The teachings herein relate to an electrostatic linear ion trap mass spectrometer (ELIT-MS). More particularly the teachings herein relate to systems and methods for reducing higher-order harmonics in an electrostatic linear ion trap (ELIT). The systems and methods disclosed herein include new methods of measuring the induced current from an ELIT and new configurations of an ELIT.
ELIT-MS
An ELIT-MS is a type of mass spectrometer that achieves a high mass resolution. An ELIT-MS includes an ELIT for performing mass analysis of ions. In an ELIT, electric current induced by oscillating ions in the trap is detected. The measured frequency of oscillation of the ions is used to calculate the mass-to-charge ratio (m/z) of the ions. For example, a Fourier transform is applied to the measured induced current.
Dziekonski et al., Int. J. Mass Spectrom. 410 (2016) p 12-21, (the “Dziekonski Paper”) describes an exemplary ELIT. The Dziekonski Paper is incorporated by reference herein.
In ELIT 100, ions are introduced axially and oscillate axially between first set of reflectron plates 110 and second set of reflectron plates 120. Pickup electrode 115 is used to measure the induced current produced by the oscillating ions. A Fourier transform is applied to the induced current signal measured from pickup electrode 115 to obtain the oscillation frequency. From the oscillation frequency or frequencies, the m/z of one or more ions can be calculated.
The voltages applied to the reflectron plates at either end of the ELIT produce an electric field 330. Electric field 330 can be expressed as E=4K/eL, where K is the kinetic energy of ions (ZeV), L is length 340, and e is a single proton charge of 1.602×10−19. It should be specified that this assumes a perfectly linear electric field in the reflectrons as is shown in
Ideally, the trajectory of ions in an ELIT can be expressed as a semi-sinusoidal waveform where the frequency, f, is equal to √{square root over (K/8 mL2)}, when the electric field in the reflectrons is linear and follows E=4K/eL.
The sinusoidal trajectory of an ion in an ELIT is detected by measuring the induced current on a pickup electrode, such as pickup electrode 115 of
As described above, the frequencies calculated from the induced current in an ELIT are used to determine the m/z values of ions. For example, the m/z value of an ion is calculated from the oscillation frequency, f, of an ion in an ELIT according to m/z=eV/2f2L2, under the assumptions of the previous equations. As a result, higher order frequencies can be misidentified as fundamental frequencies and, in turn, incorrect m/z values. Also, higher order frequencies of one ion can interfere with fundamental frequencies of other ions confounding the identification of the correct m/z values of those ions.
Consequently, there is a need for improved ELIT systems and methods that can reduce the higher order harmonics obtained from an ELIT.
An electrostatic linear ion trap (ELIT) for measuring induced current of one or more ions and reducing higher order frequency harmonics of the induced current by combining the induced current with measurements from reflecting reflectron plates is disclosed. A method for measuring induced current of one or more ions and reducing higher order frequency harmonics of the induced current by combining the induced current with measurements from reflecting reflectron plates in an ELIT is also disclosed.
The ELIT includes a first set of reflectron plates, a cylindrical pickup electrode, a second set of reflectron plates, a voltage power supply, and measurement circuitry. The plates of the first set of reflectron plates each includes holes in the center and are coaxially aligned along a central axis. The first set of plates includes a first inlet plate followed by a first plurality of reflection plates followed by a first plurality of trapping plates.
The cylindrical pickup electrode is positioned so that a first end of the pickup electrode is adjacent to the first inlet plate of the first set of plates. The pickup electrode is coaxially aligned with the first set of plates along the central axis.
The plates of the second set of reflectron plates also each includes holes in the center and are coaxially aligned along the central axis. The second set of plates includes a second inlet plate followed by a second plurality of reflection plates followed by a second plurality of trapping plates. The second set of plates is positioned so that the second inlet plate is adjacent to a second end of the cylindrical pickup electrode.
The voltage power supply applies separate voltages to one or more plates of the first set of plates and to one or more plates of the second set of plates. These voltages are applied in order to trap and then oscillate one or more ions between the first set of plates and the second set of plates. The one or more ions have been received along the central axis through the holes of the first set of plates, for example.
The measurement circuitry is used to measure a first induced current from the cylindrical pickup electrode, a second induced current from one or more plates of the first set of reflectron plates, and a third induced current from one or more plates of the second set of reflectron plates. The measurement circuitry combines the first measured induced current with the second measured induced current and the third measured induced current to determine an induced current of the one or more ions. The use of the second measured induced current and the third measured induced current in addition to the first measured induced current reduces higher order frequency harmonics of the induced current.
In various embodiments, the one or more plates of first set of reflectron plates include the first inlet plate and one or more plates of the first plurality of reflection plates, and the one or more plates of second set of reflectron plates include the second inlet plate and one or more plates of the second plurality of reflection plates. The first measured induced current is combined with the second measured induced current and the third measured induced current by summing the second measured induced current, the third measured induced current, and twice the first measured induced current.
In various embodiments, the one or more plates of first set of reflectron plates include one or more plates of the first plurality of trapping plates and the one or more plates of second set of reflectron plates include one or more plates of the second plurality of trapping plates. The first measured induced current is combined with the second measured induced current and the third measured induced current by subtracting the second measured induced current and the third measured induced current from the first measured induced current.
These and other features of the applicant's teachings are set forth herein.
The skilled artisan will understand that the drawings, described below, are for illustration purposes only. The drawings are not intended to limit the scope of the present teachings in any way.
Before one or more embodiments of the present teachings are described in detail, one skilled in the art will appreciate that the present teachings are not limited in their application to the details of construction, the arrangements of components, and the arrangement of steps set forth in the following detailed description or illustrated in the drawings. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting.
Systems and Methods for Reducing Harmonics in an ELIT
As described above, in an ELIT, ions are introduced axially and oscillate axially between a first set of reflectron plates and a second set of reflectron plates. A pickup electrode is used to measure the induced current produced by the oscillating ions. A Fourier transform is then applied to the induced current signal measured from the pickup electrode to obtain the oscillation frequency. From the oscillation frequency or frequencies, the mass-to-charge ratio (m/z) of one or more ions can be calculated.
Unfortunately, however, the induced current measured for each ion is typically not a perfect sinusoid. As a result, higher order harmonics or frequencies are found for each ion. These higher-order harmonics can result in the misidentification of the m/z value for an ion. Also, higher order harmonics or frequencies of one ion can interfere with fundamental frequencies of other ions confounding the identification of the correct m/z values of those ions.
Consequently, there is a need for improved ELIT systems and methods that can reduce the higher order harmonics obtained from an ELIT.
In various embodiments, higher order harmonics are reduced by measuring the induced current on the reflectron plates as well as on the pickup electrode and summing these induced currents. It is theorized that the short pickup electrode at the center of a conventional ELIT, such as the one shown in
Arrow 730 points to a parabola of semi-sinusoidal trajectory 701. The parabolas of semi-sinusoidal trajectory 701 represent the trajectory of the ion when the ion is within the reflectron plates of the ELIT.
where x is the position (parameter) from the center of the field free region, and X0: position of the inlet plates of the reflectors (311 and 321) from the field free region. In the reflectors, the intensity of induced charge 810 has the form,
here Xmax is the position that the ions can be reached (or maximum distance) from the center of the field free region. In the case of an example, X0 is 22.0 mm, a half of the length of the field free region, L=44 mm. Note that when the ion is between −22.0 and +22.0, the amplitude is positive. This is when the ion is between the reflectron plates or in the field free region. When the position of the ion is less than −22.0 or greater than +22.0, the ion is within one of the two sets of reflectron plates and the amplitude is negative. The ideal pick up profile 810 gives perfect sinusoidal induced charge when an ion is traveling the ideal ELIT electrode that produced semi-sinusoidal trajectory in
Performing a Fourier transform on the almost perfect or ideal sinusoidal, such as measured induced current 910, greatly reduces higher order harmonics.
Comparing induced charge 1110 and induced charge 810 shows how the conventional ELIT of
Further, the comparison of induced charge 1110 and induced charge 810 shows that, when an ion is between −22.0 and +22.0 or in the field free region of the conventional ELIT of
ELIT for Reducing Higher Order Harmonics by Adding Measurements from Reflecting Plates
The plates of first set of reflectron plates 1210 each includes holes in the center and are coaxially aligned along central axis 1260. First set of plates 1210 includes first inlet plate 1211 followed by a first plurality of reflection plates and, in turn, followed by a first plurality of trapping plates. The first plurality of reflection plates include plates 1212, 1213, 1214, and 1215. The first plurality of trapping plates include plates 1216, 1217, 1218, and 1219. Plate 1291 is not part of the ELIT and is only used for simulation purposes.
Cylindrical pickup electrode 1230 is positioned so that a first end of pickup electrode 1230 is adjacent to first inlet plate 1211 of first set of plates 1210 and pickup electrode 1230 is coaxially aligned with first set of plates 1210 along central axis 1260.
The plates of second set of reflectron plates 1220 also each includes holes in the center and are coaxially aligned along central axis 1260. Second set of plates 1220 includes second inlet plate 1221 followed by a second plurality of reflection plates and, in turn, followed by a second plurality of trapping plates. The second plurality of reflection plates include plates 1222, 1223, 1224, and 1225. The second plurality of trapping plates include plates 1226, 1227, 1228, and 1229. Plate 1292 is not part of the ELIT and is only used for simulation purposes. Second set of plates 1220 is positioned so that second inlet plate 1221 is adjacent to a second end of cylindrical pickup electrode 1230.
Voltage power supply 1240 applies pulsed voltages to one or more plates of first set of plates 1210 and one or more plates of second set of plates 1220 are held at their static trapping potentials. In this manner, the accepted m/z range of the device is extended. In this case, voltage power supply 1240 applies separate voltages to nine plates of first set of trapping plates 1210 and to nine plates of second set of plates 1220. Inlet plates 1211 and 1221 can have a zero voltage, for example. These voltages are applied in order to trap and then oscillate one or more ions between first set of plates 1210 and second set of plates 1220. The one or more ions have been received along central axis 1260 through the holes of first set of plates 1210, for example.
Voltage power supply 1240 can be one power supply with multiple outputs that can supply multiple different voltages as shown in
The voltages applied to the reflectron plates at either end of the ELIT produce an electric field 1310. Electric field 1310 causes the one or more ions that are introduced axially into the ELIT to oscillate along path 1350 between the reflectron plates at either end of the ELIT. Essentially, the voltages applied to the reflectron plates at either end of the ELIT produce a potential well for the one or more ions.
Returning to
Measurement circuitry 1250 can be one circuit for detecting, filtering, and combining the measured induced currents or can be two or more separate circuits, for example.
Various additional embodiments also further reduce higher order frequency harmonics of the induced current.
In various embodiments, one or more plates of first set of reflectron plates 1210 include first inlet plate 1211 and one or more plates (1212, 1213, and 1214) of the first plurality of reflection plates, and one or more plates of second set of reflectron plates 1210 include second inlet plate 1221 and one or more plates (1222, 1223, and 1224) of the second plurality of reflection plates.
In various embodiments, first measured induced current 1251 is combined with second measured induced current 1252 and third measured induced current 1253 by summing second measured induced current 1252, third measured induced current 1253, and twice first measured induced current 1251. In other words, first measured induced current 1251 is multiplied by 2 and summed with second measured induced current 1252 and third measured induced current 1253 to calculate the induced current. The factor of 2 further reduces higher order frequency harmonics of the induced current.
In various embodiments, second measured induced current 1252 and third measured induced current 1253 are adjusted to have the same phase before second measured induced current 1252 and third measured induced current 1253 are summed with twice first measured induced current 1251. For example, the phase of second measured induced current 1252 or third measured induced current 1253 is shifted 180° before second measured induced current 1252 and third measured induced current 1253 are summed with twice first measured induced current 1251.
In various embodiments, cylindrical pickup electrode 1230 includes circular plate 1231 in the middle of cylindrical pickup electrode 1230 and circular plate 1231 has a hole in the center. Circular plate 1231 further reduces higher order frequency harmonics of the induced current.
In various embodiments, the diameter of cylindrical pickup electrode 1230 is half the length of the distance between first set of plates 1210 and the second set of plates 1220. In other words, the diameter of cylindrical pickup electrode 1230 is half the length of the field free region. These dimensions further reduce higher order frequency harmonics of the induced current.
In various embodiments, the hole diameter of the one or more plates of the first plurality of reflection plates is larger than the hole diameter of the other plates of first set of plates 1210, and the hole diameter of the one or more plates of the second plurality of reflection plates is larger than the hole diameter of the other plates of second set of plates 1220. For example, as shown in
In various embodiments, first inlet plate 1211 further includes first focusing lens 1271 around the hole of first inlet plate 1211 to focus the one or more ions radially. Similarly, second inlet plate 1221 further includes second focusing lens 1272 around the hole of second inlet plate 1221 to focus the one or more ions radially.
Returning to
Plot 600 of
Plot 1000 of
Combined induced charge 2310 and induced charge 810 are very similar in shape.
This shows that the ELIT of
Plot 1100 of
Method for Reducing Higher Order Harmonics in an ELIT by Adding Measurements from Reflecting Plates
In step 2610 of method 2600, one or more ions are received along a central axis through holes in the center of a first set of reflectron plates. The plates of the first set of plates are coaxially aligned along the central axis. The first set of plates includes a first inlet plate followed by a first plurality of reflection plates followed by a first plurality of trapping plates.
A cylindrical pickup electrode is positioned so that a first end of the pickup electrode is adjacent to the first inlet plate of the first set of plates. The pickup electrode is coaxially aligned with the first set of plates along the central axis.
A second set of reflectron plates with holes in the center are coaxially aligned with the pickup electrode along the central axis. The second set of plates includes a second inlet plate followed by a second plurality of reflection plates followed by a second plurality of trapping plates. The second set of plates is positioned so that the second inlet plate is adjacent to a second end of the cylindrical pickup electrode.
In step 2620, separate voltages are applied to one or more plates of the first set of plates and to one or more plates of the second set of plates using a voltage power supply. These voltages are applied in order to trap and oscillate the one or more ions that have been received between the first set of plates and the second set of plates.
In step 2630, a first induced current is measured from the cylindrical pickup electrode, a second induced current is measured from one or more plates of the first set of reflectron plates, and a third induced current is measured from one or more plates of the second set of reflection plates using measurement circuitry. Further, the first measured induced current is combined with the second measured induced current and the third measured induced current to determine an induced current of the one or more ions and reduce higher order frequency harmonics of the induced current using the measurement circuitry.
In various embodiments, the one or more plates of the first set of reflectron plates include the first inlet plate and one or more plates of the first plurality of reflection plates and the one or more plates of the second set of reflectron plates include the second inlet plate and one or more plates of the second plurality of reflection plates.
In various embodiments, combining the first measured induced current with the second measured induced current and the third measured induced current includes summing the second measured induced current, the third measured induced current, and twice the first measured induced current.
ELIT for Reducing Higher Order Harmonics by Subtracting Measurements from Trapping Plates
Common-mode or environmental signals are induced along the signal path of a conventional Fourier transform ELIT from sources such as radiofrequency power supplies, mains voltage, turbomolecular pumps, etc. These noise sources generate peaks in the mass spectrum after Fourier transformation which do not result from the detection of an ion. Existing experimental detection schemes for a conventional electrostatic linear ion trap rely upon non-differential detection using a central pickup electrode.
In various embodiments, a technique is disclosed for differentially detecting the image current of an ion within an ELIT using an operational amplifier, thereby minimizing common-mode signals and false peaks in the mass spectrum. By utilizing detection electrodes near the ion turning point, or trapping electrodes in the reflectron, a nearly sinusoidal signal is preserved, thereby minimizing peaks corresponding to harmonic frequencies and simplifying data processing.
The measured induced image current out of differential amplifier 2730 is the difference between the two inputs, i.e., A-B, which is Fourier transformed and calibrated to generate a mass spectrum. The magnitude of the induced current (>200 f A/charge at m/z 525) is virtually identical to the induced current measured from
The detected noise of the measurement technique of
In Fourier transform mass spectrometry, differential detection minimizes common-mode signals from environmental sources (e.g., mains voltage, RF pickup, or pumps). Additionally, by using the trapping reflectron electrodes near the ion turning points as detectors, nearly sinusoidal signals are observed, minimizing harmonic content and false peaks. This also allows for standard FFT processing which can easily display the derived mass spectrum in real-time and allows the user to know exactly how the mass spectrum is generated (software transparency). In summary, differential detection lowers the noise floor of the induced image charge measurement, reduces the number of charges that need to be injected, reduces space charge effects, reduces common-mode noise, provides a real-time mass spectrum, and generates a mass spectrum of higher integrity.
The plates of first set of reflectron plates 1210 each includes holes in the center and are coaxially aligned along central axis 1260. First set of plates 1210 includes first inlet plate 1211 followed by a first plurality of reflection plates and, in turn, followed by a first plurality of trapping plates. The first plurality of reflection plates include plates 1212, 1213, 1214, and 1215. The first plurality of trapping plates include plates 1216, 1217, 1218, and 1219. Plate 1291 is not part of the ELIT and is only used for simulation purposes.
Cylindrical pickup electrode 1230 is positioned so that a first end of pickup electrode 1230 is adjacent to first inlet plate 1211 of first set of plates 1210 and pickup electrode 1230 is coaxially aligned with first set of plates 1210 along central axis 1260.
The plates of second set of reflectron plates 1220 also each includes holes in the center and are coaxially aligned along central axis 1260. Second set of plates 1220 includes second inlet plate 1221 followed by a second plurality of reflection plates and, in turn, followed by a second plurality of trapping plates. The second plurality of reflection plates include plates 1222, 1223, 1224, and 1225. The second plurality of trapping plates include plates 1226, 1227, 1228, and 1229. Plate 1292 is not part of the ELIT and is only used for simulation purposes. Second set of plates 1220 is positioned so that second inlet plate 1221 is adjacent to a second end of cylindrical pickup electrode 1230.
Voltage power supply 1240 applies pulsed voltages to one or more plates of first set of plates 1210 and one or more plates of second set of plates 1220 are held at their static trapping potentials. In this manner, the accepted m/z range of the device is extended. In this case, voltage power supply 1240 applies separate voltages to nine plates of first set of trapping plates 1210 and to nine plates of second set of plates 1220. Inlet plates 1211 and 1221 can have a zero voltage, for example. These voltages are applied in order to trap and then oscillate one or more ions between first set of plates 1210 and second set of plates 1220. The one or more ions have been received along central axis 1260 through the holes of first set of plates 1210, for example.
Voltage power supply 1240 can be one power supply with multiple outputs that can supply multiple different voltages as shown in
Measurement circuitry 2850 is used to measure first induced current 2851 from cylindrical pickup electrode 1230, second induced current 2852 from one or more plates of the first set of reflectron plates, and third induced current 2853 from one or more plates of the second set of reflectron plates. Measurement circuitry 2850 combines first measured induced current 2851 with second measured induced current 2852 and third measured induced current 2853 to determine an induced current of the one or more ions. The use of second measured induced current 2852 and third measured induced current 2853 in addition to first measured induced current 2851 reduces higher order frequency harmonics of the induced current.
In various embodiments, one or more plates of first set of reflectron plates 1210 include one or more plates (1216, 1217, and 1218) of the first plurality of trapping plates and one or more plates of second set of reflectron plates 1220 include one or more plates (1226, 1227, and 1228) of the second plurality of trapping plates.
In various embodiments, measurement circuitry 2850 combines first measured induced current 2851 with second measured induced current 2852 and third measured induced current 2853 by subtracting second measured induced current 2852 and third measured induced current 2853 from first measured induced current 2851.
In various embodiments, measurement circuitry 2850 includes differential transimpedance amplifier 2855. Cylindrical pickup electrode 1230 is capacitively coupled to a first input of differential transimpedance amplifier 2855 and the one or more plates (1216, 1217, and 1218) of the first plurality of trapping plates and the one or more plates (1226, 1227, and 1228) of the second plurality of trapping plates are each capacitively coupled to a second input of differential transimpedance amplifier 2855 to perform the subtraction.
A comparison of combined induced current 2910 of
Method for Reducing Higher Order Harmonics in an ELIT by Adding Measurements from Trapping Plates
Returning to
In various embodiments, the one or more plates of the first set of reflectron plates include one or more plates of the first plurality of trapping plates and the one or more plates of the second set of reflectron plates include one or more plates of the second plurality of trapping plates.
In various embodiments, combining the first measured induced current with the second measured induced current and the third measured induced current includes subtracting the second measured induced current and the third measured induced current from the first measured induced current.
While the present teachings are described in conjunction with various embodiments, it is not intended that the present teachings be limited to such embodiments. On the contrary, the present teachings encompass various alternatives, modifications, and equivalents, as will be appreciated by those of skill in the art.
Further, in describing various embodiments, the specification may have presented a method and/or process as a particular sequence of steps. However, to the extent that the method or process does not rely on the particular order of steps set forth herein, the method or process should not be limited to the particular sequence of steps described. As one of ordinary skill in the art would appreciate, other sequences of steps may be possible. Therefore, the particular order of the steps set forth in the specification should not be construed as limitations on the claims. In addition, the claims directed to the method and/or process should not be limited to the performance of their steps in the order written, and one skilled in the art can readily appreciate that the sequences may be varied and still remain within the spirit and scope of the various embodiments.
The present application claims the benefit of U.S. Patent Application No. 62/562,597, filed on Sep. 25, 2017, the entire contents of which are incorporated herein by reference.
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PCT/IB2018/057017 | 9/13/2018 | WO | 00 |
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WO2019/058226 | 3/28/2019 | WO | A |
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