This invention relates to a method and apparatus for scanning an ion trap mass spectrometer
The performance of ion trap mass spectrometers may deteriorate as the number of trapped ions increases above an optimum range. The result can be broadening of mass spectral features, shifts in apparent m/z, and, in severe cases, ejection of ions at unexpected β-values in the stability diagram. Ion ejection at unexpected a-, q-value combinations can lead to a complete loss of m/z information
In accordance with an aspect of an embodiment of the present invention, there is provided a method of operating a mass spectrometer system having an ion trap and a downstream mass spectrometer. The method comprises (a) providing a plurality of groups of ions to the ion trap; (b) selecting a first mass-to-charge ratio; (c) configuring the downstream mass spectrometer to filter out one of (i) ions having a first unselected mass-to-charge ratio different from the first mass-to-charge ratio, and (ii) mass signals for ions having the first unselected mass-to-charge ratio different from the first mass-to-charge ratio; and, (d) ejecting a first group of ions of the first mass-to-charge ratio from the ion trap to the downstream mass spectrometer.
In accordance with a further embodiment of the present invention, there is provided a mass spectrometer system comprising (a) an ion trap for receiving and trapping a plurality of groups of ions; (b) a downstream mass spectrometer for receiving ions ejected from the ion trap; (c) an input means for receiving a selected mass-to-charge ratio; and, (d) a controller for receiving the selected mass-to-charge ratio from the input means and for controlling both the ion trap and the downstream mass spectrometer based on the selected mass-to-charge ratio such that the ion trap is operable to eject a selected group of ions of the selected mass-to-charge ratio from the ion trap, and the downstream mass spectrometer is configured to filter out one of (i) ions having a first unselected mass-to-charge ratio different from the first mass-to-charge ratio, and (ii) mass signals for ions having the first unselected mass-to-charge ratio different from the first mass-to-charge ratio The controller is linked for communication with the input means, the ion trap and the downstream mass spectrometer.
These and other features of the applicant's teachings are set forth herein.
The skilled person in the art will understand that the drawings, described below, are for illustration purposes only. The drawings are not intended to limit the scope of the applicant's teachings in any way.
a illustrates a mass spectrum for an Agilent test solution containing predominant ions at m/z=622, 922 and 1522, obtained using a linear ion trap;
b illustrates a mass spectrum of the Agilent test solution containing predominant ions at m/z=622, 922 and 1522, obtained using a linear ion trap together with a downstream transmission mass spectrometer, operating at a mass difference of 0 amu relative to the linear ion trap, in accordance with a first aspect of the present invention;
a illustrates a mass spectrum for a solution of Na+ adducts of polypropylene glycols obtained using a linear ion trap;
b illustrates a mass spectrum for a solution of Na+ adducts of polypropylene glycols obtained using a linear ion trap and a downstream transmission mass spectrometer operating at a mass difference of 0 amu relative to the linear ion trap in accordance with a second aspect of the present invention;
Referring to
In some cases, fringing fields between neighboring pairs of rod sets may distort the flow of ions. Stubby rods Q1a are provided between orifice plate IQ1 and elongated rod set Q1 to focus the flow of ions into the elongated rod set Q1.
Ions can be collisionally cooled in Q0, which may be maintained at a pressure of approximately 8×10−3 torr Both the linear ion trap mass spectrometer Q1 and the downstream transmission mass spectrometer Q3 are capable of operation as conventional transmission RF/DC multipole mass spectrometers. Q2 is a collision cell in which ions collide with a collision gas to be fragmented into products of lesser mass. Typically, ions may be trapped in the linear ion trap mass spectrometer Q1 using RF voltages applied to the multipole rods, and barrier voltages applied to the end aperture lenses 18.
Many ion trap mass spectrometer systems employ a type of ion gating, which impedes filling the ion trap with too many ions. One possible problem with these ion gating techniques is that they determine the appropriate number of ions with which to fill the ion trap by conducting an extra mass scan. This step requires additional time, and leads to reduced instrument duty cycle, effective scan speed, and overall sensitivity. In accordance with some aspects of some embodiments of the present invention, the downstream transmission mass spectrometer Q3 is operated in conjunction with the linear ion trap Q1 with a mass difference of zero. In other words, the downstream transmission mass spectrometer can be, and in some embodiments is, configured to filter out unselected ions. Ions that are ejected from the linear ion trap Q1 at unexpected a-, q-values can thereby be filtered out and not transmitted by the downstream transmission mass spectrometer Q3.
To provide the mass spectra of
Spectra were then acquired for various solutions under space charge conditions with downstream transmission mass spectrometer Q3 sometimes operating in (i) not resolving, RF only mode, and sometimes in (ii) resolving mode scanning synchronously with the linear ion trap Q1 with a mass difference of 0 amu.
a shows a mass spectrum of an Agilent test solution containing predominant ions at m/z=622, 922 and 1522 obtained by scanning the linear trap Q1 and the downstream transmission mass spectrometer Q3 synchronously with downstream transmission mass spectrometer Q3 not resolving. In other words, linear ion trap Q1 was scanned to sequentially eject ions of m/z 622, 922 and 1522, to ion pipe Q2 and from thence to downstream transmission mass spectrometer Q3 These ejected ions were not resolved in downstream transmission mass spectrometer Q3 and were ejected to detector 30.
The mass spectrum of
b shows a mass spectrum of the Agilent test solution containing predominant ions at m/z 622, 922 and 1522, obtained by scanning the linear trap Q1 and the downstream transmission mass spectrometer Q3 synchronously with downstream transmission mass spectrometer Q3 in resolving mode with an approximately 3 amu wide transmission window. With the mass spectrum of
Referring to
The number of Na+ adducts of polypropylene glycols within the linear ion trap was kept high. Consequently, ions of unselected a-, q-values were ejected from linear ion trap Q1, thereby providing the broadened mass spectral features of
b shows a mass spectrum of the Na+ adducts of polypropylene glycols. The mass spectrum of
Referring to
From multipole rod set 418, ions may be axially ejected through orifice plate 420 into collision cell 422. In some embodiments of the invention, collision cell 422 acts simply as an ion pipe without collision gas to transfer ions from multipole rod set 418 to a downstream multipole rod set 424. In other embodiments of the invention, collision cell 422 may be replaced by other intermediate ion optical elements, or can be omitted entirely such that ions from quadrupolar rod set 418 are ejected directly into downstream transmission multipole rod set 424.
In the embodiment shown in
In operation, multiple groups of ions, each such group having a different m/z, are supplied by ion source 50 to multipole rod set 418 via orifice plate 404, skimmer 408, vacuum chamber 410 containing rod set 412, orifice plate 413 and stubby rod set 416. Ions can be collisionally cooled in rod set 412, which, as with rod sets Q0 in
As discussed above, when the number of trapped ions stored in multipole rod set 418 exceeds an optimum range, ions that have a mass-to-charge ratio different from that selected may also be ejected. By linking scanning of the multipole rod set 418 and the downstream transmission multipole rod set 424, with a small transmission window, say about 3 amu, the downstream transmission rod set 424 can be used to filter out these inadvertently ejected ions of unselected mass-to-charge ratios. As shown in
Referring to
In operation, multiple groups of ions, each such group having a different m/z, are supplied by ion source 50 to multipole rod set 518 via orifice plate 504, skimmer plate 508, vacuum chamber 510, orifice plate 513 and stubby rod set 516. Then, a first mass-to-charge ratio is selected either by a user or automatically, and input into input device 530. Input device 530 then communicates the selected first mass-to-charge ratio to controller 532. As shown, and similar to system 400, a power supply 534 for multipole rod set 518 can provide RF, resolving DC and auxiliary AC to multipole rod set 518.
The controller 532 controls power supply 534 to configure multipole rod set 518 to eject a group of ions having a first mass-to-charge ratio. However, as discussed above, when the number of trapped ions stored in multipole rod set 518 exceeds an optimum range, ions that have a mass-to-charge ratio different from that selected may also be ejected. All of these ions are ejected from multipole rod set 518 and from downstream collision cell 522 or other intermediate ion optical elements, at a known time, such that the ions enter an inlet aperture 523 of time-of-flight mass spectrometer 524 at a known time. Within the time-of-flight mass spectrometer 524, all of the ions are subjected to the same electrical field, and are allowed to drift in a region of constant electrical energy. As a result, the ions will traverse this drift region in a time and arrive at a detector 525 in a time window that depends upon their m/z ratios. In some embodiments, controller 532 can control the detector 525 of time-of-flight mass spectrometer 524 to detect only those ions that traverse the drift zone 527 of the time-of-flight mass spectrometer 524 in an amount of time that ions of the first selected m/z will take. Alternatively, the detector 525 may detect both the selected and unselected ions. A time window for the selected ions to reach the detector 525 would also be determined. Then, all of the signals received outside of this time window, which would typically correspond to ions of unselected m/z being detected by detector 525, would be filtered out.
Referring to
The operation of the downstream mass spectrometer in filtering out ions of unselected mass-to-charge ratio will differ depending upon the type of system used. For example, if the downstream mass spectrometer is a quadrupole mass spectrometer, or other multipole mass spectrometer that physically filters out the unselected ions (generally referred to as an ion guide), then, in step 608, suitable RF and DC drive voltages are provided to the downstream ion guide to radially confine and transmit the first group of ions while filtering out ions having an unselected mass-to-charge ratio. The first group of ions would then be detected in step 6100n the other hand, if the downstream mass spectrometer is, for example, a time-of-flight mass spectrometer, then step 608 would involve determining an amount of time it takes for the first group of ions to traverse a drift zone of the time-of-flight mass spectrometer to reach the detector. Then, mass signals from the detector that are received within a certain time window, corresponding to the amount of time it takes for the first group of ions to traverse the drift zone along with a margin of variation, would be accepted, while mass signals from the detector that are received outside this time window would be filtered out.
Other variations and modifications of the invention are possible. For example, while in the foregoing description, reference is made to a linear ion trap, it will be appreciated that ion traps other than linear ion traps may be used. In particular, space charge problems may be even more likely to arise in ion traps other than linear ion traps. Accordingly, aspects of the present invention may also be applied to ion traps other than linear ion traps. Further, mass spectrometers or ion guides other than quadrupole mass spectrometers can be used to provide space-based ion separation. For example, mass spectrometers having more than four rods may be used. All such modifications or variations are believed to be within the sphere and scope of the invention as defined by the claims.
The application claims the benefit of U.S. Provisional Application Ser. No. 60/738,986, filed Nov. 23, 2005, the entire contents of which is hereby incorporated by reference
Number | Date | Country | |
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60738986 | Nov 2005 | US |