Rf Ion Trap Research Articles

Selective Gas-Phase Depletion of Chemical Contaminants in Dissolved Organic Matter Increases Compositional Coverage by FT-ICR Mass Spectrometry.

Fourier transform ion cyclotron resonance mass spectrometry of dissolved organic matter (DOM) extracted from environmental samples provides molecular speciation that enables visualization of compositional trends in the fate and cycling of biogenic and anthropogenic organics. Often, chemical contamination is introduced during field sampling (i.e., remote locations, cannot use glass). Further, preconcentration of DOM by solid-phase extraction often results in chemical contamination. When chemical noise is a dominant fraction of the ion signal, mass spectral performance is degraded by reduction of the ion trap analyte accumulation capacity and enhanced ion cloud dephasing during ICR detection. We have developed gas-phase ion depletion of unwanted chemical contaminants during ion injection into the linear RF ion trap of the hybrid linear ion trap 21 T FT-ICR mass spectrometer that improves detection of analytes by removing unwanted chemical noise. We demonstrate improvements in signal-to-noise ratio, dynamic range, and the number of observed analytes in dissolved organic matter samples that results in a 40-100% increase in the number of identified analytes. In many cases, the number of peaks observed per nominal mass more than doubles over select m/z regions. This gas-phase "clean-up" can salvage precious samples challenged by sampling location, sample volume, or collection protocols that cannot be avoided and maximizes the compositional information obtained. Further, this approach is generalizable and extendable to any hybrid linear ion trap instrument platform (e.g., LTQ-Orbitrap or linear ion trap-TOF). We highlight the power of gas-phase depletion with electrospray ionization, but this method is also applicable to other ionization modes.

A Radio-Frequency Ion Trap System for the Multi-Reflection Time-of-Flight Mass Spectrometer at SHANS and Its Offline Commissioning

To precisely measure atomic masses and select neutron-deficient isotopes produced by fusion evaporation reactions, an MRTOF-MS (multi-reflection time-of-flight mass spectrometer) at the SHANS (Spectrometer for Heavy Atom and Nuclear Structure) is being developed. One of the key parts, an RF ion trap system with the aim to provide brilliant ion pulses with a low energy spread and narrow pulse width for ion preparation prior to injection into the MRTOF mass analyzer, has been constructed and commissioned offline successfully. The principle, construction details and test results are reported. Pulsed beams of 39K1+, 85,87Rb1+ and 133Cs1+ ions have been tested and the amplitudes and frequencies of the RF signals, DC voltages, helium gas pressure and time parameters have been scanned. The corresponding time spreads have reached 0.252 µs, 0.394 µs and 0.450 µs, respectively.

State Readout of a Trapped Ion Qubit Using a Trap-Integrated Superconducting Photon Detector.

We report high-fidelity state readout of a trapped ion qubit using a trap-integrated photon detector. We determine the hyperfine qubit state of a single ^{9}Be^{+} ion held in a surface-electrode rf ion trap by counting state-dependent ion fluorescence photons with a superconducting nanowire single-photon detector fabricated into the trap structure. The average readout fidelity is 0.9991(1), with a mean readout duration of 46 μs, and is limited by the polarization impurity of the readout laser beam and by off-resonant optical pumping. Because there are no intervening optical elements between the ion and the detector, we can use the ion fluorescence as a self-calibrated photon source to determine the detector quantum efficiency and its dependence on photon incidence angle and polarization.

Tagging fullerene ions with helium in a cryogenic quadrupole trap

Helium tagging of charged C60q+ ions (q = 1–3) has been used for measuring electronic and infrared gas phase spectra, allowing astronomers to improve the identification of fullerenes in space. Here, we present a detailed study of the attachment of He to cold mass selected fullerene ions. Experiments were performed in the temperature variable radio frequency (rf) ion trap ISORI at high He densities and a few K. For all three charge states, the ternary rate coefficients for forming He-C60q+ are below 10−31 cm6s–1 and all three show temperature dependences, proportional to exp(-T/T0) with T0.< 1.5 K. While most of our knowledge on the interaction of C60+ with He atoms comes from ab initio calculations, from gas phase ion mobility experiments, and from fullerene ions ejected from He-droplets, the sequential addition of He to C60q+ in ter- or maybe bimolecular collisions provides complementary information. Our experimental results are tentatively explained with difficulties to form and stabilize the short-lived He-fullerene complexes while relaxation of hot fullerenes in collisions with cold He seems to be rather efficient. Severe restrictions are due to the fact that thermalized C60q+ ions behave like fast rotating rigid spheres. Despite the low efficiency in attaching the first He, measurements reveal a fast subsequent growth as soon as a few He atoms stick to the fullerene. In the case of triply charged ions, almost all primaries can be quickly converted into the particular structure He32-C603+. IR excitation of this thermalized complex with one 1329 cm-1 photon provides interesting insight into the decay kinetics.

OH+ Formation in the Low-temperature O+(4S) + H2 Reaction

Abstract Formation of OH+ in collisions of ground-state O+(4S) ions with normal H2 has been studied using a variable temperature 22-pole RF ion trap. From 300 to 30 K the measured reaction rate coefficient is temperature-independent, with a small decrease toward 15 K. The recent wave packet calculation predicts a slightly steeper temperature dependence. The rate coefficients at 300 and 15 K are almost the same, (1.4 ± 0.3) × 10−9 cm3 s−1 and (1.3 ± 0.3) × 10−9 cm3 s−1, respectively. The influence of traces of the two metastable ions, O+(2D) and O+(2P), has been examined by monitoring the H+ products of their reactions with H2, as well as by chemically probing them with N2 reactant gas.

Formation of H2O+ and H3O+ Cations in Reactions of OH+ and H2O+ with H2: Experimental Studies of the Reaction Rate Coefficients from T = 15 to 300 K

Abstract and cations play a significant role in the chemistry of the cold interstellar medium and hence their hydrogen abstraction reactions with have to be included in ion chemical models. The reactions lead directly or indirectly to ions that subsequently recombine with electrons and dissociate into H atoms and . The experiments described in this paper provide rate coefficients ( and ) for the reactions of and with over a wide temperature range (from 15 to 300 K). A cryogenic 22-pole RF ion trap instrument was employed for this purpose. It was found that increases from at 17 K to at 263 K while is nearly constant, varying from at 17 K to at 218 K.

A radio-frequency ion trap with string electrodes.

A radio-frequency (rf) ion trap with string electrodes is introduced. In this trap configuration, the rf electrodes are made of narrow metal strings, by which a negligibly small portion of light-induced fluorescence (LIF) is blocked. Then the LIF collection solid angle can be maximized. In the demonstration, barium ions are trapped and laser-cooled in the rf trap with string electrodes successfully, and the crystallization is confirmed by the LIF spectrum.

Preparation of Labile Ni+(cyclam) Cations in the Gas Phase Using Electron-Transfer Reduction through Ion-Ion Recombination in an Ion Trap and Structural Characterization with Vibrational Spectroscopy.

Gas-phase ion chemistry methods that capture and characterize the degree of activation of small molecules in the active sites of homogeneous catalysts form a powerful new tool to unravel how ligand environments affect reactivity. A key roadblock in this development, however, is the ability to generate the fragile metal oxidation states that are essential for catalytic activity. Here we demonstrate the preparation of the key Ni(I) center in the widely used cyclam scaffold using ion–ion recombination as a gas-phase alternative to electrochemical reduction. The singly charged Ni+(cyclam) coordination complex is generated by electron transfer from fluoranthene and azobenzene anions to doubly charged Ni2+(cyclam), using the electron-transfer dissociation protocol in a commercial quadrupole ion trap instrument and in a custom-built octopole RF ion trap. The successful preparation of the Ni+(cyclam) cation is verified through analysis of its vibrational spectrum obtained using the infrared free electron laser FELIX.

Identification and Partial Structural Characterization of Mass Isolated Valsartan and Its Metabolite with Messenger Tagging Vibrational Spectroscopy.

Recent advances in the coupling of vibrational spectroscopy with mass spectrometry create new opportunities for the structural characterization of metabolites with great sensitivity. Previous studies have demonstrated this scheme on 300 K ions using very high power free electron lasers in the fingerprint region of the infrared. Here we extend the scope of this approach to a single investigator scale as well as extend the spectral range to include the OH stretching fundamentals. This is accomplished by detecting the IR absorptions in a linear action regime by photodissociation of weakly bound N2 molecules, which are attached to the target ions in a cryogenically cooled, rf ion trap. We consider the specific case of the widely used drug Valsartan and two isomeric forms of its metabolite. Advantages and challenges of the cold ion approach are discussed, including disentangling the role of conformers and the strategic choices involved in the selection of the charging mechanism that optimize spectral differentiation among candidate structural isomers. In this case, the Na+ complexes are observed to yield sharp resonances in the high frequency NH and OH stretching regions, which can be used to easily differentiate between two isomers of the metabolite. Graphical Abstract ᅟ.

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*

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.

A Linear Trap for Studying the Interaction of Nanoparticles with Supersaturated Vapors

We present and characterize a versatile device for studying the controlled interaction of free nanoparticles with supersaturated vapors. It utilizes an rf-ion trap for storing a cloud (>108 particles) of singly charged nanoparticles in the sub 10-nm size regime and combines it with a static supersaturation chamber operating at low pressure in free molecular flow regime. This allows for the stable production of a homogeneous zone of variable saturation that can reach very high levels of supersaturation (S > 104). Compared with diffusion chambers, much higher saturations and more homogeneous saturation fields can be achieved, and convective flow is not an issue. The analysis of adsorption and nucleation processes on the surface of nanoparticles can be performed by mass spectrometry and optical spectroscopy. We discuss the general function principle of the device and demonstrate that it is well suited for studying water adsorption and deposition ice nucleation on metal oxide nanoparticles under the condition...

Generating nonclassical photon states via longitudinal couplings between superconducting qubits and microwave fields

Besides the conventional transverse couplings between superconducting qubits (SQs) and electromagnetic fields, there are additional longitudinal couplings when the inversion symmetry of the potential energies of the SQs is broken. We study nonclassical-state generation in a SQ which is driven by a classical field and coupled to a single-mode microwave field. We find that the classical field can induce transitions between two energy levels of the SQs, which either generate or annihilate, in a controllable way, different photon numbers of the cavity field. The effective Hamiltonians of these classical-field-assisted multiphoton processes of the single-mode cavity field are very similar to those for cold ions, confined to a coaxial RF-ion trap and driven by a classical field. We show that arbitrary superpositions of Fock states can be more efficiently generated using these controllable multiphoton transitions, in contrast to the single-photon resonant transition when there is only a SQ-field transverse coupling. The experimental feasibility for different SQs is also discussed.

Controlled synthesis and analysis of He–H+3 in a 3.7 K ion trap

Complexes of the triatomic hydrogen ion with helium were synthesised in a low-temperature 22-pole rf ion trap at He number densities of up to 1016 cm−3. Absolute ternary rate coefficients for sequentially attaching He atoms have been determined from the growth of complexes with increasing storage time. The number of helium-tagged ions is significantly reduced when increasing the nominal temperature from 4 to 25 K. Competition between attachment and dissociation via collisions leads to stationary Hen–H+3 (n up to 9) distributions. State-specific excitation of the trapped H+3 ions via IR transitions significantly reduces the formation of complexes. Tuning the laser to Δv2 = 1 transitions in the range of 2726 cm−1 leads to LIICG lines, i.e., to spectra caused by laser-induced inhibition of complex growth. In addition, almost 100 lines have been found between 2700 and 2765 cm−1, which are attributed to laser-induced dissociation of the in situ formed He–H+3 complex ions. These lines are not yet assigned; however, their absorption strength, statistics and predissociation lifetimes provide interesting information on both the stable complexes as well as on scattering resonances in low-energy H+3+He collisions. New calculations of the potential energy surface will help to analyse the dissociation spectrum. There are some indications that para-H+3 is enriched under the conditions of the present experiment.

Performance evaluation of a dual linear ion trap-Fourier transform ion cyclotron resonance mass spectrometer for proteomics research

A novel dual cell linear ion trap Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) and its performance characteristics are reported. A linear ion trap-Fourier transform ion cyclotron resonance mass spectrometer has been modified to incorporate a LTQ-Velos mass spectrometer. This modified instrument features efficient ion accumulation and fast MS/MS acquisition capabilities of dual cell linear RF ion trap instruments coupled to the high mass accuracy, resolution, and dynamic range of a FT-ICR for improved proteomic coverage. The ion accumulation efficiency is demonstrated to be an order of magnitude greater than that observed with LTQ-FT Ultra instrumentation. The proteome coverage with yeast was shown to increase over the previous instrument generation by 50% (100% increase on the peptide level). In addition, many lower abundance level yeast proteins were only detected with this modified instrument. This novel configuration also enables beam type CID fragmentation using a dual cell RF ion trap mass spectrometer. This technique involves accelerating ions between traps while applying an elevated DC offset to one of the traps to accelerate ions and induce fragmentation. This instrument design may serve as a useful option for labs currently considering purchasing new instrumentation or upgrading existing instruments. A novel hybrid mass spectrometer that allows increased MS/MS acquisition rates with high mass measurement accuracy and new ion fragmentation methods greatly improves the number of proteins, posttranslational modifications and protein-protein interactions that can be identified from cells.

State Specific Stabilization of H+ + H2(j) Collision Complexes

Stabilization of H3(+) collision complexes has been studied at nominal temperatures between 11 and 33 K using a 22-pole radio frequency (rf) ion trap. Apparent binary rate coefficients, k(*) = kr + k3[H2], have been measured for para- and normal-hydrogen at number densities between some 10(11) and 10(14) cm(-3). The state specific rate coefficients extracted for radiative stabilization, kr(T;j), are all below 2 × 10(-16) cm(3) s(-1). There is a slight tendency to decrease with increasing temperature. In contrast to simple expectations, kr(11 K;j) is for j = 0 a factor of 2 smaller than for j = 1. The ternary rate coefficients for p-H2 show a rather steep T-dependence; however, they are increasing with temperature. The state specific ternary rate coefficients, k3(T;j), measured for j = 0 and derived for j = 1 from measurements with n-H2, differ by an order of magnitude. Most of these surprising observations are in disagreement with predictions from standard association models, which are based on statistical assumptions and the separation of complex formation and competition between stabilization and decay. Most probably, the unexpected collision dynamics are due to the fact that, at the low translational energies of the present experiment, only a small number of partial waves participate. This should make exact quantum mechanical calculations of kr feasible. More complex is three-body stabilization, because it occurs on the H5(+) potential energy surface.

Resonant charge transfer of 3He2 + with 4He(1s2) at energies below 1 eV

The rate coefficient of resonant charge transfer between 3He2 + and 4He, at energies below 1 eV, was measured using an rf ion trap and time-of-flight mass spectrometry. We obtain a resonant charge transfer rate coefficient of 5.9 ± 0.6 × 10−10 cm3 s−1 at an equivalent temperature of 1200 K. The measured value compares favourably to existing calculations. This measurement extends our knowledge to a broader spectrum of energies as it provides information on the rate coefficients at a low energy and adds to our understanding of the charge transfer process of 3He2 +, α-particles, with He encountered in astrophysics and nuclear fusion.

Spatial distribution of ions in a linear octopole radio-frequency ion trap in the space-charge limit

We have explored the spatial distribution of an ion cloud trapped in a linear octopole radio-frequency (rf) ion trap. The two-dimensional distribution of the column density of stored silver dimer cations was measured via photofragment-ion yields as a function of the position of the incident laser beam over the transverse cross section of the trap. The profile of the ion distribution was found to be dependent on the number of loaded ions. Under high ion-loading conditions with a significant space-charge effect, ions form a ring profile with a maximum at the outer region of the trap, whereas they are localized near the center axis region at low loading of the ions. These results are explained quantitatively by a model calculation based on equilibrium between the space-charge-induced potential and the effective potential of the multipole rf field. The maximum adiabaticity parameter \eta_max is estimated to be about 0.13 for the high ion-density condition in the present octopole ion trap, which is lower than typical values reported for low ion densities; this is probably due to additional instability caused by the space charge.

Reaction dynamics of temperature-variable anion water clusters studied with crossed beams and by direct dynamics

We present a study of the different product channels in the reactions of OH and OH-(H2O) with methyl iodide over a range of collision energies. Direct dynamics classical trajectory simulations are employed to obtain an atomistic comparison with the experimental results. For the experiments we have combined a crossed beam ion imaging setup with a multipole rf ion trap. The trap allows us to prepare the molecular and cluster ions with a controlled internal temperature and thus provides well-defined initial conditions for reaction experiments at low collision energy. Changing the internal temperature of the cluster ions was found to have a profound effect on their reactivity.

Pulsed Multiple Reaction Monitoring Approach to Enhancing Sensitivity of a Tandem Quadrupole Mass Spectrometer

Liquid chromatography (LC)-triple quadrupole mass spectrometers operating in a multiple reaction monitoring (MRM) mode are increasingly used for quantitative analysis of low-abundance analytes in highly complex biochemical matrixes. After development and selection of optimum MRM transitions, sensitivity and data quality limitations are largely related to mass spectral peak interferences from sample or matrix constituents and statistical limitations at low number of ions reaching the detector. Herein, we report on a new approach to enhancing MRM sensitivity by converting the continuous stream of ions from the ion source into a pulsed ion beam through the use of an ion funnel trap (IFT). Evaluation of the pulsed MRM approach was performed with a tryptic digest of Shewanella oneidensis strain MR-1 spiked with several model peptides. The sensitivity improvement observed with the IFT coupled in to the triple quadrupole instrument is based on several unique features. First, ion accumulation radio frequency (rf) ion trap facilitates improved droplet desolvation, which is manifested in the reduced background ion noise at the detector. Second, signal amplitude for a given transition is enhanced because of an order-of-magnitude increase in the ion charge density compared to a continuous mode of operation. Third, signal detection at the full duty cycle is obtained, as the trap use eliminates dead times between transitions, which are inevitable with continuous ion streams. In comparison with the conventional approach, the pulsed MRM signals showed 5-fold enhanced peak amplitude and 2-3-fold reduced chemical background, resulting in an improvement in the limit of detection (LOD) by a factor of ∼4-8.

Escape of high mass ions due to initial thermal energy and its implications for axially symmetric RF ion trap mass analyzer design

Abstract This paper investigates the loss of high mass ions due to their initial thermal energy in ion trap mass analyzers. It provides an analytical expression for estimating the percentage loss of ions of a given mass at a particular temperature, in a trap operating under a predetermined set of conditions. The expression we developed can be used to study the loss of ions due to its initial thermal energy in traps which have nonlinear fields as well as those which have linear fields. The expression for the percentage of ions lost is shown to be a function of the temperature of the ensemble of ions, ion mass and ion escape velocity. An analytical expression for the escape velocity has also been derived in terms of the trapping field, drive frequency and ion mass. Because the trapping field is determined by trap design parameters and operating conditions, it has been possible to study the influence of these parameters on ion loss. The parameters investigated include ion temperature, magnitude of the initial potential applied to the ring electrode (which determines the low mass cut-off), trap size, dimensions of apertures in the endcap electrodes and RF drive frequency. Our studies demonstrate that ion loss due to initial thermal energy increases with increase in mass and that, in the traps investigated, ion escape occurs in the radial direction. Reduction in the loss of high mass ions is favoured by lower ion temperatures, increasing low mass cut-off, increasing trap size, and higher RF drive frequencies. However, dimensions of the apertures in the endcap electrodes do not influence ion loss in the range of aperture sizes considered.