CORE Metadata, citation and similar papers at core.ac.uk Provided by Elsevier - Publisher Connector FOCUS:QUADRUPOLE ION TRAPS A Two-Dimensional Quadrupole Ion Trap Mass Spectrometer Jae C. Schwartz and Michael W. Senko LC and LC/MS Division, Thermo Finnigan, San Jose, CA, USA John E. P. Syka LC and LC/MS Division, Thermo Finnigan, Charlottesville, VA, USA The use of a linear or two-dimensional (2-D) quadrupole ion trap as a high performance mass spectrometer is demonstrated. Mass analysis is performed by ejecting ions out a slot in one of the rods using the mass selective instability mode of operation. Resonance ejection and excitation are utilized to enhance mass analysis and to allow isolation and activation of ions for MSn capability. Improved trapping efficiency and increased ion capacity are observed relative to a three-dimensional (3-D) ion trap with similar mass range. Mass resolution comparable to 3-D traps is readily achieved, including high resolution at slower scan rates, although adequate mechanical tolerance of the trap structure is a requirement. Additional advantages of 2-D over 3-D ion traps are also discussed and demonstrated. (J Am Soc Mass Spectrom 2002, 13, 659–669) © 2002 American Society for Mass Spectrometry wo dimensional (2-D) radio frequency multipole Despite the previously described advantages and the ion traps have been used for several years for the recent progress with 2-D ion traps in hybrid instru- Tstudy of spectroscopic and other physical prop- ments, only a few examples have appeared using these erties of ions [1,2]. The earliest application of 2-D traps as stand-alone mass spectrometers. Senko et al. multipole ion traps in mass spectrometry involved the recently demonstrated image current detection with FT use of the collision cell of a triple quadrupole instru- analysis in a 2-D ion trap which utilized independent ment for studying ion-molecule reactions [3]. More detection electrodes between the quadrupole rods [17]. recently, multipole ion traps have been used in mass Although promising results were presented, space spectrometers as part of hybrid systems including Fou- charge effects were found to limit this configuration’s rier transform ion cyclotron resonance (FTICR) [4–7], ultimate performance as the motion of the ions is time-of-flight (TOF) [8–11], and standard three-dimen- largely restricted to one of the symmetry planes of the sional (3-D) ion trap mass spectrometers [12,13]. Several device. The relative insensitivity of the image current of the quadrupole based 2-D ion traps are capable of ion detection scheme precluded the use of lower num- mass selective isolation and activation of ions including bers of trapped ions to avoid such space charge effects. MS3 analysis [7,9–11]. Welling et al. demonstrated two variations of mass Syka and Fies have described the theoretical advan- selective instability in a stand-alone 2-D quadrupole ion tages of 2-D versus 3-D quadrupole ion traps for Fourier trap [18]. The first method, referred to as “q-scanning”, transform mass spectrometry [14]. These advantages exploited the field penetration of the detector between include reduced space charge effects due to the in- the quadrupole rods to allow for ion extraction using a creased ion storage volume, and enhanced sensitivity downward ramp of the RF voltage. This allowed rela- for externally injected ions due to higher trapping tively quick scanning of a broad mass range (1 second efficiencies. Bier and Syka described several forms of scan from 20–1000 m/z), but produced mass spectral linear and circular 2-D ion traps with larger ion capacity resolution of only five to six. The second method, to be used as mass spectrometers [15] using the mass referred to as “secular scanning”, used frequency swept selective instability mode of operation [16] similar to parametric excitation to eject ions between the quadru- that used in all commercial 3-D quadrupole ion trap pole rods. Although the scan rate was 100x slower than instruments. the q-scan, a resolution of 800 at m/z 130 was obtained. Lammert et al. have presented preliminary results using a toroidal ion trap with mass selective instability Published online April 26, 2002 [19]. Although this trap did not use the linear geometry Address reprint requests to Jae C. Schwartz, Thermo Finnigan, 355 River Oaks Parkway, San Jose, CA 95134, USA. E-mail: jschwartz@ of traditional 2-D ion traps, the quadrupolar trapping thermofinnigan.com potential was two dimensional in nature, and did © 2002 American Society for Mass Spectrometry. Published by Elsevier Science Inc. Received February 8, 2002 1044-0305/02/$20.00 Revised March 11, 2002 PII S1044-0305(02)00384-7 Accepted March 11, 2002 660 SCHWARTZ ET AL. J Am Soc Mass Spectrom 2002, 13, 659–669 Figure 1. Basic design of the two-dimensional linear ion trap. provide the benefit of increased ion storage capacity. Recently, Hager has demonstrated a novel ion trapping mode of operation on a modified triple quadruopole [20]. Fringe field effects caused by lenses at the ends of the quadrupole, normally considered detrimental, are exploited to eject trapped ions axially in a mass depen- dent fashion. Figure 2. Simion simulation of the resonance excitation field Here we apply many of the ideas for mass spectral comparing (a) a three section device and (b) a single section device analysis with 2-D quadrupole ion traps previously with end plates for axial trapping. described by this laboratory [14,15]. The 2-D ion trap described here is capable of operating in a manner lenses. As shown, the radial dipole field has a signifi- analogous to a conventional 3-D ion trap, but also cant axial component in the region near the end lenses. demonstrates distinct and unique operational character- In this region, ions will experience some axial excita- istics. Experimental data is provided to support the tion, which could lead to unintended axial ejection. This predicted advantages of an increased ion storage capac- approach to avoiding fringe field effects is similar to ity and enhanced trapping efficiency of externally in- that utilized in FTICR cell design for reducing undesir- jected ions. General performance and capabilities of the able axial ejection [21]. A similar distortion also occurs instrumental configuration are demonstrated along to the quadrupolar trapping potential at the end of the with other unique advantages of this type of mass single section device. This distortion has recently been spectrometer. exploited to generate spectra through mass selective axial ejection [20]. Experimental A 0.25mm high slot was cut along the middle 30 mm of the center section of one rod for ion ejection. To help The basic design of the 2-D ion trap used in this work is compensate for the detrimental field effects due to the depicted in Figure 1. The quadrupole structure has presence of the slot, the rod with the slot and the rod hyperbolic rod profiles with an r0 of 4 mm, similar to opposite it (the X rods) were moved out from the center that used in the Finnigan TSQ 700 series triple quadru- 0.75 mm beyond their normal position. This appears to pole instrument, but each rod is cut into three axial have analogous effects to the “stretch” in most commer- sections of 12, 37, and 12 mm length. The three sections, cial 3D ion traps [22] and is the subject of ongoing each with a discreet DC level, allow containment of the investigation and optimization. The length of the center ions along the axis in the central section of the device, section was limited so that the exiting beam of ions avoiding any possible fringe field distortions to the would be collected by the standard detection system of trapping and resonance excitation fields. a commercial Thermo Finnigan LCQ 3-D (San Jose, The ability to avoid fringe field distortions for the California) ion trap. This detector system includes a dipole resonance excitation field is shown in Figure 2a. conversion dynode held at Ϫ15 kV (for positive ions) All three sections of the top rod have 1V applied, and all and a channeltron electron multiplier. In order to assure three sections of the bottom rod have Ϫ1V applied. that ions are efficiently focused onto the detector, the Application of appropriate potentials to the end sec- ion optics simulation program Simion was used to tions restricts ions to the center section of the trap, examine the trajectories of ions exiting the 2-D ion trap. where the dipole field has no axial component. For the Examples are shown in Figure 3 where 100 eV and 10 single section trap shown in Figure 2b, the axial trap- keV ions [23], distributed along the entire length of the ping potential has to be created by voltages on the end slot, are all focussed onto the Ϫ15kV dynode cup. J Am Soc Mass Spectrom 2002, 13, 659–669 TWO-DIMENSIONAL QUADRUPOLE ION TRAP 661 ions. For the RF and AC signals applied to each rod, the voltages need to be applied equally across all segments of the rod to minimize any unintended axial fields. The appropriate combination of the above potentials results in nine separate voltages applied to the twelve elec- trodes. In initial experiments, the RF electronic system of an LCQ was adapted to apply the main RF voltage to only the Y quadrupole rods. A tri-filar (three-wire) RF transformer coil was constructed which allowed the coupling of three DC voltages for the three axial sec- Figure 3.(a) Simion simulation of 100 eV ions exiting the 2-D tions of the Y rod set with the main quadrupolar RF.