Electrostatic Linear Ion Trap Research Articles

Realization of Higher Resolution Charge Detection Mass Spectrometry.

Charge detection mass spectrometry (CD-MS) allows mass distributions to be measured for heterogeneous samples that cannot be analyzed by conventional MS. With CD-MS, the m/z and charge are measured for individual ions using a detection cylinder embedded in an electrostatic linear ion trap (ELIT). Imprecision in both the m/z and charge measurements contribute to the mass resolution. However, if the charge can be measured with a precision of <0.2 e the charge state can be assigned with a low error rate and the mass resolving power only depends on the m/z resolution. Prior to this work, the best resolving power demonstrated experimentally for CD-MS was 700. Here we demonstrate a resolving power of >14,600, 20-times higher than the previous best. Trajectory simulations were used to optimize the geometry and electrostatic potentials of the ELIT. We found conditions where the energy dependence of the oscillation frequency becomes parabolic, and then operated with a nominal ion energy at the minimum of the parabola. The 14,600 resolving power was obtained with a beam collimator before the ELIT. With the collimator removed, the resolving power of the optimized ELIT is 7300, which is still an order of magnitude higher than the previous best. The resolving power was demonstrated by resolving the isotope distributions for peptides and proteins. High resolution CD-MS measurements were then used to resolve the glycans on a monoclonal antibody and applied to the analysis of hepatitis B virus capsids. The results indicate that procedures for adduct removal need to be improved for the full benefit of the higher resolving power to be realized for higher mass species. However, these results represent a key step toward using CD-MS to analyze very complex protein mixtures where charge states are not well resolved in the m/z spectrum because of congestion from numerous overlapping peaks.

Tandem mass spectrometry using continuous-wave infrared multiphoton dissociation in an electrostatic linear ion trap.

The electrostatic linear ion trap (ELIT) can be operated as a multi-reflection time-of-flight (MR-TOF) or Fourier transform (FT) mass analyzer. It has been shown to be capable of performing high-resolution mass analysis and high-resolution ion isolations. Although it has been used in charge-detection mass spectrometry (CDMS), it has not been widely used as a conventional mass spectrometer for ensemble measurements of ions, or for tandem mass spectrometer. The advantages of tandem mass spectrometer with high-resolution ion isolations in the ELIT have thus not been fully exploited. A homebuilt ELIT was modified with BaF2 viewports to facilitate transmission of a laser beam at the turnaround point of the second ion mirror in the ELIT. Fragmentation that occurs at the turnaround point of these ion mirrors should result in minimal energy partitioning due to the low kinetic energy of ions at these points. The laser was allowed to irradiate ions for a period of many oscillations in the ELIT. Due to the low energy absorption of gas-phase ions during each oscillation in the ELIT, fragmentation was found to occur over a range of oscillations in the ELIT generating a homogeneous ion beam. A mirror-switching pulse is shown to create time-varying perturbations in this beam that oscillate at the fragment ion characteristic frequencies and generate a time-domain signal. This was found to recover FT signal for protonated pYGGFL and pSGGFL precursor ions. Fragmentation at the turnaround point of an ELIT by continuous-wave infrared multiphoton dissociation (cw-IRMPD) is demonstrated. In cases where laser power absorption is low and fragmentation occurs over many laps, a mirror-switching pulse may be used to recover varying time-domain signal. The combination of laser activation at the turnaround points and mirror-switching isolation allows for tandem MS in the ELIT.

Surface-induced dissociation of protein complex ions in a modified electrostatic linear ion trap

The electrostatic linear ion trap (ELIT) is a device that can provide mass analysis via frequency measurement, followed by Fourier transformation from the frequency domain to the time domain, or via time measurement in a multi-reflection time-of-flight measurement. ELIT devices have been demonstrated to be capable of relatively high mass measurement resolution as well as high-resolution ion isolation capabilities. We have been exploring the possibility of developing the ELIT geometry as a stand-alone high-performance tandem mass spectrometer for native mass spectrometry (MS) studies. In this context, it is desirable to use an activation method capable of dissociating the high-mass complexes encountered in native MS. To this end, we describe the implementation of surface-induced dissociation (SID) in an ELIT and describe initial results for protein complexes generated under native conditions in which ion isolation, fragmentation, and product ion mass analysis all occur within the ELIT.

Electrostatic Linear Ion Trap Optimization Strategy for High Resolution Charge Detection Mass Spectrometry.

Single ion mass measurements allow mass distributions to be recorded for heterogeneous samples that cannot be analyzed by conventional mass spectrometry. In charge detection mass spectrometry (CD-MS), ions are detected using a conducting cylinder coupled to a charge sensitive amplifier. For optimum performance, the detection cylinder is embedded in an electrostatic linear ion trap (ELIT) where trapped ions oscillate between end-caps that act as opposing ion mirrors. The oscillating ions generate a periodic signal that is analyzed by fast Fourier transforms. The frequency yields the m/z, and the magnitude provides the charge. With a charge precision of 0.2 elementary charges, ions can be assigned to their correct charge states with a low error rate, and the m/z resolving power determines the mass resolving power. Previously, the best mass resolving power achieved with CD-MS was 300. We have recently increased the mass resolving power to 700, through the better optimization of the end-cap potentials. To make a more dramatic improvement in the m/z resolving power, it is necessary to find an ELIT geometry and end-cap potentials that can simultaneously make the ion oscillation frequency independent of both the ion energy and ion trajectory (angular divergence and radial offset) of the entering ion. We describe an optimization strategy that allows these conditions to be met while also adjusting the signal duty cycle to 50% to maximize the signal-to-noise ratio for the charge measurement. The optimized ELIT provides an m/z resolving power of over 300 000 in simulations. Coupled with the high precision charge determination available with CD-MS, this will yield a mass resolving power of 300 000. Such a high mass resolving power will be transformative for the analysis of heterogeneous samples.

Higher Resolution Charge Detection Mass Spectrometry.

Charge detection mass spectrometry is a single particle technique where the masses of individual ions are determined from simultaneous measurements of each ion's m/z ratio and charge. The ions pass through a conducting cylinder, and the charge induced on the cylinder is detected. The cylinder is usually placed inside an electrostatic linear ion trap so that the ions oscillate back and forth through the cylinder. The resulting time domain signal is analyzed by fast Fourier transformation; the oscillation frequency yields the m/z, and the charge is determined from the magnitudes. The mass resolving power depends on the uncertainties in both quantities. In previous work, the mass resolving power was modest, around 30-40. In this work we report around an order of magnitude improvement. The improvement was achieved by coupling high-accuracy charge measurements (obtained with dynamic calibration) with higher resolution m/z measurements. The performance was benchmarked by monitoring the assembly of the hepatitis B virus (HBV) capsid. The HBV capsid assembly reaction can result in a heterogeneous mixture of intermediates extending from the capsid protein dimer to the icosahedral T = 4 capsid with 120 dimers. Intermediates of all possible sizes were resolved, as well as some overgrown species. Despite the improved mass resolving power, the measured peak widths are still dominated by instrumental resolution. Heterogeneity makes only a small contribution. Resonances were observed in some of the m/z spectra. They result from ions with different masses and charges having similar m/z values. Analogous resonances are expected whenever the sample is a heterogeneous mixture assembled from a common building block.

Dynamic Calibration Enables High-Accuracy Charge Measurements on Individual Ions for Charge Detection Mass Spectrometry.

Charge detection mass spectrometry (CDMS) depends on the measurement of the charge induced on a cylinder by individual ions by means of a charge-sensitive amplifier. For high-accuracy charge measurements, the detection cylinder is embedded in an electrostatic linear ion trap (ELIT), and the ions oscillate back and forth through the cylinder so that multiple measurements are made. To assign the charge state with a low error rate, the charge of each ion must be determined with an uncertainty (root-mean-square deviation) of around 0.2 elementary charges. We show here that high-accuracy charge measurements can be achieved for large ions by dynamic calibration of the charge measurement using an internal standard. The internal standard is generated by irradiating the detection cylinder, by means of a small antenna, with a radiofrequency signal. Using this approach, we have obtained a relative charge uncertainty of around 5 × 10-4, allowing charge-state resolution to be achieved for single ions with up to 500 charges. In another application of this approach, the detection cylinder is irradiated with a signal that counteracts the transients generated when the potentials on the ELIT end-caps are switched to trapping mode. Using this approach, the dead time after switching (during which the signal cannot be analyzed) has been reduced by more than an order of magnitude. With charge-state resolution for ions with up to 500 charges, we were able to calibrate the charges precisely. The results show that the response of the charge-sensitive amplifier with dynamic calibration is linear to within a small fraction of an elementary charge.

Ion-Ion Interactions in Charge Detection Mass Spectrometry.

Charge detection mass spectrometry (CDMS) is a single-particle technique where the masses of individual ions are determined by simultaneously measuring their mass-to-charge ratio (m/z) and charge. Ions are usually trapped inside an electrostatic linear ion trap (ELIT) where they oscillate back and forth through a detection cylinder, generating a periodic signal that is analyzed by fast Fourier transforms. The oscillation frequency is related to the ion's m/z, and the magnitude is related to the ion's charge. In early work, multiple ion trapping events were discarded because there was a question about whether ion-ion interactions affected the results. Here, we report trajectory calculations performed to assess the influence of ion-ion interactions when multiple highly charged ions are simultaneously trapped in an ELIT. Ion-ion interactions cause trajectory and energy fluctuations that lead to variations in the oscillation frequencies that in turn degrade the precision and accuracy of the m/z measurements. The peak shapes acquire substantial high and low m/z tails, and the average m/z shifts to a higher value as the number of trapped ions increases. The effects of the ion-ion interactions are proportional to the product of the charges and the square root of the number of trapped ions and depend on the ions' m/z distribution. For the ELIT design examined here, ion-ion interactions limit the m/z resolving power to several hundred for a typical homogeneous ion population.

Dramatic Improvement in Sensitivity with Pulsed Mode Charge Detection Mass Spectrometry.

Charge detection mass spectrometry (CDMS) is emerging as a valuable tool to determine mass distributions for heterogeneous and high-mass samples. It is a single-particle technique where masses are determined for individual ions from simultaneous measurements of their mass-to-charge ratio (m/z) and charge. Ions are trapped in an electrostatic linear ion trap (ELIT) and oscillate back and forth through a detection cylinder. The trap is open and able to trap ions for a small fraction of the total measurement time so most of the ions (>99.8%) in a continuous ion beam are lost. Here, we implement an ion storage scheme where ions are accumulated and stored in a hexapole and then injected into the ELIT at the right time for them to be trapped. This pulsed mode of operation increases the sensitivity of CDMS by more than 2 orders of magnitude, which allows much lower titer samples to be analyzed. A limit of detection of 3.3 × 108 particles/mL was obtained for hepatitis B virus T = 4 capsids with a 1.3 μL sample. The hexapole where the ions are accumulated and stored is a significant distance from the ion trap so ions are dispersed in time by their m/z values as they travel between the hexapole and the ELIT. By varying the delay time between ion release and trapping, different windows of m/z values can be trapped.

Simultaneous Isolation of Nonadjacent m/z Ions Using Mirror Switching in an Electrostatic Linear Ion Trap.

Simultaneous isolation of ions of disparate mass-to-charge (m/z) ratios is demonstrated via appropriately timed pulsing of entrance and exit ion mirrors in an electrostatic linear ion trap (ELIT) mass spectrometer. Manipulation of the voltages of the entrance and exit mirrors, referred to as "mirror switching", has been demonstrated as a method in which ions can be both captured and isolated. High resolution isolation (>35 000) was previously demonstrated by selective gating of trapping electrodes to avoid ion lapping while closely spaced ions could continue to separate [ Johnson et al. Anal. Chem. 2019 , 91 , 8789 ]. In this work, we demonstrate that advantage can be taken of the ion lapping phenomenon in an ELIT to enable the simultaneous isolation of ions of disparate m/z ratios using mirror switching. This process is demonstrated with minimal ion loss using isotopologues of three carborane compounds ranging in m/z from 320 to 1020. Simultaneous isolation is demonstrated with the isolation of two and three peaks in separate isotopic distributions as well as with the isolation of alternating isotopologues within the same distribution. Such simultaneous isolation experiments are particularly useful when conducting experiments in which a mass calibrant is needed or when multiplexing in a tandem MS workflow.

Mirror Switching for High-Resolution Ion Isolation in an Electrostatic Linear Ion Trap.

Ion isolation was achieved via selective pulsing of the entrance and exit ion mirrors in an electrostatic linear ion trap mass spectrometer (ELIT). Mirror switching has been described previously as a method for capturing injected ions in ELIT devices. After ion trapping, mirror switching can be used as a method for ion isolation of successively narrower ranges of mass-to-charge (m/z) ratio. By taking advantage of the spatial separation of ions in an ELIT device, pulsing of the entrance and/or exit mirrors can release unwanted ions while continuing to store ions of interest. Furthermore, mirror switching can be repeated multiple times to isolate ions of very similar m/z values with minimal loss of the stored ions, as is demonstrated by the isolation of protonated l-glutamine and l-lysine (Δ m/z = 0.0364) from a mixture of the two amino acid ions and the isobaric mixture of [PC P-18:0/22:6] and [PC 19:0/19:0] (Δ m/z = 0.0575). As isolation is accomplished due to the spatial/temporal separation of ion packets within the ELIT, multiple reflection-time-of-flight (MR-TOF) mass spectra are shown to demonstrate separation in the ELIT at the time of isolation. An isolation resolution of greater than 35 000 fwhm is demonstrated here using a 5.25 in. ELIT. This resolution corresponds to the fwhm resolution necessary to reduce contaminant overlap of an equally abundant adjacent ion to 1% or less of the isolated ion intensity.

A Miniaturized Fourier Transform Electrostatic Linear Ion Trap Mass Spectrometer: Mass Range and Resolution.

Mass resolution (M/ΔMFWHM) was increased by reducing the axial length of a Fourier transform electrostatic linear ion trap (FT-ELIT) mass spectrometer. The increase in mass resolution corresponds directly to increased axial ion frequencies in the FT-ELIT. Increased mass resolution was demonstrated for equivalent transient lengths in a 5.25″ versus 2.625″ ELIT using the isotopes of [bradykinin+2H]2+ and [insulin+5H]5+ as test ions. Both bradykinin and insulin show mass resolution increases of ~ 90% allowing baseline resolution of the [insulin+5H]5+ isotopes after only 300ms of data acquisition. Relative changes in mass/charge range were explored using mirror switching to trap ions injected axially into the ELIT. When trapping ions using mirror switching, the mass/charge range in a FT-ELIT mass spectrometer for a given switch time is determined by the time required for fast ions to enter and exit the trap after one reflection versus the time it takes for slow ions to enter the trap. By reducing the length of the FT-ELIT mass spectrometer while maintaining a constant distance from the point from which ions are initially accelerated to the entrance mirror, only the low m/z limit is affected for a given mirror switching time. For the two ELIT lengths examined here, the effective mass/charge range at any given switch time is reduced from m/zlow-8.9*m/zlow for the 5.25″ ELIT to m/zlow-5.2*m/zlow for the 2.625″ ELIT. Graphical Abstract.

Optimized Electrostatic Linear Ion Trap for Charge Detection Mass Spectrometry.

In charge detection mass spectrometry (CDMS), ions are passed through a detection tube and the m/z ratio and charge are determined for each ion. The uncertainty in the charge and m/z determinations can be dramatically reduced by embedding the detection tube in an electrostatic linear ion trap (ELIT) so that ions oscillate back and forth through the detection tube. The resulting time domain signal can be analyzed by fast Fourier transforms (FFTs). The ion's m/z is proportional to thesquare of the oscillation frequency, and its charge is derived from the FFT magnitude. The ion oscillation frequency is dependent on the physical dimensions of the trap as well as the ion energy. A new ELIT has been designed for CDMS using the central particle method. In the new design, the kinetic energy dependence of the ion oscillation frequency is reduced by an order of magnitude. An order of magnitude reduction in energy dependence should have led to an order of magnitude reduction in the uncertainty of the m/z determination. In practice, a factor of four improvements was achieved. This discrepancy is probably mainly due to the trajectory dependence of the ion oscillation frequency. The new ELIT design uses a duty cycle of 50%. We show that a 50% duty cycle produces the lowest uncertainty in the charge determination. This is due to the absence of even-numbered harmonics in the FFT, which in turn leads to an increase in the magnitude of the peak at the fundamental frequency. Graphical Abstract ᅟ.

Fourier-Transform MS and Closed-Path Multireflection Time-of-Flight MS Using an Electrostatic Linear Ion Trap.

An electrostatic linear ion trap (ELIT) has been configured to allow for the simultaneous acquisition of mass spectra via Fourier transform (FT) techniques (frequency measurement) and via time-of-flight (TOF; time measurement). In the former case, the time-domain image charge derived from a pick-up electrode in the field-free region of the ELIT is converted to frequency-domain data via Fourier transformation (i.e., FT-ELIT MS). In the latter case, the time difference between ion injection into the ELIT and ion detection after release from the ELIT using a microchannel plate (MCP) enables the acquisition of multireflection time-of-flight mass spectra (MR-TOF MS). The ELIT geometry facilitates the acquisition of both types of data simultaneously because the detection schemes are independent and do not preclude one another. The two MS approaches exhibit a degree of complementarity. Resolution increases much faster with time with the MR-TOF approach, for example, but the closed-path nature of executing MR-TOF in an ELIT limits both the m/z range and the peak capacity. For this reason, the FT-ELIT MS approach is most appropriate for wide m/z range applications, whereas MR-TOF MS can provide advantages in a "zoom-in" mode in which moderate resolution (M/ΔMfwhm ≈ 10000) at short analysis times (10 ms) is desirable.

Determination of Collision Cross Sections Using a Fourier Transform Electrostatic Linear Ion Trap Mass Spectrometer.

Collision cross sections (CCSs) were determined from the frequency-domain linewidths in a Fourier transform electrostatic linear ion trap. With use of an ultrahigh-vacuum precision leak valve and nitrogen gas, transients were recorded as the background pressure in the mass analyzer chamber was varied between 4× 10-8 and 7 × 10-7 Torr. The energetic hard-sphere ion-neutral collision model, described by Xu and coworkers, was used to relate the recorded image charge to the CCS of the molecule. In lieu of our monoisotopically isolating the mass of interest, the known relative isotopic abundances were programmed into the Lorentzian fitting algorithm such that the linewidth was extracted from a sum of Lorentzians. Although this works only if the isotopic distribution is known a priori, it prevents ion loss, preserves the high signal-to-noise ratio, and minimizes the experimental error on our homebuilt instrument. Six tetraalkylammonium cations were used to correlate the CCS measured in the electrostatic linear ion trap with that measured by drift-tube ion mobility spectrometry, for which there was an excellent correlation (R 2 ≈ 0.9999). Although the absolute CCSs derived with our method differ from those reported, the extracted linear correlation can be used to correct the raw CCS. With use of [angiotensin II]2+ and reserpine, the corrected CCSs (334.9 ± 2.1 and 250.1 ± 0.5, respectively) were in good agreement with the reported ion mobility spectrometry CCSs (335 and 254.3, respectively). With sufficient signal-to-noise ratio, the CCSs determined are reproducible to within a fraction of a percent, comparable to the uncertainties reported on dedicated ion mobility instruments. Graphical Abstract ᅟ.

Utility of Higher Harmonics in Electrospray Ionization Fourier Transform Electrostatic Linear Ion Trap Mass Spectrometry.

Mass resolution (M/ΔM fwhm) is observed to linearly increase with harmonic order in a Fourier transform electrostatic linear ion trap (ELIT) mass spectrometer. This behavior was predicted by Grosshans and Marshall for frequency-multiple detection in a Fourier transform ion cyclotron resonance mass spectrometer only for situations when the prominent mechanism for signal decay is ion ejection from the trap. As the analyzer pressure in our ELIT chamber is relatively high, such that collisional scattering and collision-induced dissociation are expected to underlie much of the ion loss, we sought to explore the relationship between harmonic order and mass resolution. Mass resolutions of 36 900 (fundamental), 75 850 (2nd harmonic), and 108 200 (3rd harmonic) were obtained for GdO+ (avg. m/z 173.919) with a transient length of 300 ms. To demonstrate that the mass resolution was truly increasing with harmonic order, the unresolved isotopes at the fundamental distribution of cytochrome c+8 (m/z ∼ 1549) were nearly baseline, resolved at the third harmonic (mass resolution ≈ 23 000) with a transient length of only 200 ms. This experiment demonstrates that, when the ion density is sufficiently low, ions with frequency differences of less than 4 Hz remain uncoalesced. Higher harmonics can be used to increase the effective mass resolution for a fixed transient length and thereby may enable the resolution of closely spaced masses, determination of a protein ion's charge state, and study of the onset of peak coalescence when the resolution at the fundamental frequency is insufficient.

Voltage-induced frequency drift correction in fourier transform electrostatic linear ion trap mass spectrometry using mirror-switching

Ion capture from an external nano-electrospray ionization source in a Fourier transform electrostatic linear ion trap has been effected by mirror-switching. This capture method can suffer from time-dependent frequency shifts in the measured ion motion, which compromises mass resolution when using Fourier transform techniques for mass determination. This phenomenon was determined to be a result of the transient voltage recovery of the power supplies used for mirror-switching in response to a pulsed capacitive load, for which several examples are shown. A circuit, based on the AD210AN isolation amplifier, was fabricated to compensate for the voltage perturbation induced by mirror-switching by superimposing the inverted perturbation to the electric field of the opposing reflectron. In doing so, the dependence of the ions path length and frequency on the power supply output was greatly reduced throughout data acquisition. With this circuit enabled, no frequency shifts were observed in the mass spectrum when using mirror-switching, and thus pressure-limited theoretical resolutions were achieved. For example, an absorption mode resolving power of greater than 50,000M/ΔM FWHM was observed for iodide (m/z 126.9) at a transient length of 300 milliseconds. The use of mirror-switching led to a much greater m/z range than in-trap potential lift for a single ion injection which is demonstrated via simulation and experimental results. This correction method is simple to implement and does not require user intervention once properly tuned.

A dual detector Fourier transform electrostatic linear ion trap utilizing in-trap potential lift

Ion capture from an external nano-electrospray ionization source in an electrostatic linear ion trap has been effected by in-trap potential lift so as to avoid a time-dependent frequency drift of trapped ions. This phenomenon was observed when using mirror switching for capturing ions and compromised the mass resolution when using Fourier transform techniques for mass determination. A dual image charge detection approach was also implemented to compensate for losses in mass resolution associated with increasing the length of the electrostatic trap to accommodate the lift region. The potential lift approach for ion capture led to no detectable frequency shifts, thereby enabling the achievement of pressure-limited theoretical resolutions. For example, a resolution of roughly 11,000M/ΔM FWHM was observed for a carborane anion population of average m/z=520 at a transient length of 125ms. The use of the dual detector approach led to an increase (∼12%) in the ion frequencies used for mass analysis, which more than compensated for the effect of increasing the length of the electrostatic trap. Although the implementation of the potential lift approach and dual detectors were successful in their objectives, these changes resulted in a narrower m/z range for a single ion injection event relative to mirror switching. Furthermore, the dual detector approach resulted in a higher noise floor and a more complicated frequency spectrum due to asymmetries in the electric fields of the ion trap.

Injecting electrospray ions into a Fourier transform electrostatic linear ion trap

A Fourier transform electrostatic linear ion trap (FT-ELIT) is a mass analyzer consisting of a field free region with a reflectron on each side. Ions bounce back and forth and a signal is generated using a centrally located image charge pickup electrode. In this report we describe a technique for injecting packets of ions produced by dim sources such as electrospray ionization (ESI) into an FT-ELIT. The technique involves accumulating and thermalizing ions in a collision cell. The collision cell is equipped with a set of electrodes that enables the creation of an axial electric field that is used to concentrate the accumulated ions near the exit. Further concentration is achieved by reducing the potential on the exit lens of the collision cell prior to ion ejection. We demonstrate that these concentration techniques significantly increase signal intensity. We also use ion optical simulations to show that the signal intensity increases because the concentration increases the spatial charge density of the injected ion cloud not only by compressing the ion cloud in the collision cell, but also by decreasing the time required to eject the ions from the collision cell. We also demonstrate that the concentration techniques do not broaden the kinetic energy distribution of the injected ions; therefore, the concentration does not degrade resolution. Using these injection techniques, we are able to analyze ions produced by ESI ranging from 300 to 2200m/z in a single injection with high signal-to-noise ratio using FT-ELIT.

Tandem mass spectrometry in an electrostatic linear ion trap modified for surface-induced dissociation.

A variety of ion traps are used in mass spectrometry. A key feature shared by most of them is the ability to perform tandem mass spectrometry (MS/MS). The Orbitrap is perhaps the most notable ion trap in which MS/MS has yet to be performed. An electrostatic linear ion trap (ELIT) is analogous to an orbitrap in that ions are trapped using solely electrostatic fields. However, the relatively simple ion motion within an ELIT facilitates analysis of fragment ions produced within the device. In this report, we describe an ELIT to which we have added a target for surface induced dissociation (SID). When combined with our previously described method for isolating a precursor ion trapped in an ELIT,1 this apparatus enables MS/MS to be performed. Measurement of product ion m/z is facilitated by the fact that the ELIT is isochronous over the energy range of 1850-2000 eV so that changes to ion energy during SID do not cause major m/z shifts. We demonstrate MS/MS by isolating and dissociating each compound in a four component mixture of tetraalkylphosphonium cations. We also discuss the optimization of collision energy and the length of time that the SID target is available for collision, two parameters that are important in the performance of these experiments.

Square wave modulation of a mirror lens for ion isolation in a Fourier transform electrostatic linear ion trap mass spectrometer

Isolation of ions is a critical step in tandem mass spectrometry experiments. In electrostatic linear ion trap mass spectrometers, isolation is typically performed either using a timed ion selector, or by using a periodic electric field orthogonal to the axis of ion motion. In the latter case, the frequency of the field is matched to an ion of interest and the phase is such that the field is zero when the ions of interest are passing through the affected region. The periodic field method has the advantage that it is easier to isolate a single ion from a complex mixture. Here we describe an isolation method that produces essentially identical results to the orthogonal field method, but does not require the addition of any electrodes to the ion path. Instead, the periodic signal (a high voltage square wave) is applied to a lens that is a constituent of one of the ion mirrors. The square wave alters the energy of contaminant ions causing them to be lost from the trap. We demonstrate isolation of ions from a complex mixture using the square wave modulation technique. We also demonstrate an isolation resolution of 200 by isolating isotopes of a small molecule. We also characterize the performance of this method as a function of amplitude and time. An amplitude as low as 200V applied for 1ms can result in high-quality isolations using this method. We also discuss important considerations for those wishing to implement the method on other instruments.