Phase synchronization of an ion ensemble by frequency sweep excitation in Fourier transform ion cyclotron resonance

The Fourier transform ion cyclotron resonance (FT-ICR) signal is produced by the coherent motion of a population of ions. The ability to produce a well-defined ion packet by excitation of an initially random ion ensemble is a major limiting factor of high mass FT-ICR. Ions must be both resonant and in phase with the applied radio frequency excitation field to be accelerated to radii suitable for detection by FT-ICR. Synchronization of the phase angles of an ensemble of ions occurs by off-resonant acceleration during frequency swept excitation. Results from computer-simulated ion trajectories suggest that phase synchronization of the ion packet prior to resonant excitation results in better spatial definition of the ion ensemble.     

Elimination of z-ejection in Fourier transform ion cyclotron resonance mass spectrometry by radio frequency electric field shimming

In Fourier transform ion cyclotron resonance (FT/ICR) mass spectrometry, coherent ion cyclotron orbital motion is produced by resonant radio frequency (rf) electric field excitation. However, because the excitation electrodes are of finite dimensions, the desired transverse (to the applied magnetic field) rf electric field is accompanied by an rf electric field component along the z- (magnetic field) direction, resulting in mass-dependent z-ejection and mass-dependent FT/ICR mass spectral peak relative magnitudes. Addition of several "guard wires" of voltage-divided rf amplitude allows the rf electric field to be "shimmed" to near-perfect uniformity. In this paper (see also the accompanying paper by Russell et al.), we introduce two types of rf-shimmed ion traps. In the first type, guard wires are placed only in front of the trapping electrodes. In the second type, guard wire rings are placed inside the detector and trapping electrodes. For either arrangement, simion simulations were used to adjust the rf voltages applied (by use of voltage dividers) to the guard wires or rings so as to produce an optimally uniform rf field within the trap. The virtual elimination of z-excitation is confirmed by plots of magnitude-mode relative peak height vs ICR orbital radius. Because the guard wires (or rings) tend to shield the ions from the trapping electrode potential, the shift in ICR frequency with trapping voltage is also reduced, but not as well as by a screened trap.(ABSTRACT TRUNCATED AT 250 WORDS)     

A "screened" electrostatic ion trap for enhanced mass resolution, mass accuracy, reproducibility, and upper mass limit in Fourier transform ion cyclotron resonance mass spectrometry

Until now, it was thought that the optimal static electromagnetic ion trap for Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry should be designed to produce a quadrupolar electrical potential, for which the ion cyclotron frequency is independent of the ion's preexcitation location within the trap. However, a quadrupolar potential results in a transverse (to the magnetic field) electric field that increases linearly with distance from the center of the trap. That radially linear electric field shifts the observed ICR frequency, increases the ICR orbital radius, and ultimately limits the highest mass-to-charge ratio ion that can be contained within the trap. In this paper, we propose a new static electromagnetic ion "trap" in which grounded screens placed just inside the usual "trapping" plates produce a good approximation to a "particle-in-a-box" potential (rather than the quadrupolar "harmonic oscillator" potential). SIMION calculations confirm that the electric potential of the screened trap is near zero almost everywhere within the trap. For our screened orthorhombic (2.5 in. X 2 in. X 2 in.) trap, the experimental ICR frequency shift due to trapping voltage is reduced by a factor of approximately 100, and the experimental variation of ICR frequency with ICR radius is reduced by a factor of approximately 10 compared to a conventional (unscreened) 2-in. cubic ion trap.(ABSTRACT TRUNCATED AT 250 WORDS)     

Electron capture dissociation in a radio frequency ion trap

We report on the first evidence of electron capture dissociation (ECD) in a radio frequency (rf) ion trap. Peptide ions, [substance P]2+, trapped in a two-dimensional, linear rf ion trap were cleaved by electrons injected along the central axis of the trap. Along the axis, the rf field component was zero and a magnetic field of 50 mT was applied. This electron injection scheme keeps the energy of the electrons below 1 eV, preventing them from heating by the rf field. The present ECD efficiency is approximately 4% by irradiation of electron current of 0.2 microA for 80 ms. ECD in rf traps may open high-throughput and low-cost ECD applications to obtain molecular structure information complementary to collision-induced dissociation.     

Charge capacity limitations of radio frequency ion guides in their use for improved ion accumulation and trapping in mass spectrometry

The use of radio frequency (rf) ion guides as "linear" two-dimensional ion traps and ion guides for ion storage and accumulation, respectively, is becoming increasingly important for realizing improved sensitivity in mass spectrometry. Analytical relationships describing the ion accumulation operation mode of rf ion guides are reported. Comparisons are made between the rf quadrupole ion guide, higher-order rf multipoles and rf stacked ring ion guides, in terms of the charge capacity limitations due to the instability of ions, rf focusing efficiency limits, and effects due to rf ion heating (i.e., collisional activation due to rf oscillations of ions). Analytical relations for the stored charge quantity are derived in the low ion energy approximation, which is shown to be reasonable for the systems considered. The ion density spatial distribution is derived, an exponential form of which proved to provide a good approximation for high-order rf multipoles and stacked ring rf ion guides. The limit on the stored charge dependence upon rf is shown to be directly related to the thermal dissociation thresholds for the ions being studied; the limitation is weaker for higher-order multipoles and stacked ring ion guides. These results suggest that rf quadrupoles provide an optimum configuration when accumulation of a moderate ion density is sufficient (below 10(9) elementary charges/m). Alternatively, accumulation of an appreciable density for more fragile species, such as noncovalent complexes, may be realized using higher-order multipoles and stacked ring ion guides.     

A new calculation of the ion velocity shift in a vortex resonance experiment in He II

We calculate the shift in velocity of an ion trapped on a vortex, line in He II when, in addition to a dc electric field directed along the line, an ac field is applied perpendicular to the line. We employ a model of the ion on a line first introduced by Ohmi and Usui and used by them to calculate the dc mobility. The ion drift velocity in the presence of the ac field exhibits a nearly flat plateau as a function of dc field and a canted dip as a function of frequency. The present calculation differs in some details from the earlier one and permits a more reliable estimate of the change in velocity.This work is supported in part by two grants from the National Science Foundation: DMR 72-03221 A01 and GH-34890.     

Generation of single-cycle pulses spaced by an integer number of molecular periods

Abstract

Previous work has shown that a new light source consisting of mutually coherent spectral sidebands ranging from 2.94 μm to 195 nm can be obtained by adiabatic preparation of a molecular ensemble in a single vibrational superposition state. Molecular motion modulated the refractive index and thus led to the frequency modulation of the driving beat-note. The resulting sidebands were equidistant and separated by a frequency equal to the modulation frequency. In the present work we extend this idea by applying more input fields to the molecular ensemble. We take two input fields separated by one half of the modulation frequency, such that their second harmonics drive the molecular ensemble. The proposed approach results in generating an equidistant comb of frequencies separated by a fraction (1/4) of the modulation frequency. Moreover, the intensity of the generated train of pulses increases by the inverse of the same factor. An important feature of the generated comb is that it reaches zero frequency, and as a consequence allows for control of the absolute phase, or the phase of the carrier with respect to the envelope. Since many physical processes, for example photoionization of molecules by intense laser pulses, are influenced by the time dependence of the electric field (and not the envelope), control of absolute phase will become an important issue for few-cycle pulses.     

Modification of trapping potential by inverted sidekick electrode voltage during detection to extend time-domain signal duration for significantly enhanced fourier transform ion cyclotron resonance mass resolution

Applying an inverted voltage to the "sidekick" electrodes during ion cyclotron resonance detection improves both Fourier transform ion cyclotron resonance (FT-ICR) mass spectral signal-to-noise ratio (at fixed resolving power) and resolving power (at fixed signal-to-noise ratio). The time-domain signal duration increases by up to a factor of 2. The method has been applied to 7-T FT-ICR MS of electrosprayed positive ions from substance P and human growth hormone protein ( approximately 22 000 Da, m/Deltam50% 200 000), without the need for pulsed cooling gas inside the ICR trap. The modification can be easily adapted to any FT-ICR instrument equipped with sidekick electrodes. The present effects are shown to be comparable to electron field modification by injection of an electron beam during ICR detection, reported by Kaiser and Bruce (Kaiser, N. K.; Bruce, J. E. Anal. Chem. 2005, 77, 5973-5981.). Although the exact mechanism is not fully understood, computer simulations show that a flattening of the radial potential gradient along the magnetic field direction in the ICR trap may contribute to the effects. This study not only provides a way to enhance the quality of FT-ICR mass spectra but also offers insight into understanding of ion motions inside an ICR ion trap.     

Magnetic field contribution to the Lorentz model

The classical Lorentz model of dielectric dispersion is based on the microscopic Lorentz force relation and Newton's second law of motion for an ensemble of harmonically bound electrons. The magnetic field contribution in the Lorentz force relation is neglected because it is typically small in comparison with the electric field contribution. Inclusion of this term leads to a microscopic polarization density that contains both perpendicular and parallel components relative to the plane wave propagation vector. The modified parallel and perpendicular polarizabilities are both nonlinear in the local electric field strength.     

High-resolution field desorption/ionization fourier transform ion cyclotron resonance mass analysis of nonpolar molecules

We report the first field desorption ionization broadband high-resolution (m/Deltam(50%) approximately 65 000) mass spectra. We have interfaced a field ionization/field desorption source to a home-built 9.4-T FT-ICR mass spectrometer. The instrumental configuration employs convenient sample introduction (in-source liquid injection) and external ion accumulation. We demonstrate the utility of this configuration by generating high-resolution positive-ion mass spectra of C(60) and a midboiling crude oil distillate. The latter contains species not accessible by common soft-ionization methods, for example, low-voltage electron ionization, electrospray ionization, and matrix-assisted laser desorption/ionization. The present work demonstrates significant advantages of FI/FD FT-ICR MS for analysis of nonpolar molecules in complex mixtures.     

Instrumentation and method for ultrahigh resolution field desorption ionization fourier transform ion cyclotron resonance mass spectrometry of nonpolar species

We describe the construction and application of a 9.4-T FT-ICR mass spectrometer interfaced to a commercial field desorption ion source for high-resolution, high-mass accuracy measurements of nonpolar species. The FT-ICR MS instrument includes a liquid injection field desorption ionization source, octopole ion guides, external octopole ion trap capable of an axial potential gradient for ion ejection, capacitively coupled open cylindrical ion trap, and pulsed gas valve for ion cooling. Model compound responses with regard to various source and instrument conditions provide a basis for interpretation of broadband mass spectra of complex mixtures. As an example, we demonstrate broadband speciation of a Gulf Coast crude oil, with respect to numerous heteroatomic classes, compound types (rings plus double bonds), and carbon number distributions.     

Negative ion motion in normal and superfluid 3He

We report the first measurements of negative ion motion in the superfluid phases of ³He and in the normal phase below 17 mK. Refrigeration was achieved with nuclear demagnetization of copper and we used a pulsed NMR platinum powder thermometer immersed in the liquid. In the A phase the longitudinal resonance frequency provided an additional high-resolution thermometer. In the normal phase we observed a strictly temperature-independent mobility. In the superfluid phases we found two velocity regimes. For small applied electric fields the velocity is a linear function of the field and the corresponding mobility increases monotonically toward lower temperatures. At high electric fields the velocity is a nonlinear function of the field as a result of the pair-breaking effect of the moving ion. Available theoretical calculations are only in partial agreement with our results.This work was supported financially by the Academy of Finland.Guggenheim Fellow on leave from Cornell University, Ithaca, New York.On leave from Regensburg University, Regensburg, West Germany, supported by Deutsche Forschungsgemeinschaft and Finnish Ministry of Education.     

Capillary electrophoresis-fourier transform ion cyclotron resonance mass spectrometry for the identification of cationic metabolites via a pH-mediated stacking-transient isotachophoretic method

Capillary electrophoresis-mass spectrometry (CE-MS) is still widely regarded as an emerging tool in the field of metabolomics and metabolite profiling. A major reason for this is a reported lack of sensitivity of CE-MS when compared to gas chromatography-mass spectrometry GC/MS and liquid chromatography-mass spectrometry. The problems caused by the lack of sensitivity are exacerbated when CE is coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), due to the relatively low data acquisition rate of FT-ICR MS. Here, we demonstrate the use of an online CE sample preconcentration method that uses a combination of pH-mediated stacking and transient isotachophoresis, coupled with FT-ICR MS to improve the overall detection of cationic metabolites in the bacterium Desulfovibrio vulgaris Hildenborough. This method showed a significant increase in signal-to-noise ratio when compared to CE normal sample stacking, while providing good separation efficiency, reproducibility, and linearity. Detection limits for selected amino acids were between 0.1 and 2 microM. Furthermore, FT-ICR MS detection consistently demonstrated good mass resolution and sub-ppm mass accuracy.     

Magnetization reversal in Pt/Co(0.5 nm)/Pt nano-platelets patterned by focused ion beam lithography

Arrays of ultrathin Pt/Co(0.5 nm)/Pt nano-platelets with lateral sizes ranging from 30 nm to 1 μm have been patterned by focused ion beam (FIB) lithography under a weak Ga(+) ion fluence. From polar magneto-optical Kerr microscopy it is demonstrated that nano-platelets are ferromagnetic with perpendicular anisotropy down to a size of 50 nm. The irradiation process creates a magnetically soft ring at the nano-platelet periphery in which domain nucleation is initiated at a low field. The magnetization reversal in nano-platelets can be interpreted using a confined droplet model. All of the results prove that ultimate FIB patterning is suitable for preparing discrete magnetic recording media or small magnetic memory elements and nano-devices.     

Self-consistent particle simulation of radio frequency SF6 discharges: Role of ion recombination

The role of positive−negative ion recombination in simulating radio frequency (rf) SF₆ discharges is investigated based on Nanbu and Denpoh's theory [J. Phys. Soc. Jpn. 1998; 67: 1288]. The model of ion recombination is combined with the Particle-in-Cell/Monte Carlo (PIC/MC) simulation. Results show that the ion recombination is a dominant factor in simulating a steady rf discharge of SF₆. A criterion determining whether a periodic steady state is reached is proposed based on the ion recombination rate. It is found that the ion recombination rapidly increases as the gas pressure increases. From 25 to 50 m Torr, the loss of positive ions caused by ion recombination becomes comparable with that lost from collisions with electrodes.     

Characterization of an improved electrodynamic ion funnel interface for electrospray ionization mass spectrometry.

An improved electrodynamic ion funnel for ion focusing at high pressure (> 1 Torr) has been developed for a triple quadrupole mass spectrometer and its performance compared with that of an earlier prototype previously reported. The ion funnel consists of a series of ring electrodes of progressively smaller internal diameters to which rf and dc electric potentials are co-applied. The new design utilizes ring electrodes possessing larger internal diameters that taper down to a relatively larger exit aperture. In the 1-10 Torr pressure range, the new design provides significant improvement in low m/z ion transmission. Additionally, the overall ion transmission range is improved by linked scanning of the ion funnel's rf voltage concomitantly with the scanning of the quadrupole mass analyzer. Transmission of a noncovalent complex through the interface demonstrated that excessive ion heating was not problematic. Computer simulations of ion transport support the ion funnel design and help explain the relative performance of both designs. Both ion simulations and experimental results are in accord and indicate close to 100% ion transmission efficiency for electrosprayed biopolymer ions through the interface and into the mass analyzer.     

Superimposition of a magnetic field around an ion guide for electron ionization time-of-flight mass spectrometry

A new electron ionization source was developed for orthogonal acceleration time-of-flight mass spectrometry (TOFMS) based on the superimposition of a magnetic field around a radio frequency-only (rf-only) ion guide. The cylindrically symmetric magnetic field compresses the electron beam from the electron source into a long narrow volume along the ion guide axis. The magnetic field also helps to maintain a narrow energy distribution of electrons that penetrate the full length of the ion guide despite the influence of the radial rf field. Ionization occurs inside the ion guide with improved efficiency resulting from efficient use of electrons, prolonged interaction time, and nontraditionally large ionization volume. At the same time, the rf field effectively focuses ions radially and confines them to the axis of the ion guide by collisional focusing, leading to high ion transmission efficiency. Furthermore, the source can also be operated in a trap-and-pulse mode to improve the ion sampling duty cycle of orthogonal acceleration TOFMS. To validate the design concept of this new ion source, a simple prototype using a single set of cylindrical rods was constructed and retrofitted to an orthogonal acceleration TOFMS. A significant increase in ion signal intensity was observed by operating the source in a pulsed ion extraction mode. Low detection limits (for example, 12 fg for toluene) were determined at 12.5 spectra s(-1) in the full spectrum mode.     

Evidence for selective resputtering as the growth mechanism of pair-order anisotropy in amorphous TbFe films

Processing conditions for rf magnetron sputter-deposited amorphous TbFe films in which an atomic scale structural anisotropy (ASSA) results as a natural consequence of selective resputtering at the film surface during growth are presented. The ASSA, measured using polarization-dependent X-ray absorption fine structure with quantitative modelling via a parametrized nonlinear least squares fitting, is described as a pair order anisotropy (POA) where a statistical preference exists for like atom pairs in-plane and unlike atom pairs perpendicular to the film plane. The perpendicular magnetic anisotropy (PMA) energy increases with increasing POA for samples grown using decreasing rf power and increasing working gas pressure. The POA directly reflects the anisotropic electrostatic environment at the rare earth site which is required for PMA to result from a single ion anisotropy mechanism.     

Surface-induced dissociation of ions produced by matrix-assisted laser desorption/ionization in a fourier transform ion cyclotron resonance mass spectrometer

Intermediate pressure matrix-assisted laser desorption/ionization (MALDI) source was constructed and interfaced with a 6-T Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially configured for surface-induced dissociation (SID) studies. First MALDI-SID results in FT-ICR are presented, demonstrating unique advantages of SID over conventional FT-ICR MS ion activation techniques for structural characterization of singly protonated peptide ions. Specifically, we demonstrate that SID on a diamond surface results in a significantly better sequence coverage for singly protonated peptides than SORI-CID. A combination of two effects contributes to the improved sequence coverage: shattering of peptide ions on surfaces opens up a variety of dissociation channels at collision energies above 40 eV, and second, wide internal energy distribution deposited by collision with a stiff diamond surface provides an efficient mixing between the primary reaction channels that are dominant at low internal energies and extensive fragmentation at high internal excitation that results from shattering. Activation of MALDI-generated ions by collisions with surfaces in FT-ICR MS is a new powerful method for characterization and identification of biomolecules     

Radial structure of low pressure rf capacitive discharges

This paper studies the glow intensity distribution of the discharge plasma against the tube radius and reports the radial profiles of electron temperature and plasma concentration in the rf capacitive discharge registered with a Langmuir probe. An abrupt increase of electron temperature and glow intensity near the tube wall in the weak-current α-mode of the rf capacitive discharge is revealed, the radial distribution of plasma concentration and ion flow to the electrodes possessing a maximum near the radial sheath boundary. In the γ-mode of the rf capacitive discharge the electron temperature decrease in the total plasma volume leads to an electric field weakening and the peak of the glow intensity near the tube wall vanishes. The radial sheath thickness in the α-mode of the rf capacitive discharge obtained with 2D simulation experiences pulsations during the rf field period, the changing radial electric field heating electrons and increasing the plasma concentration near the boundary of the radial sheath.