Plasma source ion trap mass spectrometry: Enhanced abundance sensitivity by resonant ejection of atomic ions

An experimental study of resonant ion excitation in an rf quadrupole ion trap is reported. Atomic ions are generated in an inductively coupled plasma and injected into the ion trap where, after collisional cooling, they are irradiated by a low-voltage, dipole coupled waveform. Single frequency, narrowband, and broadband excitation pulses have been used. Absorption lineshapes (plots of observed ion signal versus excitation frequency) are shown for variations in buffer gas pressure and the amplitude and duration of the single frequency pulses. The absorption lineshapes are usually asymmetric and tail toward lower frequencies. At sufficiently low buffer gas pressure or potential well depth, the lineshapes broaden and become more asymmetric to the point that absorption by ions with adjacent mass-to-charge ratios overlaps. This overlapping absorption reduces the selectivity with which a single mass-to-charge ratio ion can be excited and ejected relative to nearby mass-to-charge ratio ions. The rate of ion ejection is different on the low versus high frequency edges of the absorption lines. This difference in ejection rates provides an important key to understanding the shape of the absorption lines. All of these observations are explained in terms of the known kinematic behavior of ions in real traps, that is, traps with substantial higher order symmetry components in the trapping field (“nonlinear” fields). The importance of the nonlinearity of the trapping field in understanding the observed lineshapes and their time dependencies is discussed. We also report resonant ejection results obtained using multiple frequency (narrow or broad bandwidth) excitation. Multiple frequency excitation allows ions with different mass-to-charge ratio values to be ejected from the trap using one excitation waveform. The finite ion storage capacity of the ion trap is thereby reserved for the ion(s) of interest. We show that ejection of ⁸⁹Y ions can be ～ 10⁵ times more efficient than ejection of ions at either m/z 88 or 90.     

A secondary ion microprobe ion trap mass spectrometer

An ion trap mass analyzer has been attached to an organic secondary ion microprobe. A pressure differential >100 can be maintained between the ion trap and microprobe. The well-focused secondary ion beam can transit a small (2 mm) diameter tube, but gas flow from ion trap to microprobe is impeded. This pressure differential allows the microprobe to retain imaging capability. Ion trap and microprobe data systems are integrated by taking advantage of the highly reproducible periodicity of the ion trap operating in resonant ejection mode and asynchronous signal and data acquisition afforded by commercially available interface cards. Secondary ion mass spectra and images obtained indicate an approximately 10-fold improvement in sensitivity, although preliminary evidence indicates low (<1%) trapping efficiency. Image data acquisition using the ion trap for mass analysis requires at least 10 times as much time compared to using a quadrupole mass filter because the mass-selected instability mode is used for mass analysis, i.e., mass resolution in the ion trap is not continuous as it is in the quadrupole.     

Suspended trapping gas chromatography I fourier transform mass spectrometry for analysis of complex organic mixtures

The superior sensitivity, dynamic range, and mass measurement accuracy of suspended trapping pulse sequences for gas chromatography combined with Fourier transform mass spectrometry (GC/FTMS) separations of complex organic mixtures is demonstrated. By combining intense ionization conditions with a suspended trapping event prior to detection the working range of the trapped ion cell is increased by 10³. Improved detection limits are shown for the GC/FTMS separation of a peppermint oil, with the suspended trapping total ion chromatogram yielding 28 peaks, compared with 15 with a conventional trapping pulse sequence. A fivefold to fifteenfold improvement in signal-to-noise for suspended trapping measurements is also demonstrated with comparison spectra from separations of an unleaded gasoline sample. Suspended trapping spectra show little mass discrimination when an external ion reservoir is used, and chromatographic peak heights differ from conventional spectra by less than 30% if the initial ion population is within the space charge limit of the cell. Finally, average wide band mass measurement errors for components differing in concentration by several orders of magnitude are improved by a factor of 6 to 20 with suspended trapping compared with conventional trapping. For example, average errors of 8.7 ppm are obtained for a suspended trapping GC/FTMS separation of peppermint oil from a single calibration table in which the analysis is performed in the absence of calibrant.     

Competition between resonance ejection and ion dissociation during resonant excitation in a quadrupole ion trap

The competition between ion dissociation and ion ejection during resonant excitation in a quadrupole ion trap is investigated. Ions of similar mass but with a range of critical energies for the onset of dissociation have been examined. The effects of the amplitude and duration of the resonant excitation, the well depth in which the ions are trapped, and the pressure and nature of the collision gas are explored. Once the onset of ion ejection is reached, the rate of ion ejection increases with increased amplitude of the resonant excitation signal. The rate of ejection decreases or stays constant as a function of the duration of the resonant excitation, depending upon the ion species being excited. Increasing the trapping well depth increases the relative amount of dissociation versus ejection as does increasing the pressure of the bath gas. Adding heavier bath gases lowers the onset of ion dissociation and raises the onset of ion ejection.     

Electron capture dissociation Fourier transform ion cyclotron resonance mass spectrometry in the electron energy range 0-50 eV

Electron capture dissociation (ECD) of polypeptide cations was obtained with pencil and hollow electron beams for both sidekick and gas-assisted dynamic ion trapping (GADT) using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) with an electrostatic ion transfer line. Increasing the number of trapped ions by multiple ICR trap loads using GADT improved the ECD sensitivity in comparison with sidekick ion trapping and ECD efficiency in comparison with single ion trap load by GADT. Furthermore, enhanced sensitivity made it possible to observe ECD in a wide range of electron energies (0-50 eV). The degree, rate and fragmentation characteristics of ECD FTICR-MS were investigated as functions of electron energy, electron irradiation time, electron flux and ion trapping parameters for this broad energy range. The results obtained show that the rate of ECD is higher for more energetic (>1 eV) electrons. Long electron irradiation time with energetic electrons reduces average fragment ion mass and decreases efficiency of formation of c- and z-type ions. The obtained dependencies suggest that the average fragment ion mass and the ECD efficiency are functions of the total fluence of the electron beam (electron energy multiplied by irradiation time). The measured electron energy distributions in low-energy ECD and hot ECD regimes are about 1 eV at full width half maximum in employed experimental configurations.     

Selective ion isolation/rejection over a broad mass range in the quadrupole ion trap

Techniques are presented for mass-selective ion manipulation over a wide mass range in a three-dimensional quadrupole. The methods use an auxiliary, low-amplitude radio-frequency signal applied to the endcap electrodes. This signal is either held at a single frequency as the fundamental radio-frequency trapping amplitude is ramped or swept over a frequency range while the fundamental radio-frequency trapping amplitude is held at a fixed level. Ion isolation and ejection are demonstrated for ions formed within the ion trap using electron ionization and for ions injected into the ion trap formed either by an air-sustained glow discharge or by electrospray. Mass-selective ion ejection is used to reduce matrix-ion-induced space charge during ion injection, thereby producing signal enhancement for the detection of 2, 4, 6-trinitrotoluene in air. Mass-selective isolation of ions with mass-to-charge ratios above the normal operating range (m / z 650) for the ion trap is also demonstrated after injection of myoglobin ions formed via electrospray.     

Investigation into factors affecting precision in ion trap mass spectrometry using different scan directions and axial modulation potential amplitudes

Electrospray ionization mass spectra obtained from different scan directions are observed to be dependent on the axial modulation potential amplitudes used for resonant ejection and on the positive deviation caused by higher even-multipole fields present in most commercial ion traps. The axial modulation voltage influences the dissociation of ions during resonant ejection and the observed mass shifts. The higher even-multipole fields in commercial ion traps are known to influence resonant ejection from the ion trap and can cause a loss in mass resolution for peaks in reverse scan mass spectra compared with that obtained by the forward scan. However, along with the dissociation of ions during resonant ejection causing a loss in resolution, the possibility of resolving an isotopic distribution is also shown to be influenced by the mass shifts caused by the space charge. These mass shifts differ depending on the scan direction employed. A significant loss in resolution can also result from resonant ejection using non-optimal axial modulation voltages. We also present results showing the ejection of ions at betaz = 1/2 using the reverse scan mode without the axial modulation voltage. Ion ejection at betaz = 1/2 is uncommon in commercial (stretched ion traps) with the conventional analytical scan without the use of a frequency of the axial modulation voltage corresponding to this non-linear resonance.     

Trajectory compensation in an autoresonant trap mass spectrometer

The auto-resonant trap mass spectrometer, ART-MS, utilizes electrostatic ion trapping within an anharmonic potential well. Ions are detected after mass selective trap ejection with auto-resonant driving employing only low-power rf electronics. We identify the major limiting factor in the mass resolution of these instruments. Whilst keeping in the spirit of maintaining a rapid scan rate, low cost, lightweight instrument, with minimal required machining tolerances, we introduce a method for much improving the mass resolutions of an ART-MS. The addition of two electrodes has enabled an improvement in the mass resolution by a factor of ～4. The scheme significantly reduces the effects of a finite sized trap and compensates for the influence of radial variation in natural oscillating frequencies within the trap. Compensation can be implemented with a wide range of designs and is not limited by the size of the trap.     

Novel linear ion trap mass analyzer composed of four planar electrodes

A novel linear ion trap mass analyzer was developed using just four elongated planar electrodes, mounted in parallel, and employing an RF potential for ion trapping in the radial and axial directions. Mass analysis was achieved using the mass-selective instability scan with ion ejection in the radial direction. The performance of this new device was characterized in comparison with the 6-electrode rectilinear ion trap (RIT) from which it is derived. The 4-electrode trap gives optimum performance in an asymmetric geometry, just like the original optimized 6-electrode RIT. The strong RF fringing fields at the ends of the RF rods account for axial ion trapping without use of extra electrodes or an axial DC voltage. Field calculations and simulations have been carried out to study the trapping potential inside RITs with various configurations. Demonstrated capabilities include analysis of externally injected ions with mass resolution in excess of 1000 and a mass/charge range of 650 Th as well as tandem mass spectrometry capabilities. The geometric simplicity and performance characteristics of the 4-electrode RIT make it particularly attractive in the development of next generation miniaturized mass spectrometers.     

Miniature toroidal radio frequency ion trap mass analyzer

A miniature ion trap mass analyzer is reported. The described analyzer is a 1/5-scale version of a previously reported toroidal radio frequency (rf) ion trap mass analyzer. The toroidal ion trap operates with maximum rf trapping voltages about 1 kVp-p or less; however despite the reduced dimensions, it retains roughly the same ion trapping capacity as conventional 3D quadrupole ion traps. The curved geometry provides for a compact mass analyzer. Unit-mass resolved mass spectra for n-butylbenzene, xenon, and naphthalene are reported and preliminary sensitivity data are shown for naphthalene. The expected linear mass scale with rf amplitude scan is obtained when scanned using a conventional mass-selective instability scan mode combined with resonance ejection.     

Origin of mass shifts in the quadrupole ion trap: dissociation of fragile ions observed with a hybrid ion trap/mass filter instrument

A novel hybrid tandem mass analyzer, coupling a quadrupole ion trap with a quadrupole mass filter, has been constructed to permit mass analysis of ions ejected from the ion trap. The initial application of this instrument is the investigation of the origin of mass shifts in the ion trap due to ion fragility. We hypothesize that fragile ions undergo mass shifts, characterized by peak fronting, due to early ejection from the quadrupole ion trap. As these ions come into resonance with the ejection frequency, they gain kinetic energy, collide with buffer gas molecules and thus can dissociate to produce fragment ions. These fragment ions will not be stable within the ion trap as they are situated past the stability boundary at q(z) = 0. 908. Consequently the fragment ions are ejected prematurely. This results in an apparent mass shift due to peak fronting. The experiments reported here clearly document the production of fragment ions as the origin of mass shifts during the resonant ejection of fragile ions. Copyright 2000 John Wiley & Sons, Ltd.     

Space-charge effects with mass-selective axial ejection from a linear quadrupole ion trap

Methods to reduce mass shifts caused by space charge with mass‐selective axial ejection from a linear quadrupole ion trap are investigated. For axial ejection, dipole excitation is applied to excite ions at q ≈ 0.85. The trapping radiofrequency (rf) voltage is scanned to bring ions of different m/z values into resonance for excitation. In the fringing field at the quadrupole exit, excited ions gain axial kinetic energy, overcoming the trapping potential, and are ejected from the trap. Space charge causes the frequencies of ion oscillation to decrease. Thus, greater rf voltages are required to bring ions into resonance for excitation and ejection, and the ions shift to higher apparent masses in a mass spectrum. At the same time, the peaks broaden, lowering resolution. The effects of injection q value, ejection q value, excitation amplitude, quadrupole dc voltages applied to the electrodes, applying an rf voltage to the exit lens, and scan speed, on mass shifts have been studied experimentally. Most experiments were done with only ions of protonated reserpine (m/z 609.3 and its isotopic peaks) in the trap. Some experiments were done with ions of protonated reserpine and ions of m/z 622 in the trap. In general, the mass shifts are reduced with higher ejection q values, higher excitation amplitudes, with quadrupole dc applied, and at higher scan speeds. The application of quadrupole dc appears to increase the ion cloud temperature, which lowers mass shifts. Thus, a proper choice of operating conditions can reduce, but not eliminate, mass shifts caused by space charge. Copyright © 2011 John Wiley & Sons, Ltd.     

Direct observation of trapping motion in elongated fourier-transform mass spectrometry trapped ion cells

Measurements by Fourier-transform mass spectrometry (FTMS) have been used to measure trapping oscillation profiles in elongated trapped ion cells of length 10–43 cm. Trapping periods extracted from these profiles are found to vary linearly with cell length for elongated cells. This is in contrast with the prediction based on a quadrupolar approximation of the electric field that trapping period should increase exponentially with increased cell length. An alternate analytical expression for trapping motion is derived that better accounts for the motion of ions with sufficient energy to approach the trap plates. Calculated trapping frequencies are within a few percent of values determined from ion trajectory simulations for any combination of cell length, trap potential, ion mass, and ion kinetic energy. The new expression also explains the experimentally determined trapping data obtained in elongated cells. This expression predicts an average axial energy near 0.6 eV for the ions that are preferentially detected by FTMS with the specific pulse sequence employed. Department of Chemistry,     

Laser-induced fluorescence for ion tomography in a Penning trap

Laser-induced ion fluorescence of laser-desorbed Ba⁺ ions provides a measure of the relative number of ions near the center of the Penning trap of a Fourier transform ion cyclotron resonance mass spectrometer. Here, we report the detection of Penning-trapped ions by ion fluorescence, subject to radially outward ion cloud expansion (because of ion-neutral collisions), radially inward ion cloud compression (because of quadrupolar axialization), and the effects of buffer gas pressure and electrostatic trapping potential on those processes. At high pressure and high trapping voltage, radial ejection is far more rapid than axial ejection; quadrupolar axialization increases the number of ions near the center of the trap as well as the length of time that ions may be trapped; higher pressure results in faster magnetron radial expansion; and the choice of azimuthal quadrupolar excitation waveform significantly affects the efficacy of axialization. Based on these results, we suggest that directly detected laser-induced ion fluorescence provides a general new tool for mapping the ion distribution and its time evolution in response to various excitatory and damping effects.     

新型三角形电极圆环离子阱的理论模拟研究

圆环离子阱由于其离子储存能力明显优于相同体积下的三维离子阱,近年来被认为是离子阱小型化发展的另一个重要方向。为进一步优化圆环形离子阱的质谱性能,特别是质量分辨能力,本研究提出了一种由三角形电极构建的新型圆环离子阱,它由两个完全等同的、截面为三角形的圆环电极及两个大小不等的圆筒型电极所组成,离子通过共振激发方式弹出。通过理论模拟和对电极结构的优化,获得了具有非对称性的三角形电极结构,通过改善圆环结构,优化电场分布,提高了离子引出效率和离子阱的质量分辨能力,其中一种最优化结构的圆环离子阱对m/z 609离子的质量分辨率达到1486。     

Computer simulation of the gap-tripole ion trap with linear injection, 3D ion accumulation,and versatile packet ejection

The behavior of a completely new ion trap is shown with SIMION 7.0 simulations. The simulated trap, which was a mix of a linear and a 3D trap, was made by axially setting two ion guides with a gap between them. Each guide consisted of three rods with three symmetrically delayed radio frequency (rf) voltages (tripole). The "injected" ions were linearly contained by pulsed potentials on the entrance and exit plates. Then the three-dimensional (3D) rf field in the gap, which was created by the tripole special rod arrangement, could trap the ions when the translational energy was dampened by collisions with low-pressure nitrogen. Because the injected ions were trapped in the small gap, the trapping cycle could be repeated many times before ion ejection, so a high concentrated ion cloud could be obtained. This trapping and accumulation methodology is not possible in most conventional multipole linear traps with even number of poles. Compared with quadrupole linear trap at the same rf amplitude, tripole lost more ions due to strong charge repulsion in the ion cloud. However, tripole could catch up the ions at higher voltage. Radial and axial mass-independent ejection of the ions localized in the tripole gap was very simple, compared with conventional linear ion traps that need extra and complicated electrodes for effective axial ejection.     

Mass selective ejection by axial resonant excitation from a linear ion trap

We describe a new mass selective ejection method from a linear ion trap, which we call axial resonant excitation (AREX). A set of vane lenses are inserted between each quadrupole rod to produce electrostatic potential that is approximately harmonic along the central axis of the quadrupole field. After ions with specific m/z are resonantly oscillated in the axial direction, the ions are mass selectively ejected in the axial direction. At a high scan rate of 11 Th/ms, AREX achieved a high ejection efficiency of more than 60%, which is more than three times higher than a conventional mass selective axial ejection method from a linear trap using fringing field.     

Resonant excitation in a low-pressure linear ion trap

It has been shown that through the process of resonant excitation the fragmentation of ions confined in a low-pressure (<0.05 mTorr) linear ion trap (LIT) can be accomplished while maintaining both high fragmentation efficiency and high resolution of excitation. The ion reserpine, 609.23 Da, has been fragmented with efficiencies greater than 90% while a higher mass ion, a homogeneously substituted triazatriphosphorine of mass 2721.89 Da, has been fragmented with 48% efficiency. This was accomplished by extended resonant excitation by low-amplitude auxiliary RF signals. Computer modelling of ion trajectories and analysis of the trapping potentials have demonstrated that a reduction in neutralization of ions on the rods (or losses on the rods) and increased fragmentation is a consequence of higher order terms in the potential introduced by the round-rod geometry of the LIT.     

The tripole linear ion trap with highly efficient orthogonal ion ejection designed by computer simulations

An ion guide, consisting of three rods carrying three alternating current (AC) voltages symmetrically delayed, called a tripole, was used as a linear ion trap (LIT) and studied by computer simulations. Radial containment of ions was also demonstrated with the pseudopotential which was calculated by approximating the tripole electric potential to the multipoles expansion. This work found a new analyte concentrator, which performs effective ion ejection, and is suitable for use with time-of-flight mass spectrometry. The efficiency of the overall process from the trapping until the ejection was higher than 90%, although some degree of ion spatial and kinetic energy spread which can be corrected with a reflectron was obtained. The reason for the ejection of this tripole linear ion trap (tLIT) lies in the high space available between the rods. The ejection is optimized with the application of focusing voltages, especially suitable for a tripole symmetry (one electrode has a pulse offset voltage and the other two have a fraction of that pulse). The beam is finally well parallelized with a rectangular Einzel lens.     

Characterization of an Electron Ionization Source Trap Operating in the Presence of a Magnetic Field Through Computer Simulation

We explore the feasibility of conducting electron ionization (EI) in a radio-frequency (rf) ion source trap for mass spectrometry applications. Electrons are radially injected into a compact linear ion trap in the presence of a magnetic field used essentially to lengthen the path of the electrons in the trap. The device can either be used as a stand-alone mass spectrometer or can be coupled to a mass analyzer. The applied parallel magnetic field and the oscillating rf electric field produced by the trap give rise to a set of coupled Mathieu equations of motion. Via numerical simulations, electron trajectories are studied under varying intensities of the magnetic field in order to determine the conditions that enhance ion production. Likewise, the dynamic behavior of the ions are investigated in the proposed EI source trap and the fast Fourier transform FFT formalism is used to obtain the frequency spectrum from the numerical simulations to study the motional frequencies of the ions which include combinations of the low-frequency secular and the high-frequency micromotion with magnetron and cyclotron frequencies. The dependence of these motional frequencies on the trapping conditions is examined and particularly, the limits of applying a radial magnetic field to the EI ion trap are characterized.