunxian; Hu, Jiangtao; Chen, Zhiqiong

    2015-05-01

    A new method combining dispersive-solid phase purification procedure with ultra high performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry was developed for simultaneous determination of 18 preservative residues in vegetables. The new method not only had the advantages of dispersive-solid phase purification procedure such as high recoveries, easy operation, rapid analysis, little solvent usage and wide analysis range of preservatives, but also had the advantages of ultra high performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry to be operated in positive mode and negative mode simultaneously. The method was validated for the following representative matrices: radish (tuber), tomato (eggplant fruit), cabbage (leafy), cowpea (bean), cucumber (melon) and so on. Samples were extracted with hexane-ethyl acetate (1:2, v/v), and then detected by ultra high performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry after being cleaned up with dispersive-solid phase purification procedure. Significant matrix effects were compensated by using the matrix-matched calibration curves. 18 preservatives showed good linearity over the range of 5.0-100.0 μg/L with correlation coefficients of 0.9904-1.000. The limits of detections were in the range of 0.04-4.16 μg/kg and the limits of quantity were in the range of 0.13-13.85 μg/kg. The recoveries of 18 preservatives ranged from 76.0% to 120.0% with the spiked levels of 2, 4 and 10 μg/kg into homogenized vegetables, and the relative standard deviations (RSDs) ranged from 0.3% to 14.8%. Compared with the reported literatures, the method is more rapid, simple, highly sensitive, reliable and can meet testing requirements of 18 preservative residues in vegetables.

  10. Prospects for quantum computation with trapped ions

    SciTech Connect

    Hughes, R.J.; James, D.F.V.

    1997-12-31

    Over the past decade information theory has been generalized to allow binary data to be represented by two-state quantum mechanical systems. (A single two-level system has come to be known as a qubit in this context.) The additional freedom introduced into information physics with quantum systems has opened up a variety of capabilities that go well beyond those of conventional information. For example, quantum cryptography allows two parties to generate a secret key even in the presence of eavesdropping. But perhaps the most remarkable capabilities have been predicted in the field of quantum computation. Here, a brief survey of the requirements for quantum computational hardware, and an overview of the in trap quantum computation project at Los Alamos are presented. The physical limitations to quantum computation with trapped ions are discussed.

  11. Miniaturized gas chromatograph-Paul ion trap system: applications to environmental monitoring

    NASA Technical Reports Server (NTRS)

    Shortt, B. J.; Darrach, M. R.; Holland, Paul M.; Chutjian, A.

    2004-01-01

    A miniature gas chromatograph (GC) and miniature Paul ion trap (PT) mass spectrometer system has been developed for identifying and quantifying chemical species present in closed environments having a complex mixture of gases.

  12. Simultaneous qualitative and quantitative analysis of 21 mycotoxins in Radix Paeoniae Alba by ultra-high performance liquid chromatography quadrupole linear ion trap mass spectrometry and QuEChERS for sample preparation.

    PubMed

    Xing, Yanyan; Meng, Wenting; Sun, Wanyang; Li, Dongxiang; Yu, Zhiguo; Tong, Ling; Zhao, Yunli

    2016-09-15

    A high-throughput method for simultaneous qualitative and quantitative analysis of 21 mycotoxins in Radix Paeoniae Alba (RPA) was developed by coupling the modified QuEChERS method with ultra-high performance liquid chromatography quadrupole linear ion trap mass spectrometry (UHPLC-QqLIT-MS). The 21 mycotoxins were extracted and cleaned up using QuEChERS-based procedure, then further separated on a C18 column and detected by a hybrid triple quadrupole linear ion trap mass spectrometer equipped with electrospray ionization source in the multiple reaction monitoring-information dependent acquisition-enhanced product ion (MRM-IDA-EPI) mode. Under this technique, 13 mycotoxins were detected using acetonitrile and water containing 0.1% formic acid as the mobile phase in positive mode while the other 8 mycotoxins were detected using acetonitrile and water containing 0.1% ammonia as the mobile phase in negative mode. The calibration curves of all analytes showed good linearity (r(2)>0.995) within test ranges. The limits of detection and quantification ranged from 0.031 to 5.4μg/kg and 0.20 to 22μg/kg, respectively. Additionally, recoveries were all above 75.3% with relative standard deviations within 15%. The method proposed herein with significant advantages including simple pretreatment, rapid determination as well as high sensitivity, accuracy and throughput would be a preferred candidate for the determination and quantification of multi-class mycotoxin contaminants in real samples. PMID:27500642

  13. Trapped Ion Quantum Computing with Microwaves

    NASA Astrophysics Data System (ADS)

    Randall, Joe; Weidt, Sebastian; Standing, Eamon; Webster, Simon; Lake, Kim; Murgia, David; Navickas, Tomas; Lekitsch, Bjoern; Hughes, Marcus; Sterling, Robin; de Motte, Darren; Giri, Gouri; Rodriguez, Andrea; Webb, Anna; Rattanasonti, Hwanjit; Srinivasan, Prasanna; Kraft, Michael; Maclean, Jessica; Mellor, Chris; Hensinger, Winfried

    2015-03-01

    To this point, entanglement operations in trapped ion qubits have been predominantly performed with lasers. However, this becomes problematic when scaling to large numbers of qubits due to the challenging engineering required. The use of stable and easily controllable microwaves to drive entanglement gates can overcome this problem. We will present our work towards implementing multi-qubit entanglement gates using microwaves in an experimental setup that produces a static magnetic field gradient of 24 T/m over an ion string. We will first present a scheme for preparing and manipulating dressed-state qubits and qutrits that are highly robust to decoherence from magnetic field fluctuations. We will also present our work experimentally demonstrating motional sideband transitions and Schrödinger cat states using microwaves in conjunction with the magnetic field gradient, as well as sideband cooling to the ground state of motion using dressed-states. Furthermore, we will show our latest results in creating microfabricated ion trap chips towards large scale quantum computing and simulation.

  14. Stability Diagrams for Paul Ion Traps Driven by Two-Frequencies.

    PubMed

    Possa, Gabriela C; Roncaratti, Luiz F

    2016-07-14

    In this paper, we present and discuss stability diagrams for Paul traps driven by two ac voltages. In contrast to a typical Paul trap, here we suggest a secondary ac voltage whose frequency is twice the frequency of the primary one. The ratio between their amplitudes can be used to expand the region of stability and to access different states of motion of trapped ions. This provides a further mechanism to trap, cool, and manipulate single ions and also to improve the experimental framework where ion clouds and crystals can be prepared and controlled. Such approach opens the possibility of designing more sophisticated trapping architectures, leading to a wide variety of applications on ion trap research and mass analysis techniques.

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

    PubMed

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

    2014-10-01

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

  16. Ultraviolet Photodissociation Induced by Light-Emitting Diodes in a Planar Ion Trap.

    PubMed

    Holden, Dustin D; Makarov, Alexander; Schwartz, Jae C; Sanders, James D; Zhuk, Eugene; Brodbelt, Jennifer S

    2016-09-26

    The first application of light-emitting diodes (LEDs) for ultraviolet photodissociation (UVPD) mass spectrometry is reported. LEDs provide a compact, low cost light source and have been incorporated directly into the trapping cell of an Orbitrap mass spectrometer. MS/MS efficiencies of over 50 % were obtained using an extended irradiation period, and UVPD was optimized by modulating the ion trapping parameters to maximize the overlap between the ion cloud and the irradiation volume.

  17. Ultraviolet Photodissociation Induced by Light-Emitting Diodes in a Planar Ion Trap.

    PubMed

    Holden, Dustin D; Makarov, Alexander; Schwartz, Jae C; Sanders, James D; Zhuk, Eugene; Brodbelt, Jennifer S

    2016-09-26

    The first application of light-emitting diodes (LEDs) for ultraviolet photodissociation (UVPD) mass spectrometry is reported. LEDs provide a compact, low cost light source and have been incorporated directly into the trapping cell of an Orbitrap mass spectrometer. MS/MS efficiencies of over 50 % were obtained using an extended irradiation period, and UVPD was optimized by modulating the ion trapping parameters to maximize the overlap between the ion cloud and the irradiation volume. PMID:27605434

  18. Ball-grid array architecture for microfabricated ion traps

    NASA Astrophysics Data System (ADS)

    Guise, Nicholas D.; Fallek, Spencer D.; Stevens, Kelly E.; Brown, K. R.; Volin, Curtis; Harter, Alexa W.; Amini, Jason M.; Higashi, Robert E.; Lu, Son Thai; Chanhvongsak, Helen M.; Nguyen, Thi A.; Marcus, Matthew S.; Ohnstein, Thomas R.; Youngner, Daniel W.

    2015-05-01

    State-of-the-art microfabricated ion traps for quantum information research are approaching nearly one hundred control electrodes. We report here on the development and testing of a new architecture for microfabricated ion traps, built around ball-grid array (BGA) connections, that is suitable for increasingly complex trap designs. In the BGA trap, through-substrate vias bring electrical signals from the back side of the trap die to the surface trap structure on the top side. Gold-ball bump bonds connect the back side of the trap die to an interposer for signal routing from the carrier. Trench capacitors fabricated into the trap die replace area-intensive surface or edge capacitors. Wirebonds in the BGA architecture are moved to the interposer. These last two features allow the trap die to be reduced to only the area required to produce trapping fields. The smaller trap dimensions allow tight focusing of an addressing laser beam for fast single-qubit rotations. Performance of the BGA trap as characterized with 40Ca+ ions is comparable to previous surface-electrode traps in terms of ion heating rate, mode frequency stability, and storage lifetime. We demonstrate two-qubit entanglement operations with 171Yb+ ions in a second BGA trap.

  19. Ball-grid array architecture for microfabricated ion traps

    SciTech Connect

    Guise, Nicholas D. Fallek, Spencer D.; Stevens, Kelly E.; Brown, K. R.; Volin, Curtis; Harter, Alexa W.; Amini, Jason M.; Higashi, Robert E.; Lu, Son Thai; Chanhvongsak, Helen M.; Nguyen, Thi A.; Marcus, Matthew S.; Ohnstein, Thomas R.; Youngner, Daniel W.

    2015-05-07

    State-of-the-art microfabricated ion traps for quantum information research are approaching nearly one hundred control electrodes. We report here on the development and testing of a new architecture for microfabricated ion traps, built around ball-grid array (BGA) connections, that is suitable for increasingly complex trap designs. In the BGA trap, through-substrate vias bring electrical signals from the back side of the trap die to the surface trap structure on the top side. Gold-ball bump bonds connect the back side of the trap die to an interposer for signal routing from the carrier. Trench capacitors fabricated into the trap die replace area-intensive surface or edge capacitors. Wirebonds in the BGA architecture are moved to the interposer. These last two features allow the trap die to be reduced to only the area required to produce trapping fields. The smaller trap dimensions allow tight focusing of an addressing laser beam for fast single-qubit rotations. Performance of the BGA trap as characterized with {sup 40}Ca{sup +} ions is comparable to previous surface-electrode traps in terms of ion heating rate, mode frequency stability, and storage lifetime. We demonstrate two-qubit entanglement operations with {sup 171}Yb{sup +} ions in a second BGA trap.

  20. Numerical observation of preferred directionality in ion ejection from stretched rectilinear ion traps

    NASA Astrophysics Data System (ADS)

    Krishnaveni, A.; Kumar Verma, Neeraj; Menon, A. G.; Mohanty, Atanu K.

    2008-08-01

    We report on numerical investigations of directionality of ion ejection in stretched rectilinear ion traps (RIT). Three 4-electrode trap geometries have been investigated. In all cases, one pair of electrodes has slits at their center and the other pair has no slits. The studied traps include the RIT-S, in which the mass analyzer electrodes are symmetrically positioned around the central axis; the RIT-X, in which the mass analyzer has a stretch in the direction of the electrodes which have slits (labeled as x-direction); and the RIT-Y, in which the mass analyzer has a stretch in the direction of the electrodes which have no slits (labeled as y-direction). Our analysis has been carried out on two-dimensional (2D) fields at the centre of an infinitely long mass analyzer. The boundary element method (BEM) has been used for field computations. The trajectory of ion motion has been generated using Runge Kutta fourth order integration. Three sets of simulations have been carried out on each of the RIT-S, the RIT-X and the RIT-Y to check for directionality of ion ejection. In the first, we numerically obtain the stability region on the potential (Udc- Vrf) axes. In the second we generate an escape velocity plot with UdcD0 for different values of Vrf. In the third, we simulate the mass selective boundary ejection experiment on a single ion. In the symmetric RIT-S, as expected, all three simulations show that there is an equal probability of ion reaching the trap boundary in either of the x- or y-directions. For the stretched traps, however, the results are dramatically different. For the RIT-X, all three simulations suggest that ion destabilization at the stability boundary occurs in the x-directionE Similarly, for the RIT-Y, ions preferentially get destabilized in the y-direction. That is, ions reaching the trap boundary overwhelmingly prefer the stretch direction.

  1. Penning trap mass measurements on nobelium isotopes

    SciTech Connect

    Dworschak, M.; Block, M.; Ackermann, D.; Herfurth, F.; Hessberger, F. P.; Hofmann, S.; Vorobyev, G. K.; Audi, G.; Blaum, K.; Droese, C.; Marx, G.; Schweikhard, L.; Eliseev, S.; Ketter, J.; Fleckenstein, T.; Haettner, E.; Plass, W. R.; Scheidenberger, C.; Ketelaer, J.; Kluge, H.-J.

    2010-06-15

    The Penning trap mass spectrometer SHIPTRAP at GSI Darmstadt allows accurate mass measurements of radionuclides, produced in fusion-evaporation reactions and separated by the velocity filter SHIP from the primary beam. Recently, the masses of the three nobelium isotopes {sup 252-254}No were determined. These are the first direct mass measurements of transuranium elements, which provide new anchor points in this region. The heavy nuclides were produced in cold-fusion reactions by irradiating a PbS target with a {sup 48}Ca beam, resulting in production rates of the nuclei of interest of about one atom per second. In combination with data from decay spectroscopy our results are used to perform a new atomic-mass evaluation in this region.

  2. Penning trap mass measurements on nobelium isotopes

    NASA Astrophysics Data System (ADS)

    Dworschak, M.; Block, M.; Ackermann, D.; Audi, G.; Blaum, K.; Droese, C.; Eliseev, S.; Fleckenstein, T.; Haettner, E.; Herfurth, F.; Heßberger, F. P.; Hofmann, S.; Ketelaer, J.; Ketter, J.; Kluge, H.-J.; Marx, G.; Mazzocco, M.; Novikov, Yu. N.; Plaß, W. R.; Popeko, A.; Rahaman, S.; Rodríguez, D.; Scheidenberger, C.; Schweikhard, L.; Thirolf, P. G.; Vorobyev, G. K.; Wang, M.; Weber, C.

    2010-06-01

    The Penning trap mass spectrometer SHIPTRAP at GSI Darmstadt allows accurate mass measurements of radionuclides, produced in fusion-evaporation reactions and separated by the velocity filter SHIP from the primary beam. Recently, the masses of the three nobelium isotopes No252-254 were determined. These are the first direct mass measurements of transuranium elements, which provide new anchor points in this region. The heavy nuclides were produced in cold-fusion reactions by irradiating a PbS target with a Ca48 beam, resulting in production rates of the nuclei of interest of about one atom per second. In combination with data from decay spectroscopy our results are used to perform a new atomic-mass evaluation in this region.

  3. Space charge induced nonlinear effects in quadrupole ion traps.

    PubMed

    Guo, Dan; Wang, Yuzhuo; Xiong, Xingchuang; Zhang, Hua; Zhang, Xiaohua; Yuan, Tao; Fang, Xiang; Xu, Wei

    2014-03-01

    A theoretical method was proposed in this work to study space charge effects in quadrupole ion traps, including ion trapping, ion motion frequency shift, and nonlinear effects on ion trajectories. The spatial distributions of ion clouds within quadrupole ion traps were first modeled for both 3D and linear ion traps. It is found that the electric field generated by space charge can be expressed as a summation of even-order fields, such as quadrupole field, octopole field, etc. Ion trajectories were then solved using the harmonic balance method. Similar to high-order field effects, space charge will result in an "ocean wave" shape nonlinear resonance curve for an ion under a dipolar excitation. However, the nonlinear resonance curve will be totally shifted to lower frequencies and bend towards ion secular frequency as ion motion amplitude increases, which is just the opposite effect of any even-order field. Based on theoretical derivations, methods to reduce space charge effects were proposed.

  4. Progress Towards Quantum Simulation Using Micro-fabricated Ion Traps

    NASA Astrophysics Data System (ADS)

    Wright, K.; Ji, G.; Rickerd, C.; Collins, K.; Monroe, C.

    2015-05-01

    We report on current experimental progress towards using a surface electrode trap for quantum simulation. We use a micro-fabricated trap developed collaboratively between the Georgia Tech Research Institute (GTRI) and Honeywell International known as the Ball Grid Array (BGA) trap. This trap features 96 electrodes for fine control of the DC potential as well as a small footprint allowing for tight focusing of interaction lasers. We discuss the experimental system which utilizes the BGA trap, loading of Yb171 ions in this trap, and deterministic loading of chains of five or more ions. We hope to take advantage of the features of this new trap architecture in order to perform a small scale Boson Sampling experiment. This work is performed in collaboration with the GTRI Ion Trap Group and supported by ARO with funding from the IARPA MQCO program, and the AFOSR STTR on Atom Trap Chips.

  5. Investigation of ion capture in an electron beam ion trap charge-breeder for rare isotopes

    NASA Astrophysics Data System (ADS)

    Kittimanapun, Kritsada

    Charge breeding of rare isotope ions has become an important ingredient for providing reaccelerated rare isotope beams for science. At the National Superconducting Cyclotron Laboratory (NSCL), a reaccelerator, ReA, has been built that employs an advanced Electron Beam Ion Trap (EBIT) as a charge breeder. ReA will provide rare-isotope beams with energies of a few hundred keV/u up to tens of MeV/u to enable the study of properties of rare isotopes via low energy Coulomb excitation and transfer reactions, and to investigate nuclear reactions important for nuclear astrophysics. ReA consists of an EBIT charge breeder, a charge-over-mass selector, a room temperature radio-frequency quadrupole accelerator, and a superconducting radio-frequency linear accelerator. The EBIT charge breeder features a high-current electron gun, a long trap structure, and a hybrid superconducting magnet to reach both high acceptance for injected low-charge ions as well as high-electron beam current densities for fast charge breeding. In this work, continuous ion injection and capture in the EBIT have been investigated with a dedicated Monte-Carlo simulation code and in experimental studies. The Monte-Carlo code NEBIT considers the electron-impact ionization cross sections, space charge due to the electron beam current, ion dynamics, electric field from electrodes, and magnetic field from the superconducting magnet. Experiments were performed to study the capture efficiency as a function of injected ion beam current, electron beam current, trap size, and trap potential depth. The charge state evolution of trapped ions was studied, providing information about the effective current density of the electron beam inside the EBIT. An attempt was made to measure the effective space-charge potential of the electron beam by studying the dynamics of a beam injected and reflected inside the trap.

  6. Dynamics Of Ions In A Radio-Frequency Quadrupole Trap

    NASA Technical Reports Server (NTRS)

    Prestage, John D.; Williams, Angelyn P.; Maleki, Lutfollah

    1994-01-01

    Report describes computer-simulation study of motions of various numbers of ions in Paul trap. Study part of continuing effort to understand motions of trapped charged particles (atoms, ions, molecules, or dust particles). Motions characterized in terms of heating by radio-frequency fields, formation of crystallike structures in cold clouds of trapped particles, and other phenomena important in operation of radio-frequency traps in frequency standards.

  7. Ion beam analysis of defect trapping

    NASA Astrophysics Data System (ADS)

    Swanson, M. L.; Howe, L. M.

    1983-12-01

    Channeling measurements using medium energy ions (e.g. 1 MeV He +) have been used to determine the positions of solute atoms which are displaced from lattice sites by the trapping of vacancies and self-interstitial atoms. In this way, some simple defect trapping configurations have been identified in fcc metals. One of these is the mixed dumbbell (created when a self-interstitial is trapped by a small solute atom), consisting of a host atom and solute atom stradding a normal lattice site. Another is the tetravacancy-solute atom complex, consisting of four nearest neighbour vacancies surrounding a solute atom displaced into the tetrahedral interstitial site. In addition, from detailed analyses of displacements into different crystallographic channels as a function of irradiation fluence and annealing temperature, the evolution of a variety of defect complexes containing self-interstitials or vacancies has been studied in Al, Cu, Ni, Fe, and Mg crystals. Information from channeling analyses will be compared with data obtained from measurements of electrical resistivity, Mössbauer effect, perturbed angular correlation, extended X-ray absorption fine structure, muon precession, positron annihilation and internal friction. The advantages of the different methods will be discussed.

  8. This-layer chromatography/electrospray ionization triple-quadrupole linear ion trap mass spectrometry system: analysis of rhodamine dyes separated on reversed-phase C8 plates

    SciTech Connect

    Ford, Michael J; Kertesz, Vilmos; Van Berkel, Gary J

    2005-01-01

    The direct analysis of separated rhodamine dyes on reversed-phase C{sub 8} thin-layer chromatography plates using a surface sampling/electrospray emitter probe coupled with a triple-quadrupole linear ion trap mass spectrometer is presented. This report represents continuing work to advance the performance metrics and utility of this basic surface sampling electrospray mass spectrometry system for the analysis of thin-layer chromatography plates. Experimental results examining the role of sampling probe spray end configuration on liquid aspiration rate and gas-phase ion signal generated are discussed. The detection figures-of-merit afforded by full-scan, automated product ion and selected reaction monitoring modes of operation were examined. The effect of different eluting solvents on mass spectrum signal levels with the reversed-phase C{sub 8} plate was investigated. The combined effect of eluting solvent flow-rate and development lane surface scan rate on preservation of chromatographic resolution was also studied. Analysis of chromatographically separated red pen ink extracts from eight different pens using selected reaction monitoring demonstrated the potential of this surface sampling electrospray mass spectrometry system for targeted compound analysis with real samples.

  9. Broad-Band FT-ICR MS for the Penning-Trap Mass Spectrometer MATS

    SciTech Connect

    Rodriguez, D.; Cakirli, R. B.; Schweikhard, L.; Stahl, S.; Ubieto-Diaz, M.

    2010-08-04

    Ion traps are known as ideal tools for precision measurements of fundamental particle properties. In particular, traps have been set up at Radioactive Ion Beam (RIB) facilities to investigate exotic nuclei. During the last decade this field of research has constantly grown, with currently almost a dozen ion-trap systems at RIB facilities in Europe and North America and several more planned at future accelerators projects. One of these, the Advanced Trapping System MATS will be installed at the low-energy branch for radioactive-ion beams at the Facility for Antiprotons and Ion Research (FAIR) in Darmstadt (Germany). One of the MATS features will be non-destructive ion detection based on Fourier-Transform Ion-Cyclotron-Resonance Mass Spectrometry (FT-ICR MS). A prototype of the system has been developed at the Max-Planck-Institute for Nuclear Physics in Heidelberg (Germany) and recent results are outlined in this contribution.

  10. Extending the applicability of an open-ring trap to perform experiments with a single laser-cooled ion.

    PubMed

    Cornejo, J M; Colombano, M; Doménech, J; Block, M; Delahaye, P; Rodríguez, D

    2015-10-01

    A special ion trap was initially built up to perform β-ν correlation experiments with radioactive ions. The trap geometry is also well suited to perform experiments with laser-cooled ions, serving for the development of a new type of Penning trap, in the framework of the project TRAPSENSOR at the University of Granada. The goal of this project is to use a single (40)Ca(+) ion as detector for single-ion mass spectrometry. Within this project and without any modification to the initial electrode configuration, it was possible to perform Doppler cooling on (40)Ca(+) ions, starting from large clouds and reaching single ion sensitivity. This new feature of the trap might be important also for other experiments with ions produced at radioactive ion beam facilities. In this publication, the trap and the laser system will be described, together with their performance with respect to laser cooling applied to large ion clouds down to a single ion.

  11. Towards Quantum Simulations Using a Chip Ion Trap

    NASA Astrophysics Data System (ADS)

    Cao, Chenglin; Wright, Ken; Brennan, Daniel; Ji, Geoffrey; Monroe, Christopher

    2013-05-01

    We report our current experimental progress towards using chip ion traps for quantum simulation. Current progress is being made using a micro-fabricated symmetric trap from GTRI. This trap implements a novel two level design that combines the benefits of both surface traps and linear four-rod traps. The trap has 50 electrodes which allow for the fine control of the DC potential needed to create large anharmonic potentials, to join and split ion chains and to shuttle ions along the trapping axis similar to many surface traps. However this trap also has a much deeper trapping depth than conventional surface traps and improved optical access via an angled slot through the chip wide enough to accommodate higher power laser light which could cause surface charging or damage in a traditional chip trap. These advantages should allow trapping of long ion chains. We hope to use these features as the next step in increasing the size of current quantum simulations being done at Univ of Maryland, which are aimed at exploring quantum phenomena in spin systems in a regime inaccessible to classical simulation. This work is supported by grants from the U.S. Army Research Office with funding from the DARPA OLE program, IARPA, and the MURI program; and the NSF Physics Frontier Center at JQI. We acknowledge the GTRI team of J. Amini, K. Brown, A. Harter, F. Shaikh, R. Slusher, and C. Volin for the fabrication of the trap.

  12. Integrated Diffractive Optics for Surface Ion Traps

    NASA Astrophysics Data System (ADS)

    Streed, Erik; Ghadimi, Moji; Blums, Valdis; Norton, Benjamin; Connor, Paul; Amini, Jason; Volin, Curtis; Lobino, Mirko; Kielpinski, David

    2016-05-01

    Photonic interconnects are a bottleneck to achieving large-scale trapped ion quantum computing. We have modified a Georgia Tech Research Institute microwave chip trap by using e-beam lithography to write reflective diffractive collimating optics (80 μm x 127 μm, f=58.6 μm, λ=369.5nm) on the center electrode. The optics have an NA of 0.55 x 0.73, capturing 13.2% of the solid angle. To evaluate the optics 174Yb+ was loaded by isotope selective photo-ionization from a thermal oven and then shuttled to imaging sites. Near diffraction limited sub-wavelength ion images were obtained with an observed spot sized FWHM of 338 nm x 268 nm vs. a diffraction limit of 336 nm x 257 nm. The total photon collection efficiency was measured to be 5.2+/-1.2%. Coupling into a single mode fiber of up to 2.0+/-0.6% was observed, limited by mismatch in the coupling optics. Image mode quality indicates coupling up to 4% may be possible. Funding from Australian Research Council and IARPA.

  13. Trapped ion mode in toroidally rotating plasmas

    SciTech Connect

    Artun, M.; Tang, W.M.; Rewoldt, G.

    1995-04-01

    The influence of radially sheared toroidal flows on the Trapped Ion Mode (TIM) is investigated using a two-dimensional eigenmode code. These radially extended toroidal microinstabilities could significantly influence the interpretation of confinement scaling trends and associated fluctuation properties observed in recent tokamak experiments. In the present analysis, the electrostatic drift kinetic equation is obtained from the general nonlinear gyrokinetic equation in rotating plasmas. In the long perpendicular wavelength limit k{sub {tau}}{rho}{sub bi} {much_lt} 1, where {rho}{sub bi} is the average trapped-ion banana width, the resulting eigenmode equation becomes a coupled system of second order differential equations nmo for the poloidal harmonics. These equations are solved using finite element methods. Numerical results from the analysis of low and medium toroidal mode number instabilities are presented using representative TFTR L-mode input parameters. To illustrate the effects of mode coupling, a case is presented where the poloidal mode coupling is suppressed. The influence of toroidal rotation on a TFTR L-mode shot is also analyzed by including a beam species with considerable larger temperature. A discussion of the numerical results is presented.

  14. New ion trap for atomic frequency standard applications

    NASA Technical Reports Server (NTRS)

    Prestage, J. D.; Dick, G. J.; Maleki, L.

    1989-01-01

    A novel linear ion trap that permits storage of a large number of ions with reduced susceptibility to the second-order Doppler effect caused by the radio frequency (RF) confining fields has been designed and built. This new trap should store about 20 times the number of ions a conventional RF trap stores with no corresponding increase in second-order Doppler shift from the confining field. In addition, the sensitivity of this shift to trapping parameters, i.e., RF voltage, RF frequency, and trap size, is greatly reduced.

  15. Precision Spectroscopy on Single Cold Trapped Molecular Nitrogen Ions

    NASA Astrophysics Data System (ADS)

    Hegi, Gregor; Najafian, Kaveh; Germann, Matthias; Sergachev, Ilia; Willitsch, Stefan

    2016-06-01

    The ability to precisely control and manipulate single cold trapped particles has enabled spectroscopic studies on narrow transitions of ions at unprecedented levels of precision. This has opened up a wide range of applications, from tests of fundamental physical concepts, e.g., possible time-variations of fundamental constants, to new and improved frequency standards. So far most of these experiments have concentrated on atomic ions. Recently, however, attention has also been focused on molecular species, and molecular nitrogen ions have been identified as promising candidates for testing a possible time-variation of the proton/electron mass ratio. Here, we report progress towards precision-spectroscopic studies on dipole-forbidden vibrational transitions in single trapped N2+ ions. Our approach relies on the state-selective generation of single N2+ ions, subsequent infrared excitation using high intensity, narrow-band quantum-cascade lasers and a quantum-logic scheme for non-destructive state readout. We also characterize processes limiting the state lifetimes in our experiment, which impair the measurement fidelity. P. O. Schmidt et. al., Science 309 (2005), 749. M. Kajita et. al., Phys. Rev. A 89 (2014), 032509 M. Germann , X. Tong, S. Willitsch, Nature Physics 10 (2014), 820. X. Tong, A. Winney, S. Willitsch, Phys. Rev. Lett. 105 (2010), 143001

  16. Computer simulations of ions in radio-frequency traps

    NASA Technical Reports Server (NTRS)

    Williams, A.; Prestage, J. D.; Maleki, L.; Djomehri, J.; Harabetian, E.

    1990-01-01

    The motion of ions in a trapped-ion frequency standard affects the stability of the standard. In order to study the motion and structures of large ion clouds in a radio-frequency (RF) trap, a computer simulation of the system that incorporates the effect of thermal excitation of the ions was developed. Results are presented from the simulation for cloud sizes up to 512 ions, emphasizing cloud structures in the low-temperature regime.

  17. Off-resonance energy absorption in a linear Paul trap due to mass selective resonant quenching.

    PubMed

    Sivarajah, I; Goodman, D S; Wells, J E; Narducci, F A; Smith, W W

    2013-11-01

    Linear Paul traps (LPT) are used in many experimental studies such as mass spectrometry, atom-ion collisions, and ion-molecule reactions. Mass selective resonant quenching (MSRQ) is implemented in LPT either to identify a charged particle's mass or to remove unwanted ions from a controlled experimental environment. In the latter case, MSRQ can introduce undesired heating to co-trapped ions of different mass, whose secular motion is off resonance with the quenching ac field, which we call off-resonance energy absorption (OREA). We present simulations and experimental evidence that show that the OREA increases exponentially with the number of ions loaded into the trap and with the amplitude of the off-resonance external ac field. PMID:24289382

  18. Mass measurements with a Penning trap mass spectrometer at ISOLDE

    SciTech Connect

    Bollen, G.; Ames, F.; Schark, E.; Audi, G.; Lunney, D.; Saint Simon, M. de; Beck, D.; Herfurth, F.; Kluge, H.-J.; Kohl, A.; Schwarz, S.; Moore, R. B.; Szerypo, J.

    1998-12-21

    Penning trap mass measurements on radioactive isotopes are performed with the ISOLTRAP mass spectrometer at ISOLDE/CERN. In the last years the applicability of the spectrometer has been considerably extended. The most recent measurements were carried out on isotopes of rare earth elements and on isotopes with Z=80-85. An accuracy of {delta}m/m{approx_equal}1{center_dot}10{sup -7} was achieved.

  19. Trap door and underside of cap stone of pyramid ion ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Trap door and underside of cap stone of pyramid ion - Washington Monument, High ground West of Fifteenth Street, Northwest, between Independence & Constitution Avenues, Washington, District of Columbia, DC

  20. Ultra-stable Hg(+) trapped ion frequency standard

    NASA Technical Reports Server (NTRS)

    Prestage, John D.; Dick, G. John; Maleki, Lute

    1990-01-01

    A fieldable trapped ion frequency standard based on Hg-199(+) ions confined in a hybrid rf/dc linear ion trap is developed. This trap permits storage of large numbers of ions with reduced susceptibility to the second-order Doppler effect caused by the rf confining fields. In preliminary measurements a stability of 2 to 3 x 10(exp -15) was obtained for 10000 second averaging times. These measurements were carried out with a 120 mHz wide atomic resonance line for the 40.5 GHz clock transition with a second order Doppler shift from the rf trapping field of 6 x 10(exp -13).

  1. Resolved sideband spectra of calcium ions in a Penning trap

    NASA Astrophysics Data System (ADS)

    Goodwin, Joe; Stutter, Graham; Segal, Daniel; Thompson, Richard

    2013-03-01

    I report on recent work at Imperial College London, with laser cooled calcium-40 ion Coulomb crystals in Penning traps. Penning traps provide a number of advantages over the more common radiofrequency (RF) trap; namely the ability to trap 3-dimensional, micromotion-free ion Coulomb crystals, and the ability to produce deep traps while maintaining a large ion-electrode surface distance. While these factors should permit lower heating rates than in typical RF traps, very little research has been conducted into the behavior and control of small Coulomb crystals in Penning traps due to the experimental challenges involved. We have spent several years developing techniques to overcome these obstacles, and are now making rapid progress towards the sub-Doppler cooling and coherent control of small ion crystals. We have already observed high resolution optical spectra showing sidebands due to radial and axial motions, giving estimated temperatures close to the Doppler limit.

  2. Determination of tylosins A, B, C and D in bee larvae by liquid chromatography coupled to ion trap-tandem mass spectrometry.

    PubMed

    Bernal, J; Martín, Ma T; Toribio, L; Martín-Hernández, R; Higes, M; Bernal, J L; Nozal, M J

    2011-06-01

    A LC-MS/MS method has been developed to simultaneously quantify tylosins A, B, C and D in bee larvae, compounds currently used to treat one of the most lethal diseases affecting honey bees around the world, American Foulbrood (AFB). The influence of different aqueous media, temperature and light exposure on the stability of these four compounds was studied. The analytes were extracted from bee larvae with methanol and chromatographic separation was achieved on a Luna C(18) (150 × 4.6 mm i.d.) using a ternary gradient composed of a diluted formic acid, methanol and acetonitrile mobile phase. To facilitate sampling, bee larvae were initially dried at 60°C for 4h and afterwards, they were diluted to avoid problems of pressure. MSD-Ion Trap detection was employed with electrospray ionization (ESI). The calibration curves were linear over a wide range of concentrations and the method was validated as sensitive, precise and accurate within the limits of quantification (LOQ, 1.4-4.0 ng/g). The validated method was successfully employed to study bee larvae in field tests of bee hives treated with two formulations containing tylosin. In both cases it was evident that the minimal inhibitory concentration (MIC) had been reached. PMID:21498134

  3. Localization of double bonds in triacylglycerols using high-performance liquid chromatography/atmospheric pressure chemical ionization ion-trap mass spectrometry.

    PubMed

    Háková, Eva; Vrkoslav, Vladimír; Míková, Radka; Schwarzová-Pecková, Karolina; Bosáková, Zuzana; Cvačka, Josef

    2015-07-01

    A method for localizing double bonds in triacylglycerols using high-performance liquid chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization (APCI) was developed. The technique was based on collision-induced dissociation or pulsed Q collision-induced dissociation of the C3H5N(+•) adducts ([M + 55](+•)) formed in the presence of acetonitrile in the APCI source. The spectra were investigated using a large series of standards obtained from commercial sources and prepared by randomization. The fragmentation spectra made it possible to determine (i) the total number of carbons and double bonds in the molecule, (ii) the number of carbons and double bonds in acyls, (iii) the acyl in the sn-2 position on the glycerol backbone, and (iv) the double-bond positions in acyls. The double-bond positions were determined based on two types of fragments (alpha and omega ions) formed by cleavages of C-C bonds vinylic to the original double bond. The composition of the acyls and their positions on glycerol were established from the masses and intensities of the ions formed by the elimination of fatty acids from the [M + 55](+•) precursor. The method was applied for the analysis of triacylglycerols in olive oil and vernix caseosa.

  4. Fourier transform ion cyclotron resonance mass spectrometry: a primer.

    PubMed

    Marshall, A G; Hendrickson, C L; Jackson, G S

    1998-01-01

    This review offers an introduction to the principles and generic applications of FT-ICR mass spectrometry, directed to readers with no prior experience with the technique. We are able to explain the fundamental FT-ICR phenomena from a simplified theoretical treatment of ion behavior in idealized magnetic and electric fields. The effects of trapping voltage, trap size and shape, and other nonidealities are manifested mainly as perturbations that preserve the idealized ion behavior modified by appropriate numerical correction factors. Topics include: effect of ion mass, charge, magnetic field, and trapping voltage on ion cyclotron frequency; excitation and detection of ICR signals; mass calibration; mass resolving power and mass accuracy; upper mass limit(s); dynamic range; detection limit, strategies for mass and energy selection for MSn; ion axialization, cooling, and remeasurement; and means for guiding externally formed ions into the ion trap. The relation of FT-ICR MS to other types of Fourier transform spectroscopy and to the Paul (quadrupole) ion trap is described. The article concludes with selected applications, an appendix listing accurate fundamental constants needed for ultrahigh-precision analysis, and an annotated list of selected reviews and primary source publications that describe in further detail various FT-ICR MS techniques and applications.

  5. Test of Lorentz symmetry with trapped ions

    NASA Astrophysics Data System (ADS)

    Pruttivarasin, Thaned

    2016-05-01

    The outcome of an experiment should not depend on the orientation of the apparatus in space. This important cornerstone of physics is deeply engrained into the Standard Model of Physics by requiring that all fields must be Lorentz invariant. However, it is well-known that the Standard Model is incomplete. Some theories conjecture that at the Planck scale Lorentz symmetry might be broken and measurable at experimentally accessible energy scales. Therefore, a search for violation of Lorentz symmetry directly probes physics beyond the Standard model. We present a novel experiment utilizing trapped calcium ions as a direct probe of Lorentz-violation in the electron-photon sector. We monitor the energy between atomic states with different orientations of the electronic wave-functions as they rotate together with the motion of the Earth. This is analogous to the famous Michelson-Morley experiment. To remove magnetic field noise, we perform the experiment with the ions prepared in the decoherence-free states. Our result improves on the most stringent bounds on Lorentz symmetry for electrons by 100 times. The experimental scheme is readily applicable to many ion species, hence opening up paths toward much improved test of Lorentz symmetry in the future. (Ph. D. Advisor: Hartmut Haeffner, University of California, Berkeley).

  6. Simultaneous quantification of poly-dispersed anionic, amphoteric and nonionic surfactants in simulated wastewater samples using C18 high-performance liquid chromatography-quadrupole ion-trap mass spectrometry

    NASA Technical Reports Server (NTRS)

    Levine, Lanfang H.; Garland, Jay L.; Johnson, Jodie V.

    2005-01-01

    This paper describes the development of a guantitative method for direct and simultaneous determination of three frequently encountered surfactants, amphoteric (cocoamphoacetate, CAA), anionic (sodium laureth sulfate, SLES), and nonionic (alcohol ethoxylate, AE) using a reversed-phase C18 HPLC coupled with an ESI ion-trap mass spectrometer (MS). Chemical composition, ionization characteristics and fragmentation pathways of the surfactants are presented. Positive ESI was effective for all three surfactants in agueous methanol buffered with ammonium acetate. The method enables rapid determinations in small sample volumes containing inorganic salts (up to 3.5 g L(-1)) and multiple classes of surfactants with high specificity by applying surfactant specific tandem mass spectrometric strategies. It has dynamic linear ranges of 2-60, 1.5-40, 0.8-56 mg L(-1) with R2 egual or greater than 0.999, 0.98 and 0.999 (10 microL injection) for CAA, SLES, and AE, respectively.

  7. Rapid identif ication and comparative analysis of chemical constituents in herbal medicine Fufang decoction by ultra-high-pressure liquid chromatography coupled with a hybrid linear ion trap-high-resolution mass spectrometry.

    PubMed

    Cao, Gang; Chen, Xiaocheng; Wu, Xin; Li, Qinglin; Zhang, Hongyan

    2015-05-01

    This study was conducted to reveal the relation between herbal medicine Fufang decoction and a single drug in terms of material base. Da-Cheng-Qi decoction (DCQD) was used as a model. Ultrahigh-pressure liquid chromatography coupled with a hybrid linear ion trap-high-resolution mass spectrometry (UHPLC-LTQ-Orbitrap) was applied to detect and identify the main chemical compounds. This technique was also employed to determine the different chemical components. Under optimized liquid chromatography and mass spectrometry conditions, 64 components, including iridoids, flavonoids, anthraquinones and coumarins, were separated and tentatively characterized in Da-Cheng-Qi decoction. After decoction, the contents of 18 compounds were markedly changed, and two components were no longer detected in Fufang decoction compared with single-medicine decoction. The established method provided a good example for the rapid identification of complicated polar constituents in herbal medicine prescriptions.

  8. Characterization and quantitative analysis of phenylpropanoid amides in eggplant (Solanum melongena L.) by high performance liquid chromatography coupled with diode array detection and hybrid ion trap time-of-flight mass spectrometry.

    PubMed

    Sun, Jing; Song, Yue-Lin; Zhang, Jing; Huang, Zheng; Huo, Hui-Xia; Zheng, Jiao; Zhang, Qian; Zhao, Yun-Fang; Li, Jun; Tu, Peng-Fei

    2015-04-01

    Eggplant (Solanum melongena L.) is a famous edible and medicinal plant. Despite being widely cultivated and used, data on certain parts other than the fruit are limited. The present study focused on the qualitative and quantitative analysis of the chemical constituents, particularly phenylpropanoid amides (PAs), in eggplant. The mass fragmentation patterns of PAs were proposed using seven authentic compounds with the assistance of a hybrid ion trap time-of-flight mass spectrometer. Thirty-seven compounds (27 PAs and 10 others) were detected and plausibly assigned in the different parts of eggplant. Afterward, a reliable method based on liquid chromatography coupled with diode array detection was developed, validated, and applied for the simultaneous determination of seven PAs and three caffeoylquinic acids in 17 batches of eggplant roots with satisfactory accuracy, precision, and reproducibility, which could not only provide global chemical insight of eggplant but also offer a reliable tool for quality control.

  9. An Atomic Abacus: Trapped ion quantum computing experiments at NIST

    NASA Astrophysics Data System (ADS)

    Demarco, Brian

    2003-03-01

    Trapped atomic ions are an ideal system for exploring quantum information science because deterministic state preparation and efficient state detection are possible and coherent manipulation of atomic systems is relatively advanced. In our experiment, a few singly charged Be ions are confined by static and radio-frequency electric fields in a micro-machined linear Paul trap. The internal and motional states of the ions are coherently manipulated using applied laser light. Our current work focuses on demonstrating the necessary ingredients to produce a scalable quantum computing scheme and on simplifying and improving quantum logic gates. I will speak about a new set of experiments that was made possible by recent improvements in trap technology. A novel trap with multiple trapping regions was used to demonstrate the first steps towards a fully scalable quantum computing scheme. Single ions were ``shuttled" between trapping regions without disturbing the ion's motional and internal state, and two ions were separated from a single to two different trapping zones. Improvements in the trap manufacturing process has led to a reduction of nearly two orders of magnitude in the ion's motional heating rate, making possible two new improved logic gates. The first gate utilizes the wave-packet nature of the ions to tune the laser-atom interaction and achieve a controlled-NOT gate between a single ion's spin and motional states. The second, a two-ion phase gate, uses phase-space dynamics to produce a state-sensitive geometric phase. I will end with a quick look at experiments using a Mg ion to sympathetically cool a simultaneously trapped Be ion and a glimpse of the next generation of ions traps currently under construction.

  10. Cotrapping different species in ion traps using multiple radio frequencies

    NASA Astrophysics Data System (ADS)

    Trypogeorgos, Dimitris; Foot, Christopher J.

    2016-08-01

    We consider the stability of systems subjected to periodic parametric driving in the context of ions confined by oscillating electric fields. The behavior of these systems can be understood in terms of a pseudopotential approximation and resonances arising from parametric excitation. We investigate the key properties of a way of operating a linear Paul trap with two radio frequencies that simultaneously confines two species with extremely different charge-to-mass ratios. The theoretical calculations have been verified by molecular dynamics simulations and normal modes analysis.

  11. Doppler Sideband Spectra for Ions in a Linear Trap

    NASA Technical Reports Server (NTRS)

    Prestage, J. D.; Tjoelker, R. L.; Dick, G. J.; Maleki, L.

    1993-01-01

    We describe a spectroscopic measurement of the temperature and linear density of HG+ ions held in a linear ion trap (LIT). The inferred temperature and number result from analysis of sidebands on the 40.5 GHz resonance line.

  12. Profiling and identification of the metabolites of baicalin and study on their tissue distribution in rats by ultra-high-performance liquid chromatography with linear ion trap-Orbitrap mass spectrometer.

    PubMed

    Zhang, Jiayu; Cai, Wei; Zhou, Yuan; Liu, Ying; Wu, Xiaodan; Li, Yun; Lu, Jianqiu; Qiao, Yanjiang

    2015-03-15

    Baicalin (baicalein 7-O-glucuronide), which is one of the major bioactive constituents isolated from Scutellariae Radix, possesses many biological activities, such as antiallergic, antioxidation, and anti-inflammatory activities. In the present study, an efficient strategy was established using ultra-high-performance liquid chromatography coupled with linear ion trap-Orbitrap mass spectrometer (UPLC-LTQ-Orbitrap MS) to profile the in vivo metabolic fate of baicalin in rat plasma, urine, and various tissues. A combination of post-acquisition mining methods including extracted ion chromatogram (EIC) and multiple mass defect filters (MMDF) was adopted to identify the common and uncommon baicalin metabolites from the full mass scan data sets. Their structures were elucidated based on the accurate mass measurement, relevant drug biotransformation knowledge, the characteristic collision induced fragmentation pattern of baicalin metabolites, and bibliography data. Based on the proposed strategy, a total of 32 metabolites were observed and characterized. The corresponding reactions in vivo such as methylation, hydrolysis, hydroxylation, methoxylation, glucuronide conjugation, sulfate conjugation, and their composite reactions, were all discovered in the study. The results demonstrated that the rat liver and kidney are the most important organs for the baicalin metabolites presence. Six metabolites might play an important role in exerting pharmacological effects of baicalin in vivo. The newly discovered baicalin metabolites significantly expanded our understanding on its pharmacological effects, and could be targets for future studies on the important chemical constituents from herbal medicines.

  13. Trapped ion simulation of molecular spectrum

    NASA Astrophysics Data System (ADS)

    Shen, Yangchao; Lu, Yao; Zhang, Kuan; Zhang, Shuaining; Huh, Joonsuk; Kim, Kihwan

    2016-05-01

    Boson sampling had been suggested as a classically intractable and quantum mechanically manageable problem via computational complexity theory arguments. Recently, Huh and co-workers proposed theoretically a modified version of boson sampling, which is designed to simulate a molecular problem, as a practical application. Here, we report the experimental implementation of the theoretical proposal with a trapped ion system. As a first demonstration, we perform the quantum simulation of molecular vibronic profile of SO2, which incorporates squeezing, rotation and coherent displacements operations, and the collective projection measurement on phonon modes. This work was supported by the National Basic Research Program of China 11CBA00300, 2011CBA00301, National Natural Science Foundation of China 11374178, 11574002. Basic Science Research Program of Korea NRF-2015R1A6A3A04059773.

  14. JPL Ultrastable Trapped Ion Atomic Frequency Standards.

    PubMed

    Burt, Eric A; Yi, Lin; Tucker, Blake; Hamell, Robert; Tjoelker, Robert L

    2016-07-01

    Recently, room temperature trapped ion atomic clock development at the Jet Propulsion Laboratory (JPL) has focused on three directions: 1) ultrastable atomic clocks, usually for terrestrial applications emphasizing ultimate stability performance and autonomous timekeeping; 2) new atomic clock technology for space flight applications that require strict adherence to size, weight, and power requirements; and 3) miniature clocks. In this paper, we concentrate on the first direction and present a design and the initial results from a new ultrastable clock referred to as L10 that achieves a short-term stability of 4.5 ×10(-14)/τ(1/2) and an initial measurement of no significant drift with an uncertainty of 2.4 ×10(-16) /day over a two-week period.

  15. JPL Ultrastable Trapped Ion Atomic Frequency Standards.

    PubMed

    Burt, Eric A; Yi, Lin; Tucker, Blake; Hamell, Robert; Tjoelker, Robert L

    2016-07-01

    Recently, room temperature trapped ion atomic clock development at the Jet Propulsion Laboratory (JPL) has focused on three directions: 1) ultrastable atomic clocks, usually for terrestrial applications emphasizing ultimate stability performance and autonomous timekeeping; 2) new atomic clock technology for space flight applications that require strict adherence to size, weight, and power requirements; and 3) miniature clocks. In this paper, we concentrate on the first direction and present a design and the initial results from a new ultrastable clock referred to as L10 that achieves a short-term stability of 4.5 ×10(-14)/τ(1/2) and an initial measurement of no significant drift with an uncertainty of 2.4 ×10(-16) /day over a two-week period. PMID:27249827

  16. Four-Sector Cylindrical Radio-Frequency Ion Trap

    NASA Technical Reports Server (NTRS)

    Melbourne, Ruthann K.; Prestage, John D.; Maleki, Lutfollah

    1992-01-01

    Proposed linear radio-frequency ion trap consists of closed metal cylinder partitioned into four equal cylindrical-sector electrodes and two circular end electrodes. Features include relatively large ion-storage capacity and shielding against external fields. Used in frequency-standard laboratories to confine 199Hg+ ions electrodynamically in isolation from external environment. Similar to device described in "Linear Ion Trap for Atomic Clock" (NPO-17758).

  17. Progress Report on the Improved Linear Ion Trap Physics Package

    NASA Technical Reports Server (NTRS)

    Prestage, John D.

    1995-01-01

    This article describes the first operational results from the extended linear ion trap frequency standard now being developed at JPL. This new design separates the state selection/interrogation region from the more critical microwave resonance region where the multiplied local oscillator (LO) signal is compared to the stable atomic transition. Hg+ ions have been trapped, shuttled back and forth between the resonance and state selection traps. In addition, microwave transitions between the Hg+ clock levels have been driven in the resonance trap and detected in the state selection trap.

  18. An ion trap built with photonic crystal fibre technology

    SciTech Connect

    Lindenfelser, F. Keitch, B.; Kienzler, D.; Home, J. P.; Bykov, D.; Uebel, P.; Russell, P. St. J.

    2015-03-15

    We demonstrate a surface-electrode ion trap fabricated using techniques transferred from the manufacture of photonic-crystal fibres. This provides a relatively straightforward route for realizing traps with an electrode structure on the 100 micron scale with high optical access. We demonstrate the basic functionality of the trap by cooling a single ion to the quantum ground state, allowing us to measure a heating rate from the ground state of 787 ± 24 quanta/s. Variation of the fabrication procedure used here may provide access to traps in this geometry with trap scales between 100 μm and 10 μm.

  19. Multi-allergen detection in food by micro high-performance liquid chromatography coupled to a dual cell linear ion trap mass spectrometry.

    PubMed

    Monaci, Linda; Pilolli, Rosa; De Angelis, Elisabetta; Godula, Michal; Visconti, Angelo

    2014-09-01

    There is a raising demand for sensitive and high throughput MS based methods for screening purposes especially tailored to the detection of allergen contaminants in different food commodities. A challenging issue is represented by complex food matrices where the antibody-based kits commercially available might encounter objective limitations consequently to epitope masking phenomena due to a multitude of interfering compounds arising from the matrix. The performance of a method duly optimized for the extraction and simultaneous detection of soy, egg and milk allergens in a cookie food matrix by microHPLC-ESI-MS/MS, is herein reported. Thanks to the innovative configuration and the versatility shown by the dual cell linear ion trap MS used, the most intense and reliable peptide markers were first identified by untargeted survey experiment, and subsequently employed to design an ad hoc multi-target SRM method, based on the most intense transitions recorded for each selected precursor peptide. A sample extraction and purification protocol was optimized also including an additional step based on sonication, which resulted in a considerable improvement in the detection of milk allergen peptides. Data Dependent™ Acquisition scheme allowed to fill out a tentative list of potential peptide markers, which were further filtered upon fulfilling specific requirements. A total of eleven peptides were monitored simultaneously for confirmation purposes of each allergenic contaminant and the two most sensitive peptide markers/protein were selected in order to retrieve quantitative information. Relevant LODs were found to range from 0.1μg/g for milk to 0.3μg/g for egg and 2μg/g for soy.

  20. Multi-allergen detection in food by micro high-performance liquid chromatography coupled to a dual cell linear ion trap mass spectrometry.

    PubMed

    Monaci, Linda; Pilolli, Rosa; De Angelis, Elisabetta; Godula, Michal; Visconti, Angelo

    2014-09-01

    There is a raising demand for sensitive and high throughput MS based methods for screening purposes especially tailored to the detection of allergen contaminants in different food commodities. A challenging issue is represented by complex food matrices where the antibody-based kits commercially available might encounter objective limitations consequently to epitope masking phenomena due to a multitude of interfering compounds arising from the matrix. The performance of a method duly optimized for the extraction and simultaneous detection of soy, egg and milk allergens in a cookie food matrix by microHPLC-ESI-MS/MS, is herein reported. Thanks to the innovative configuration and the versatility shown by the dual cell linear ion trap MS used, the most intense and reliable peptide markers were first identified by untargeted survey experiment, and subsequently employed to design an ad hoc multi-target SRM method, based on the most intense transitions recorded for each selected precursor peptide. A sample extraction and purification protocol was optimized also including an additional step based on sonication, which resulted in a considerable improvement in the detection of milk allergen peptides. Data Dependent™ Acquisition scheme allowed to fill out a tentative list of potential peptide markers, which were further filtered upon fulfilling specific requirements. A total of eleven peptides were monitored simultaneously for confirmation purposes of each allergenic contaminant and the two most sensitive peptide markers/protein were selected in order to retrieve quantitative information. Relevant LODs were found to range from 0.1μg/g for milk to 0.3μg/g for egg and 2μg/g for soy. PMID:25042441

  1. Precision Penning Trap Mass Spectrometry of S, Kr and Xe

    NASA Astrophysics Data System (ADS)

    Redshaw, Matthew

    2005-04-01

    Using a phase coherent technique to measure the cyclotron frequency of single ions in a Penning trap [1], we have performed mass measurements on ^32S and the two most abundant krypton and xenon isotopes ^84Kr, ^86Kr, ^ 129Xe and ^132Xe, to relative precisions of 0.1 ppb. This is a factor of ˜10-100 improvement in precision over current values [2]. [1] M.P. Bradley, J.V. Porto, S. Rainville, J.K. Thompson, and D.E. Pritchard, PRL 83, 4510 (1999). [2] G. Audi, A.H. Wapstra, and C. Thibault, Nucl Phys A729, 337 (2003).

  2. Rapid Characterization and Identification of Flavonoids in Radix Astragali by Ultra-High-Pressure Liquid Chromatography Coupled with Linear Ion Trap-Orbitrap Mass Spectrometry.

    PubMed

    Zhang, Jing; Xu, Xiao-Jie; Xu, Wen; Huang, Juan; Zhu, Da-yuan; Qiu, Xiao-Hui

    2015-07-01

    A simple and effective method was established for separation and characterization of flavonoid constituents in Radix Astragali (RA) by combination of ultra-high-pressure liquid chromatography with LTQ-Orbitrap tandem mass spectrometry (u-HPLC-LTQ-Orbitrap-MS(n)). For three major structural types of flavonoids, the proposed fragmentation pathways and major diagnostic fragment ions of isoflavones, pterocarpans and isoflavans were investigated to trace isoflavonoid derivatives in crude plant extracts. Based on the systematic identification strategy, 48 constituents were rapidly detected and characterized or tentatively identified, many of which were first reported in RA. The u-PHLC-LTQ-Orbitrap MS(n) platform was proved as an effective tool for rapid qualitative analysis of secondary metabolite productions from natural resources.

  3. Atomic physics measurements in an electron Beam Ion Trap

    SciTech Connect

    Marrs, R.E.; Beiersdorfer, P.; Bennett, C.; Chen, M.H.; Cowan, T.; Dietrich, D.; Henderson, J.R.; Knapp, D.A.; Osterheld, A.; Schneider, M.B.

    1989-03-01

    An electron Beam Ion Trap at Lawrence Livermore National Laboratory is being used to produce and trap very-highly-charged ions (q less than or equal to 70/+/) for x-ray spectroscopy measurements. Recent measurements of transition energies and electron excitation cross sections for x-ray line emission are summarized. 13 refs., 10 figs.

  4. Advanced Quadrupole Ion Trap Instrumentation for Low Level Vehicle Emissions Measurements

    SciTech Connect

    McLuckey, S.A.

    1997-01-01

    Quadrupole ion trap mass spectrometry has been evaluated for its potential use in vehicle emissions measurements in vehicle test facilities as an analyzer for the top 15 compounds contributing to smog generation. A variety of ionization methods were explored including ion trap in situ chemical ionization, atmospheric sampling glow discharge ionization, and nitric oxide chemical ionization in a glow discharge ionization source coupled with anion trap mass spectrometer. Emphasis was placed on the determination of hydrocarbons and oxygenated hydrocarbons at parts per million to parts per billion levels. Ion trap in situ water chemical ionization and atmospheric sampling glow discharge ionization were both shown to be amendable to the analysis of arenes, alcohols, aldehydes and, to some degree, alkenes. Atmospheric sampling glow discharge also generated molecular ions of methy-t-butyl ether (MTBE). Neither of these ionization methods, however, were found to generate diagnostic ions for the alkanes. Nitric oxide chemical ionization, on the other hand, was found to yield diagnostic ions for alkanes, alkenes, arenes, alcohols, aldehydes, and MTBE. The ability to measure a variety of hydrocarbons present at roughly 15 parts per billion at measurement rates of 3 Hz was demonstrated. All of the ions with potential to serve as parent ions in a tandem mass spectrometry experiment were found to yield parent-to-product conversion efficiencies greater than 75%. The flexibility afforded to the ion trap by use of tailored wave-forms applied to the end-caps allows parallel monitoring schemes to be devised that provide many of the advantages of tandem mass spectrometry without major loss in measurement rate. A large loss in measurement rate would ordinarily result from the use of conventional tandem mass spectrometry experiments carried out in series for a large number of targeted components. These results have demonstrated that the ion trap has an excellent combination of

  5. Controlling trapping potentials and stray electric fields in a microfabricated ion trap through design and compensation

    NASA Astrophysics Data System (ADS)

    Doret, S. Charles; Amini, Jason M.; Wright, Kenneth; Volin, Curtis; Killian, Tyler; Ozakin, Arkadas; Denison, Douglas; Hayden, Harley; Pai, C.-S.; Slusher, Richart E.; Harter, Alexa W.

    2012-07-01

    Recent advances in quantum information processing with trapped ions have demonstrated the need for new ion trap architectures capable of holding and manipulating chains of many (>10) ions. Here we present the design and detailed characterization of a new linear trap, microfabricated with scalable complementary metal-oxide-semiconductor (CMOS) techniques, that is well-suited to this challenge. Forty-four individually controlled dc electrodes provide the many degrees of freedom required to construct anharmonic potential wells, shuttle ions, merge and split ion chains, precisely tune secular mode frequencies, and adjust the orientation of trap axes. Microfabricated capacitors on dc electrodes suppress radio-frequency pickup and excess micromotion, while a top-level ground layer simplifies modeling of electric fields and protects trap structures underneath. A localized aperture in the substrate provides access to the trapping region from an oven below, permitting deterministic loading of particular isotopic/elemental sequences via species-selective photoionization. The shapes of the aperture and radio-frequency electrodes are optimized to minimize perturbation of the trapping pseudopotential. Laboratory experiments verify simulated potentials and characterize trapping lifetimes, stray electric fields, and ion heating rates, while measurement and cancellation of spatially-varying stray electric fields permits the formation of nearly-equally spaced ion chains.

  6. Approach to the study of flavone di-C-glycosides by high performance liquid chromatography-tandem ion trap mass spectrometry and its application to characterization of flavonoid composition in Viola yedoensis.

    PubMed

    Cao, Jie; Yin, Chengle; Qin, Yan; Cheng, Zhihong; Chen, Daofeng

    2014-10-01

    The mass spectrometric (MS) analysis of flavone di-C-glycosides has been a difficult task due to pure standards being unavailable commercially and to that the reported relative intensities of some diagnostic ions varied with MS instruments. In this study, five flavone di-C-glycoside standards from Viola yedoensis have been systematically studied by high performance liquid chromatography-electrospray ionization-tandem ion trap mass spectrometry (HPLC-ESI-IT-MS(n)) in the negative ion mode to analyze their fragmentation patterns. A new MS(2) and MS(3) hierarchical fragmentation for the identification of the sugar nature (hexoses or pentoses) at C-6 and C-8 is presented based on previously established rules of fragmentation. Here, for the first time, we report that the MS(2) and MS(3) structure-diagnostic fragments about the glycosylation types and positions are highly dependent on the configuration of the sugars at C-6 and C-8. The base peak ((0,2) X1 (0,2) X(2)(-) ion) in MS(3) spectra of di-C-glycosides could be used as a diagnostic ion for flavone aglycones. These newly proposed fragmentation behaviors have been successfully applied to the characterization of flavone di-C-glycosides found in V. yedoensis. A total of 35 flavonoid glycosides, including 1 flavone mono-C-hexoside, 2 flavone 6,8-di-C-hexosides, 11 flavone 6,8-di-C-pentosides, 13 flavone 6,8-C-hexosyl-C-pentosides, 5 acetylated flavone C-glycosides and 3 flavonol O-glycosides, were identified or tentatively identified on the base of their UV profiles, MS and MS(n) (n = 5) data, or by comparing with reference substances. Among these, the acetylated flavone C-glycosides were reported from V. yedoensis for the first time.

  7. Ion collision crosssection measurements in quadrupole ion traps using a time-frequency analysis method.

    PubMed

    He, Muyi; Guo, Dan; Chen, Yu; Xiong, Xingchuang; Fang, Xiang; Xu, Wei

    2014-12-01

    In this study, a method for measuring ion collision crosssections (CCSs) was proposed through time-frequency analysis of ion trajectories in quadrupole ion traps. A linear ion trap with added high-order electric fields was designed and simulated. With the presence of high-order electric fields and ion-neutral collisions, ion secular motion frequency within the quadrupole ion trap will be a function of ion motion amplitude, thus a function of time and ion CCS. A direct relationship was then established between ion CCS and ion motion frequency with respect to time, which could be obtained through time-frequency analysis of ion trajectories (or ion motion induced image currents). To confirm the proposed theory, realistic ion trajectory simulations were performed, where the CCSs of bradykinin, angiotensin I and II, and ubiquitin ions were calculated from simulated ion trajectories. As an example, differentiation of isomeric ubiquitin ions was also demonstrated in the simulations. PMID:25319271

  8. Conformation-specific spectroscopy of peptide fragment ions in a low-temperature ion trap.

    PubMed

    Wassermann, Tobias N; Boyarkin, Oleg V; Paizs, Béla; Rizzo, Thomas R

    2012-06-01

    We have applied conformer-selective infrared-ultraviolet (IR-UV) double-resonance photofragment spectroscopy at low temperatures in an ion trap mass spectrometer for the spectroscopic characterization of peptide fragment ions. We investigate b- and a-type ions formed by collision-induced dissociation from protonated leucine-enkephalin. The vibrational analysis and assignment are supported by nitrogen-15 isotopic substitution of individual amino acid residues and assisted by density functional theory calculations. Under such conditions, b-type ions of different size are found to appear exclusively as linear oxazolone structures with protonation on the N-terminus, while a rearrangement reaction is confirmed for the a (4) ion in which the side chain of the C-terminal phenylalanine residue is transferred to the N-terminal side of the molecule. The vibrational spectra that we present here provide a particularly stringent test for theoretical approaches.

  9. Conformation-Specific Spectroscopy of Peptide Fragment Ions in a Low-Temperature Ion Trap

    NASA Astrophysics Data System (ADS)

    Wassermann, Tobias N.; Boyarkin, Oleg V.; Paizs, Béla; Rizzo, Thomas R.

    2012-06-01

    We have applied conformer-selective infrared-ultraviolet (IR-UV) double-resonance photofragment spectroscopy at low temperatures in an ion trap mass spectrometer for the spectroscopic characterization of peptide fragment ions. We investigate b- and a-type ions formed by collision-induced dissociation from protonated leucine-enkephalin. The vibrational analysis and assignment are supported by nitrogen-15 isotopic substitution of individual amino acid residues and assisted by density functional theory calculations. Under such conditions, b-type ions of different size are found to appear exclusively as linear oxazolone structures with protonation on the N-terminus, while a rearrangement reaction is confirmed for the a 4 ion in which the side chain of the C-terminal phenylalanine residue is transferred to the N-terminal side of the molecule. The vibrational spectra that we present here provide a particularly stringent test for theoretical approaches.

  10. A Scalable Microfabricated Ion Trap for Quantum Information Processing

    NASA Astrophysics Data System (ADS)

    Maunz, Peter; Haltli, Raymond; Hollowell, Andrew; Lobser, Daniel; Mizrahi, Jonathan; Rembetski, John; Resnick, Paul; Sterk, Jonathan D.; Stick, Daniel L.; Blain, Matthew G.

    2016-05-01

    Trapped Ion Quantum Information Processing (QIP) relies on complex microfabricated trap structures to enable scaling of the number of quantum bits. Building on previous demonstrations of surface-electrode ion traps, we have designed and characterized the Sandia high-optical-access (HOA-2) microfabricated ion trap. This trap features high optical access, high trap frequencies, low heating rates, and negligible charging of dielectric trap components. We have observed trap lifetimes of more than 100h, measured trap heating rates for ytterbium of less than 40quanta/s, and demonstrated shuttling of ions from a slotted to an above surface region and through a Y-junction. Furthermore, we summarize demonstrations of high-fidelity single and two-qubit gates realized in this trap. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000. This work was supported by the Intelligence Advanced Research Projects Activity (IARPA).

  11. Ejection of Coulomb Crystals from a Linear Paul Ion Trap for Ion-Molecule Reaction Studies.

    PubMed

    Meyer, K A E; Pollum, L L; Petralia, L S; Tauschinsky, A; Rennick, C J; Softley, T P; Heazlewood, B R

    2015-12-17

    Coulomb crystals are being increasingly employed as a highly localized source of cold ions for the study of ion-molecule chemical reactions. To extend the scope of reactions that can be studied in Coulomb crystals-from simple reactions involving laser-cooled atomic ions, to more complex systems where molecular reactants give rise to multiple product channels-sensitive product detection methodologies are required. The use of a digital ion trap (DIT) and a new damped cosine trap (DCT) are described, which facilitate the ejection of Coulomb-crystallized ions onto an external detector for the recording of time-of-flight (TOF) mass spectra. This enables the examination of reaction dynamics and kinetics between Coulomb-crystallized ions and neutral molecules: ionic products are typically cotrapped, thus ejecting the crystal onto an external detector reveals the masses, identities, and quantities of all ionic species at a selected point in the reaction. Two reaction systems are examined: the reaction of Ca(+) with deuterated isotopologues of water, and the charge exchange between cotrapped Xe(+) with deuterated isotopologues of ammonia. These reactions are examples of two distinct types of experiment, the first involving direct reaction of the laser-cooled ions, and the second involving reaction of sympathetically-cooled heavy ions to form a mixture of light product ions. Extensive simulations are conducted to interpret experimental results and calculate optimal operating parameters, facilitating a comparison between the DIT and DCT approaches. The simulations also demonstrate a correlation between crystal shape and image shape on the detector, suggesting a possible means for determining crystal geometry for nonfluorescing ions.

  12. Linear Ion Trap for the Mars Organic Molecule Analyzer

    NASA Astrophysics Data System (ADS)

    Brinckerhoff, William; Arevalo, Ricardo; Danell, Ryan; van Amerom, Friso; Pinnick, Veronica; Li, Xiang; Hovmand, Lars; Getty, Stephanie; Mahaffy, Paul; Goesmann, Fred; Steininger, Harald

    2014-05-01

    The 2018 ExoMars rover mission includes the Mars Organic Molecule Analyzer (MOMA) investigation. MOMA will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from radiative and oxidative degradation. When combined with the complement of instruments in the rover's Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds. MOMA includes a linear, or 2D, ion trap mass spectrometer (ITMS) that is designed to analyze molecular composition of (i) gas evolved from pyrolyzed powder samples and separated on a gas chromatograph and (ii) ions directly desorbed from solid samples at Mars ambient pressure using a pulsed laser and a fast-valve capillary ion inlet system. This "dual source" approach gives MOMA unprecedented breadth of detection over a wide range of molecular weights and volatilities. Analysis of nonvolatile, higher-molecular weight organics such as carboxylic acids and peptides even in the presence of significant perchlorate concentrations is enabled by the extremely short (~1 ns) pulses of the desorption laser. Use of the ion trap's tandem mass spectrometry mode permits selective focus on key species for isolation and controlled fragmentation, providing structural analysis capabilities. The flight-like engineering test unit (ETU) of the ITMS, now under construction, will be used to verify breadboard performance with high fidelity, while simultaneously supporting the development of analytical scripts and spectral libraries using synthetic and natural Mars analog samples guided by current results from MSL. ETU campaign data will strongly advise the specifics of the calibration applied to the MOMA flight model as well as the science operational procedures during the mission.

  13. Controlled collisions of a single atom and an ion guided by movable trapping potentials

    SciTech Connect

    Idziaszek, Zbigniew; Calarco, Tommaso; Zoller, Peter

    2007-09-15

    We consider a system composed of a trapped atom and a trapped ion. The ion charge induces in the atom an electric dipole moment, which attracts it with an r{sup -4} dependence at large distances. In the regime considered here, the characteristic range of the atom-ion interaction is comparable or larger than the characteristic size of the trapping potential, which excludes the application of the contact pseudopotential. The short-range part of the interaction is described in the framework of quantum-defect theory, by introducing some short-range parameters, which can be related to the s-wave scattering length. When the separation between traps is changed we observe trap-induced shape resonances between molecular bound states and vibrational states of the external trapping potential. Our analysis is extended to quasi-one-dimensional geometries, when the scattering exhibit confinement-induced resonances, similar to the ones studied before for short-range interactions. For quasi-one-dimensional systems we investigate the effects of coupling between the center of mass and relative motion, which occurs for different trapping frequencies of atom and ion traps. Finally, we show how the two types of resonances can be employed for quantum state control and spectroscopy of atom-ion molecules.

  14. Ultrahigh-performance liquid chromatography-ion trap mass spectrometry characterization of the steroidal saponins of Dioscorea panthaica Prain et Burkill and its application for accelerating the isolation and structural elucidation of steroidal saponins.

    PubMed

    Wang, Weihao; Zhao, Ye; Jing, Wenguang; Zhang, Jun; Xiao, Hui; Zha, Qin; Liu, An

    2015-03-01

    Dioscorea panthaica is a traditional Chinese medicinal herb used in the treatment of various physiological conditions, including cardiovascular disease, gastropathy and hypertension. Steroidal saponins (SS) are the main active ingredients of this herb and have effects on myocardial ischemia and cancer. The phytochemical evaluation of SS is both time-consuming and laborious, and the isolation and structural determination steps can be especially demanding. For this reason, the development of new methods to accelerate the processes involved in the identification, isolation and structural elucidation of SS is highly desirable. In this study, a new ultrahigh performance liquid chromatography-ion trap mass spectrometry (UHPLC-IT/MS(n)) method has been developed for the identification of the SS in D. panthaica Prain et Burkill. Notably, the current method can distinguish between spirostanol and furostanol-type compounds based on the fragmentation patterns observed by electrospray ionization-ion trap mass spectrometry (ESI-IT/MS(n)) analysis. UHPLC-IT/MS(n) was used to conduct a detailed investigation of the number, structural class and order of the sugar moieties in the sugar chains of the SS present in D. panthaica. The established fragmentation features were used to analyze the compounds found in the 65% ethanol fraction of the water extracts of D. panthaica. Twenty-three SS were identified, including 11 potential new compounds and six groups of isomers. Two of these newly identified SS were selected as representative examples, and their chemical structures were confirmed by (1)H and (13)C NMR analyses. This newly developed UHPLC-IT/MS(n) method therefore allowed for the efficient identification, isolation and structural determination of the SS in D. panthaica.

  15. Ultrahigh-performance liquid chromatography-ion trap mass spectrometry characterization of the steroidal saponins of Dioscorea panthaica Prain et Burkill and its application for accelerating the isolation and structural elucidation of steroidal saponins.

    PubMed

    Wang, Weihao; Zhao, Ye; Jing, Wenguang; Zhang, Jun; Xiao, Hui; Zha, Qin; Liu, An

    2015-03-01

    Dioscorea panthaica is a traditional Chinese medicinal herb used in the treatment of various physiological conditions, including cardiovascular disease, gastropathy and hypertension. Steroidal saponins (SS) are the main active ingredients of this herb and have effects on myocardial ischemia and cancer. The phytochemical evaluation of SS is both time-consuming and laborious, and the isolation and structural determination steps can be especially demanding. For this reason, the development of new methods to accelerate the processes involved in the identification, isolation and structural elucidation of SS is highly desirable. In this study, a new ultrahigh performance liquid chromatography-ion trap mass spectrometry (UHPLC-IT/MS(n)) method has been developed for the identification of the SS in D. panthaica Prain et Burkill. Notably, the current method can distinguish between spirostanol and furostanol-type compounds based on the fragmentation patterns observed by electrospray ionization-ion trap mass spectrometry (ESI-IT/MS(n)) analysis. UHPLC-IT/MS(n) was used to conduct a detailed investigation of the number, structural class and order of the sugar moieties in the sugar chains of the SS present in D. panthaica. The established fragmentation features were used to analyze the compounds found in the 65% ethanol fraction of the water extracts of D. panthaica. Twenty-three SS were identified, including 11 potential new compounds and six groups of isomers. Two of these newly identified SS were selected as representative examples, and their chemical structures were confirmed by (1)H and (13)C NMR analyses. This newly developed UHPLC-IT/MS(n) method therefore allowed for the efficient identification, isolation and structural determination of the SS in D. panthaica. PMID:25575790

  16. Measurement of the temperature of cold highly charged ions produced in an electron beam ion trap

    SciTech Connect

    Beiersdorfer, P.; Decaux, V.; Widmann, K.

    1994-09-14

    The temperature of highly charged titanium ions produced and trapped in an electron beam ion trap was determined by precisely measuring the broadening of the emission line profile caused by the thermal Doppler motion. The measured temperature ranges from about 700 eV for deeply trapped ions to about 70 eV for ions in a shallow trap. The latter value represents the lowest temperature at which the x-ray emission of collisonally excited heliumlike Ti{sup 20}+ ions has ever been recorded, and the measured transitions represent the narrowest x-ray lines observed from highly charged titanium ions.

  17. Thermal dissociation atmospheric chemical ionization ion trap mass spectrometry with a miniature source for selective trace detection of dimethoate in fruit juices.

    PubMed

    Ouyang, Yongzhong; Zhang, Xinglei; Han, Jing; Guo, Xiali; Zhu, Zhiqiang; Chen, Huanwen; Luo, Liping

    2013-01-21

    A miniature thermal dissociation atmospheric chemical ionization (TDCI) source, coupled with LTQ-MS, has been developed for rapid trace detection of pesticide residues such as dimethoate in highly viscous fruit juice samples. Instead of toxic organic solvents and the high electric field used in the conventional ionizations, an ionic liquid, a "green solvent", was employed to directly generate reagent ions in the TDCI process, followed by the proton or charge transfer with the analytes prior to the LTQ instrument for mass analysis. Trace amounts of dimethoate in fresh orange juices have been quantitatively detected, without any sample pretreatment or aid of high-pressure gas. A low limit of detection (LOD = 8.76 × 10(-11) g mL(-1)), acceptable relative standard deviation (RSD = 3.1-10.0%), and reasonable recoveries (91.2-102.8%) were achieved with this method for direct detection of dimethoate in highly viscous orange juice samples. The average analysis time for each single sample was less than 30 seconds. These experimental results showed that the miniature TDCI developed here is a powerful tool for the fast trace detection of pesticide residues in complex viscous fruit juices, with the advantage of high sensitivity, high speed, and high-throughput, ease of operation, and so on. Because of no chemical contamination and high voltage damage to the analytes and the environment, the technique has promising applications for online quality monitoring in the area of food safety. PMID:23181260

  18. Detection of reactive metabolites using isotope-labeled glutathione trapping and simultaneous neutral loss and precursor ion scanning with ultra-high-pressure liquid chromatography triple quadruple mass spectrometry.

    PubMed

    Huang, Ke; Huang, Lingyi; van Breemen, Richard B

    2015-04-01

    Metabolic activation of drugs to electrophilic species is responsible for over 60% of black box warnings and drug withdrawals from the market place in the United States. Reactive metabolite trapping using glutathione (GSH) and analysis using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) or HPLC with high resolution mass spectrometry (mass defect filtering) have enabled screening for metabolic activation to become routine during drug development. However, current MS-based approaches cannot detect all GSH conjugates present in complex mixtures, especially those present in extracts of botanical dietary supplements. To overcome these limitations, a fast triple quadrupole mass spectrometer-based approach was developed that can detect positively and negatively charged GSH conjugates in a single analysis without the need for advanced knowledge of the elemental compositions of potential conjugates and while avoiding false positives. This approach utilized UHPLC instead of HPLC to shorten separation time and enhance sensitivity, incorporated stable-isotope labeled GSH to avoid false positives, and used fast polarity switching electrospray MS/MS to detect GSH conjugates that form positive and/or negative ions. The general new method was then used to test the licorice dietary supplement Glycyrrhiza glabra, which was found to form multiple GSH conjugates upon metabolic activation. Among the GSH conjugates found in the licorice assay were conjugates with isoliquiritigenin and glabridin, which is an irreversible inhibitor of cytochrome P450 enzymes.

  19. Mass trapping with MosquiTRAPs does not reduce Aedes aegypti abundance

    PubMed Central

    Degener, Carolin Marlen; de Ázara, Tatiana Mingote Ferreira; Roque, Rosemary Aparecida; Rösner, Susanne; Rocha, Eliseu Soares Oliveira; Kroon, Erna Geessien; Codeço, Cláudia Torres; Nobre, Aline Araújo; Ohly, Jörg Johannes; Geier, Martin; Eiras, Álvaro Eduardo

    2015-01-01

    The objective of this study was to evaluate the effectiveness of Aedes aegypti mass trapping using the sticky trap MosquiTRAP (MQT) by performing a cluster randomised controlled trial in Manaus, state of Amazonas, Brazil. After an initial questionnaire and baseline monitoring of adult Ae. aegypti abundance with BG-Sentinel (BGS) traps in six clusters, three clusters were randomly assigned to the intervention arm where each participating household received three MQTs for mass trapping during 17 months. The remaining three clusters (control arm) did not receive traps. The effect of mass trapping on adult Ae. aegypti abundance was monitored fortnightly with BGS traps. During the last two months of the study, a serological survey was conducted. After the study, a second questionnaire was applied in the intervention arm. Entomological monitoring indicated that MQT mass trapping did not reduce adult Ae. aegypti abundance. The serological survey indicated that recent dengue infections were equally frequent in the intervention and the control arm. Most participants responded positively to questions concerning user satisfaction. According to the results, there is no evidence that mass trapping with MQTs can be used as a part of dengue control programs. The use of this sticky trap is only recommendable for dengue vector monitoring. PMID:25946154

  20. Structural definition of trehalose 6-monomycolates and trehalose 6,6'-dimycolates from the pathogen Rhodococcus equi by multiple-stage linear ion-trap mass spectrometry with electrospray ionization.

    PubMed

    Hsu, Fong-Fu; Wohlmann, Jens; Turk, John; Haas, Albert

    2011-12-01

    The cell wall of the pathogenic bacterium Rhodococcus equi (R. equi) contains abundant trehalose monomycolate (TMM) and trehalose dimycolate (TDM), the glycolipids bearing mycolic acids. Here, we describe multiple-stage (MS(n)) linear ion-trap (LIT) mass spectrometric approaches toward structural characterization of TMM and TDM desorbed as [M + Alk](+) (Alk = Na, Li) and as [M + X](-) (X = CH(3)CO(2), HCO(2)) ions by electrospray ionization (ESI). Upon MS(n) (n=2, 3, 4) on the [M + Alk](+) or the [M + X](-) adduct ions of TMM and TDM, abundant structurally informative fragment ions are readily available, permitting fast assignment of the length of the meromycolate chain and of the α-branch on the mycolyl residues. In this way, structures of TMM and TDM isolated from pathogenic R. equi strain 103 can be determined. Our results indicate that the major TMM and TDM molecules possess 6, and/or 6'-mycolyl groups that consist of mainly C14 and C16 α-branches with meromycolate branches ranging from C18 to C28, similar to the structures of the unbound mycolic acids found in the cell envelope. Up to 60 isobaric isomers varying in chain length of the α-branch and of the meromycolate backbone were observed for some of the TDM species in the mixture. This mass spectrometric approach provides a direct method that affords identification of various TMM and TDM isomers in a mixture of which the complexity of this lipid class has not been previously reported using other analytical methods. PMID:21972013

  1. A strategy for comprehensive identification of sequential constituents using ultra-high-performance liquid chromatography coupled with linear ion trap-Orbitrap mass spectrometer, application study on chlorogenic acids in Flos Lonicerae Japonicae.

    PubMed

    Zhang, Jia-yu; Wang, Zi-jian; Li, Yun; Liu, Ying; Cai, Wei; Li, Chen; Lu, Jian-qiu; Qiao, Yan-jiang

    2016-01-15

    The analytical methodologies for evaluation of multi-component system in traditional Chinese medicines (TCMs) have been inadequate or unacceptable. As a result, the unclarity of multi-component hinders the sufficient interpretation of their bioactivities. In this paper, an ultra-high-performance liquid chromatography coupled with linear ion trap-Orbitrap (UPLC-LTQ-Orbitrap)-based strategy focused on the comprehensive identification of TCM sequential constituents was developed. The strategy was characterized by molecular design, multiple ion monitoring (MIM), targeted database hits and mass spectral trees similarity filter (MTSF), and even more isomerism discrimination. It was successfully applied in the HRMS data-acquisition and processing of chlorogenic acids (CGAs) in Flos Lonicerae Japonicae (FLJ), and a total of 115 chromatographic peaks attributed to 18 categories were characterized, allowing a comprehensive revelation of CGAs in FLJ for the first time. This demonstrated that MIM based on molecular design could improve the efficiency to trigger MS/MS fragmentation reactions. Targeted database hits and MTSF searching greatly facilitated the processing of extremely large information data. Besides, the introduction of diagnostic product ions (DPIs) discrimination, ClogP analysis, and molecular simulation, raised the efficiency and accuracy to characterize sequential constituents especially position and geometric isomers. In conclusion, the results expanded our understanding on CGAs in FLJ, and the strategy could be exemplary for future research on the comprehensive identification of sequential constituents in TCMs. Meanwhile, it may propose a novel idea for analyzing sequential constituents, and is promising for quality control and evaluation of TCMs.

  2. A system for trapping barium ions in a microfabricated surface trap

    SciTech Connect

    Graham, R. D. Sakrejda, T.; Wright, J.; Zhou, Z.; Blinov, B. B.; Chen, S.-P.

    2014-05-15

    We have developed a vacuum chamber and control system for rapid testing of microfabricated surface ion traps. Our system is modular in design and is based on an in-vacuum printed circuit board with integrated filters. We have used this system to successfully trap and cool barium ions and have achieved ion ‘dark' lifetimes of 31.6 s ± 3.4 s with controlled shuttling of ions. We provide a detailed description of the ion trap system including the in-vacuum materials used, control electronics and neutral atom source. We discuss the challenges presented in achieving a system which can work reliably over two years of operations in which the trap under test was changed at least 10 times.

  3. Unequivocal Enantiomeric Identification and Analysis of 10 Chiral Pesticides in Fruit and Vegetables by QuEChERS Method Combined With Liquid Chromatography-Quadruple/Linear Ion Trap Mass Spectrometry Determination.

    PubMed

    He, Zeying; Peng, Yi; Wang, Lu; Luo, Ming; Liu, Xiaowei

    2015-12-01

    In this research, 10 chiral pesticides in fruits and vegetables were simultaneously determined using chiral liquid chromatography triple quadrupole-linear ion trap hybrid mass spectrometry (LC-QqLIT). The QuEChERS method was applied for sample preparation, and an enhanced product ion (EPI) scan was used to acquire tandem mass spectrometry (MS/MS) spectra for the library search. Parameters including limit of detection (LOD), limit of quantification (LOQ), linearity, relative standard deviation (RSD), and matrix effects were evaluated in five representative matrices (strawberry, leek, cowpea, tomato, and eggplant). Good linearity with coefficient of determination (r(2) ) ≥0.997 was obtained for all 20 enantiomers in these five matrices over the range from 1.0 to 250 µg L(-1) . All the recoveries at 5 and 50 µg kg(-1) (n = 5) ranged between 70% and 120% with RSD below 20%, indicating satisfactory precision. The LOQ for the enantiomers ranged between 0.05 and 1 µg kg(-1) . Based on the proposed method, 135 commonly consumed fruits and vegetables taken from markets in Guizhou province, China, were analyzed. Enantioselective degradation for the selected chiral pesticides was observed in most of the positive samples. PMID:26392120

  4. Characterization and identification of the chemical constituents from tartary buckwheat (Fagopyrum tataricum Gaertn) by high performance liquid chromatography/photodiode array detector/linear ion trap FTICR hybrid mass spectrometry.

    PubMed

    Ren, Qiang; Wu, Caisheng; Ren, Yan; Zhang, Jinlan

    2013-02-15

    In recent years tartary buckwheat has become popular healthful food due to its antioxidant, antidiabetic and antitumor activities. However, its chemical constituents have not yet been fully characterized and identified. In this paper, a novel high performance liquid chromatography coupled with photodiode array detector and linear ion trap FTICR hybrid mass spectrometry (HPLC-PDA/LTQ-FTICRMS) method was established to characterize and identify a total of 36 compounds by a single run. The retention time, maximum UV absorption wavelength, accurate mass weight and characteristic fragment ions were collected on line. To confirm the structures, 11 compounds were isolated and identified by MS and NMR experiments. 1, 3, 6, 6'-tetra-feruloyl sucrose named taroside was a new phenlypropanoid glycoside, together with 3, 6-di-p-coumaroyl-1, 6'-di-feruloyl sucrose, 1, 6, 6'-tri-feruloyl-3-p-coumaroyl sucrose, N-trans-feruloyltyramine and quercetin-3-O-[β-D-xyloxyl-(1→2)-α-L-rhamnoside] were isolated for the first time from the Fagopyrum species. The research enriched the chemical information of tartary buckwheat.

  5. Rydberg excitation of trapped strontium ions (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Hennrich, Markus; Higgins, Gerard; Pokorny, Fabian; Kress, Florian; Maier, Christine; Haag, Johannes; Colombe, Yves

    2016-04-01

    Trapped Rydberg ions are a novel approach for quantum information processing [1,2]. This idea joins the advanced quantum control of trapped ions with the strong dipolar interaction between Rydberg atoms. For trapped ions this method promises to speed up entangling interactions [3] and to enable such operations in larger ion crystals [4]. We report on the first experimental realization of trapped strontium Rydberg ions. A single ion was confined in a linear Paul trap and excited to Rydberg states (25S to 37S) using a two-photon excitation with 243nm and 308nm laser light. The transitions we observed are narrow and the excitation can be performed repeatedly which indicates that the Rydberg ions are stable in the ion trap. Similar results have been recently reported on a single photon Rydberg excitation of trapped calcium ions [5]. The tunability of the 304-309nm laser should enable us to excite our strontium ions to even higher Rydberg levels. Such highly excited levels are required to achieve a strong interaction between neighboring Rydberg ions in the trap as will be required for quantum gates using the Rydberg interaction. References [1] M. Müller, L. Liang, I. Lesanovsky, P. Zoller, New J. Phys. 10, 093009 (2008). [2] F. Schmidt-Kaler, et al., New J. Phys. 13, 075014 (2011). [3] W. Li, I. Lesanovsky, Appl. Phys. B 114, 37-44 (2014). [4] W. Li, A.W. Glaetzle, R. Nath, I. Lesanovsky, Phys. Rev. A 87, 052304 (2013). [5] T. Feldker, et al., arXiv:1506.05958

  6. Targeted analysis of multiple pharmaceuticals, plant toxins and other secondary metabolites in herbal dietary supplements by ultra-high performance liquid chromatography-quadrupole-orbital ion trap mass spectrometry.

    PubMed

    Vaclavik, Lukas; Krynitsky, Alexander J; Rader, Jeanne I

    2014-01-31

    In this study, an ultra-high performance liquid chromatography-quadrupole-orbital ion trap mass spectrometry (UHPLC-Q-orbitrap MS) method was developed and validated for simultaneous determination of 96 pharmaceuticals, plant toxins, and other plant secondary metabolites in herbal dietary supplements. Target analytes were extracted from samples using the QuEChERS (quick easy cheap effective rugged safe) procedure. The instrument was operated in full MS-data dependent tandem mass spectrometry (full MS-dd-MS/MS) acquisition mode which enabled collection of quantitative high resolution (HR) full mass spectral data and confirmatory HR MS/MS data in a single run. The method provided excellent selectivity in both full MS and dd-MS/MS mode. Under optimized collision energy settings, product ion spectra containing both precursor and two or more product ions were obtained for most of the analytes. Limits of detection (LODs) and limits of quantification (LOQs) for the method differed significantly for the examined matrices. LODs≤10μg kg(-1) and LOQs≤50μg kg(-1) were obtained for 48 to 81% of target compounds across five different matrices. With the exception of highly polar analytes, the optimized QuEChERS extraction procedure provided acceptable recoveries in the range 70%-120%. The precision of the method, characterized as the relative standard deviation (RSD, n=5), was ≤25% and ≤18% at spiking concentrations of 50μg kg(-1) and 500μg kg(-1), respectively. Because of variations in matrix effects in extracts of herbal dietary supplements that differed in composition, the method of standard additions and an approach based on dilution of matrix components followed by quantification using solvent standards were applied for quantification. The procedure was used to examine commercial dietary supplements for the 96 analytes of interest. To the best of our knowledge, this is the first report of an integrated analysis and quantification of this wide range of compounds.