DE10336500A1 - Mass spectrometer with a quadrupole ion trap and also a further ion trap and a time-of-flight mass analyzer has reduced ion loss and improved duty cycle for the mass analyzer - Google Patents

Abstract

A mass spectrometer with a quadrupole ion trap (QIT) together with a further ion trap and a time-of-flight mass analyzer is such that in a first operational mode the further ion traps receive a pulse or impulse of ions mass selectively rejected from the QIT or removed by scanning, the ratio of maximum and minimum mass-charge ratios in the impulse being set to 4 or below; and the ions captured by the QIT are collision-cooled in the further traps. Independent claims are also included for processes using spectrometers (also claimed) in which ions of different mass-charge ratios are stored in different ion traps, the ions of one mass-charge ratio are fragmented, some of the ions are captured in the first ion trap at a first lower mass cut-off limit and other ion fragments are captured in a second ion trap at a second lower mass cut-off limit, the second limit being lower than the first.

Description

The present invention relates to a mass spectrometer and a method for mass spectrometry. The preferred embodiment affects 3D quadrupole ion traps ("QIT") and time-of-flight mass analyzers ("TOF mass analyzers").

Known 3D (Paul) Quadrupole Ion Trap Mass Spectrometer have an annular shape central ring electrode and two end cap electrodes. These well-known 3D (Paul) quadrupole ion trap mass spectrometer typically have, compared to other types of mass spectrometers, such as magnetic sector and time of flight mass spectrometers, a relatively small one resolution and a relatively low mass measurement accuracy, if the full Mass range is scanned. 3D quadrupole ion traps show both in MS as well as in MS / MS operating mode a relatively high sensitivity on. There is a particular problem with 3D quadrupole ion traps in that they the disadvantage of a relatively limited Have mass range and a low cut-off limit of Mass to charge ratio below which ions are not stored within the quadrupole ion trap can be. In an MS / MS operating mode can only about a ratio saved from 3: 1 between the initial mass and the fragment mass and be recorded.

Cross acceleration Time of Flight Mass Spectrometer have against that Both the MS and MS / MS modes have higher resolution capabilities and higher mass measurement accuracies. Typically, lateral acceleration time-of-flight mass spectrometers coupled to ion sources which have a continuous ion beam provide. Segments of this continuous ion beam then extracted in the transverse direction for subsequent mass analysis. However, about 75% of the ions are not extracted and used for mass analysis are lost accordingly.

It is therefore desirable to limit the mass range address that at conventional Quadrupole ion traps always occur, and the duty cycle one To increase lateral acceleration time-of-flight mass analyzer if MS and MS / MS experiments performed become.

According to the present invention, a mass spectrometer is provided which has:
a first ion trap and a second ion trap, the first ion trap configured to have a first lower mass cutoff limit in use, and the second ion trap configured to have a second lower mass cutoff limit in use, the second lower mass cut-off limit is lower than the first lower mass cut-off limit, so that at least some ions with mass-to-charge ratios below the first lower mass cut-off limit that are not trapped in the first ion trap are trapped in the second ion trap.

The combination of two or more Ionic traps in series that limit different lower mass cutoffs have increased advantageously the total ion trapping volume or the total ion trapping capacity and thus the dynamic range of the ion capture system.

A mass spectrometer according to the preferred one embodiment is able to run both MS and MS / MS modes of operation, and it has an ion source, a series of coupled quadrupole ion traps and a lateral acceleration time-of-flight mass analyzer. The Combination of multiple quadrupole ion traps and the lateral acceleration time-of-flight mass analyzer, compared to other known arrangements, a mass spectrometer with an increased mass range (especially in MS / MS), increased sensitivity, one increased Massenmeßgenauigkeit and an elevated Mass resolution.

According to a less preferred embodiment can Fragment ions outside the first ion trap by surface-induced dissociation (SID), collision-induced dissociation (CID) or behind the source decay (PSD) are generated and then transferred to the first ion trap become.

According to the preferred embodiment, can a collision cooling with a bath gas in one or more of the ion traps and / or in the transmission area (in the transmission areas) between the ion traps can be used. Collision cooling reduced advantageously both the kinetic energy of the ions as well the kinetic energy width of the ions. The collision cooling causes also improving the capture efficiency within the ion trap, while the ions for the subsequent mass analysis in a time-of-flight mass analyzer, preferably a lateral acceleration time-of-flight mass analyzer, which can optionally have a reflectron.

The first ion trap preferably has a quadrupole ion trap on. According to one embodiment includes the first ion trap is a 3D (Paul) quadrupole ion trap with a Ring electrode and two end cap electrodes, the ring electrode and the end cap electrodes have a hyperbolic surface.

According to another embodiment the first ion trap has one or more cylindrical ring electrodes and two substantially planar end cap electrodes.

According to another embodiment the first ion trap has one, two, three or more than three ring electrodes and two substantially planar end cap electrodes.

One of the end cap electrodes can a sample or target plate exhibit. The sample or target plate can have a substrate several sample areas arranged in a microtitration format have, the distance between the samples for example is approximately or exactly 18 mm, 9 mm, 4.5 mm, 2.25 mm or 1.125 mm. To to or at least 48, 96, 384, 1536 or 6144 samples can be so be set up that they can be received on the sample or target plate. On Laser beam or an electron beam is preferably used in the Use directed at the sample or target plate.

One of the end cap electrodes of the The first ion trap can have a network or a grid.

The first ion trap can be a 2D (linear) quadrupole ion trap with several Have stick electrodes and two end electrodes.

According to others less preferred embodiments the first ion trap can have a segmented ring set with several Electrodes in which there are openings from which ions are let through or have a Penning ion trap.

A first AC or RF voltage with a first amplitude is preferably applied to the first ion trap. The first amplitude is preferably selected from the following group: (i) 0-250 Vpp, (ii) 250-500 V _pp , (iii) 500-750 V _pp , (iv) 750-1000 V _pp , (v) 1000 - 1250 V _pp , (vi) 1250 - 1500 V _pp , (vii) 1500 - 1750 V _pp , (viii) 1750 - 2000 V _pp , (ix) 2000 - 2250 V _pp , (x) 2250 - 2500 V _pp , (xi) 2500 - 2750 V _pp , (xii) 2750 - 3000 V _pp , (xiii) 3000 - 3250 V _pp , (xiv) 3250 - 3500 V _pp , (xv) 3500 - 3750 V _pp , (xvi) 3750 - 4000 V _pp , (xvii) 4000 - 4250 V _pp , (xviii) 4250 - 4500 V _pp , (xix) 4500 - 4750 V _pp , (xx) 4750 - 5000 V _pp , (xxi) 5000 - 5250 V _pp , ( xxii) 5250 - 5500 V _pp , (xxiii) 5500 - 5750 V _pp , (xxiv) 5750 - 6000 V _pp , (xxv) 6000 - 6250 V _pp , (xxvi) 6250 - 6500 V _pp , (xxvii) 6500 - 6750 V _pp , (xxviii) 6750 - 7000 V _pp , (xxix) 7000 - 7250 V _pp , (xxx) 7250 - 7500 V _pp , (xxxi) 7500 - 7750 V _pp , (xxxii) 7750 - 8000 V _pp , (xxxiii ) 8000 - 8250 V _pp , (xxxiv) 8250 - 8500 V _pp , (xxxv) 8500 - 8750 V _pp , (xxxvi) 8750 - 9000 V _pp , (xxxvii) 9000 - 9250 V _pp , (xxxviii) 9250 - 9500 V _pp , (xxxix) 9500 - 9750 V _pp , (xl) 9750 - 10000 V _pp and (xli)> 10000 V _pp .

The first AC or RF voltage preferably has one within a range selected from the following group lying frequency: (i) <100 kHz, (ii) 100-200 kHz, (iii) 200-400 kHz, (iv) 400-600 kHz, (v) 600-800 kHz, (vi) 800 - 1000 kHz, (vii) 1.0-1.2 MHz, (viii) 1.2-1.4 MHz, (ix) 1.4-1.6 MHz, (x) 1.6-1.8 MHz, (xi) 1.8-2.0 MHz and (xii)> 2.0 MHz.

The second ion trap preferably includes one Quadrupole ion trap on.

The second ion trap can be a 3D (Paul) quadrupole ion trap with a ring electrode and two end cap electrodes, where the ring electrode and the end cap electrodes are hyperbolic surface exhibit. Alternatively, the second ion trap can be cylindrical Ring electrode and two essentially planar end cap electrodes exhibit.

The second ion trap can two, three or more than three ring electrodes and two essentially have planar end cap electrodes. One or more of the end cap electrodes the second ion trap can have a net or a grid.

According to another embodiment, can the second ion trap has a 2D (linear) quadrupole ion trap include multiple stick electrodes and two end electrodes.

According to less preferred embodiments can the second ion trap a segmented ring set with several Electrodes in which there are openings from which ions are let through, or a Penning ion trap lock in.

A second AC or RF voltage with a second amplitude is preferably applied to the second ion trap. The second amplitude is preferably selected from the following group: (i) 0-250 V _pp , (ii) 250-500 V _pp , (iii) 500-750 V _pp , (iv) 750-1000 V _pp , (v) 1000 - 1250 V _pp , (vi) 1250 - 1500 V _pp , (vii) 1500 - 1750 V _pp , (viii) 1750 - 2000 V _pp , (ix) 2000 - 2250 V _pp , (x) 2250 - 2500 V _pp , (xi) 2500 - 2750 V _pp , (xii) 2750 - 3000 V _pp , (xiii) 3000 - 3250 V _pp , (xiv) 3250 - 3500 V _pp , (xv) 3500 - 3750 V _pp , (xvi) 3750 - 4000 V _pp , (xvii) 4000 - 4250 V _pp , (xviii) 4250 - 4500 V _pp , (xix) 4500 - 4750 V _pp , (xx) 4750 - 5000 V _pp , (xxi) 5000 - 5250 V _pp , (xxii) 5250 - 5500 V _pp , (xxiii) 5500 - 5750 V _pp , (xxiv) 5750 - 6000 V _pp , (xxv) 6000 - 6250 V _pp , (xxvi) 6250 - 6500 V _pp , (xxvii) 6500 - 6750 V _pp , (xxviii) 6750 - 7000 V _pp , (xxix) 7000 - 7250 V _pp , (xxx) 7250 - 7500 V _pp , (xxxi) 7500 - 7750 V _pp , (xxxii) 7750 - 8000 V _pp , ( xxxiii) 8000 - 8250 V _pp , (xxxiv) 8250 - 8500 V _pp , (xxx v) 8500 - 8750 V _pp , (xxxvi) 8750 - 9000 V _pp , (xxxvii) 9000 - 9250 V _pp , (xxxviii) 9250 - 9500 V _pp , (xxxix) 9500 - 9750 V _pp , (xl) 9750 - 10000 V _pp and (xli)> 10000 V _pp .

The second AC or RF voltage preferably has one within a range selected from the following group lying frequency: (i) <100 kHz, (ii) 100-200 kHz, (iii) 200-400 kHz, (iv) 400-600 kHz, (v) 600-800 kHz, (vi) 800 - 1000 kHz, (vii) 1.0-1.2 MHz, (viii) 1.2-1.4 MHz, (ix) 1.4-1.6 MHz, (x) 1.6-1.8 MHz, (xi) 1.8-2.0 MHz and (xii)> 2.0 MHz.

The amplitude one to the first Ion trap applied AC or RF voltage is preferred larger than the amplitude of an alternating applied to the second ion trap or RF voltage.

The amplitude of an alternating or HF voltage applied to the first ion trap is preferably at least x V _pp greater than the amplitude of an alternating voltage applied to the second ion trap. or RF voltage, where x is selected from the following group: (i) 5, (ii) 10, (iii) 20, (iv) 30, (v) 40, (vi) 50, (vii) 60, ( viii) 70, (ix) 80, (x) 90, (xi) 100, (xii) 110, (xiii) 120, (xiv) 130, (xv) 140, (xvi) 150, (xvii) 160, ( xviii) 170, (xix) 180, (xx) 190, (xxi) 200, (xxii) 250, (xxiii) 300, (xxiv) 350, (xxv) 400, (xxvi) 450, (xxvii) 500, ( xxviii) 550, (xxix) 600, (xxx) 650, (xxxi) 700, (xxxii) 750, (xxxiii) 800, (xxxiv) 850, (xxxv) 900, (xxxvi) 950 and (xxxvii) 1000.

The first ion trap and / or the second ion trap are preferably on one of the following Group selected Pressure held: (i) greater or equal to 0.0001 mbar, (ii) greater than or equal to 0.0005 mbar, (iii) greater or equal to 0.001 mbar, (iv) greater or equal to 0.005 mbar, (v) greater or equal to 0.01 mbar, (vi) greater than or equal to 0.05 mbar, (vii) greater or equal to 0.1 mbar, (viii) greater or equal to 0.5 mbar, (ix) greater or equal to 1 mbar, (x) greater or equal to 5 mbar and (xi) greater or equal 10 mbar.

The first ion trap and / or the second ion trap are preferably on one of the following Group selected Pressure maintained: (i) less than or equal to 10 mbar, (ii) less than or equal to 5 mbar, (iii) less than or equal to 1 mbar, (iv) less than or equal to 0.5 mbar, (v) less than or equal to 0.1 mbar, (vi) less than or equal to 0.05 mbar, (vii) less than or equal to 0.01 mbar, (viii) less than or equal to 0.005 mbar, (ix) less than or equal to 0.001 mbar, (x) less or equal to 0.0005 mbar and (xi) less than or equal to 0.0001 mbar.

The first ion trap and / or the second ion trap are preferably on one of the following Group selected Pressure maintained: (i) between 0.0001 and 10 mbar, (ii) between 0.0001 and 1 mbar, (iii) between 0.0001 and 0.1 mbar, (iv) between 0.0001 and 0.01 mbar, (v) between 0.0001 and 0.001 mbar, (vi) between 0.001 and 10 mbar, (vii) between 0.001 and 1 mbar, (viii) between 0.001 and 0.1 mbar, (ix) between 0.001 and 0.01 mbar, (x) between 0.01 and 10 mbar, (xi) between 0.01 and 1 mbar, (xii) between 0.01 and 0.1 mbar, (xiii) between 0.1 and 10 mbar, (xiv) between 0.1 and 1 mbar and (xv) between 1 and 10 mbar.

According to other embodiments can more Ion traps are provided in series with the first and second ion traps become. Accordingly, one third ion trap are provided, which is set up that she has a third lower mass cut-off limit when used, where the third lower mass cutoff limit is lower than the second lower mass cutoff limit, so that at least some ions with Mass-to-charge ratios below the first and second mass cutoff limits, the cannot be trapped in the first and second ion trap, be trapped in the third ion trap.

A third AC or RF voltage with a third amplitude can be applied to the third ion trap. The third amplitude is preferably selected from the following group: (i) 0-250 V _pp , (ii) 250-500 V _pp , (iii) 500-750 Vpp, (iv) 750-1000 V _pp , (v) 1000 - 1250 V _pp , (vi) 1250 - 1500 V _pp , (vii) 1500 - 1750 V _pp , (viii) 1750 - 2000 V _pp , (ix) 2000 - 2250 V _pp , (x) 2250 - 2500 V _pp , (xi) 2500 - 2750 V _pp , (xii) 2750 - 3000 V _pp , (xiii) 3000 - 3250 V _pp , (xiv) 3250 - 3500 V _pp , (xv) 3500 - 3750 V _pp , (xvi) 3750 - 4000 V _pp , (xvii) 4000 - 4250 V _pp , (xviii) 4250 - 4500 V _pp , (xix) 4500 - 4750 V _pp , (xx) 4750 - 5000 V _pp , (xxi) 5000 - 5250 V _pp , ( xxii) 5250 - 5500 V _pp , (xxiii) 5500 - 5750 V _pp , (xxiv) 5750 - 6000 V _pp , (xxv) 6000 - 6250 V _pp , (xxvi) 6250 - 6500 V _pp , (xxvii) 6500 - 6750 V _pp , (xxviii) 6750 - 7000 V _pp , (xxix) 7000 - 7250 V _pp , (xxx) 7250 - 7500 V _pp , (xxxi) 7500 - 7750 V _pp , (xxxii) 7750 - 8000 V _pp , (xxxiii ) 8000 - 8250 V _pp , (xxxiv) 8250 - 8500 V _pp , (xxxv) 8500 - 8750 V _pp , (xxxvi) 8750 - 9000 V _pp , (xxxvii) 9000 - 9250 V _pp , (xxxviii) 9250 - 9500 V _pp , (xxxix) 9500 - 9750 V _pp , (xl) 9750 - 10000 V _pp and (xli)> 10000 Vp _p .

The third AC or RF voltage preferably has a frequency in one of the following group chosen Range is: (i) <100 kHz, (ii) 100-200 kHz, (iii) 200-400 kHz, (iv) 400-600 kHz, (v) 600-800 kHz, (vi) 800 - 1000 kHz, (vii) 1.0-1.2 MHz, (viii) 1.2-1.4 MHz, (ix) 1.4-1.6 MHz, (x) 1.6-1.8 MHz, (xi) 1.8-2.0 MHz and (xii)> 2.0 MHz.

The amplitude one to the second Ion trap applied AC or RF voltage is preferred larger than the third amplitude.

A fourth ion trap can be provided which is preferably set up so that it uses a has the fourth lower mass cut-off limit, the fourth lower cutoff limit is lower than the third lower Mass cut-off limit, so that at least some ions with mass-to-charge ratios below the first, the second and third mass cutoff limits that are not in the first, the second and the third ion trap, be trapped in the fourth ion trap.

A fourth AC or RF voltage with a fourth amplitude is preferably applied to the fourth ion trap. The fourth amplitude is preferably selected from the following group: (i) 0-250 V _pp , (ii) 250-500 V _pp , (iii) 500-750 V _pp , (iv) 750-1000 V _pp , (v) 1000 - 1250 V _pp , (vi) 1250 - 1500 V _pp , (vii) 1500 - 1750 V _pp , (viii) 1750 - 2000 V _pp , (ix) 2000 - 2250 V _pp , (x) 2250 - 2500 V _pp , (xi) 2500 - 2750 V _pp , (xii) 2750 - 3000 V _pp , (xiii) 3000 - 3250 V _pp , (xiv) 3250 - 3500 V _pp , (xv) 3500 - 3750 V _pp , (xvi) 3750 - 4000 V _pp , (xvii) 4000 - 4250 V _pp , (xviii) 4250 - 4500 V _pp , (xix) 4500 - 4750 V _pp , (xx) 4750 - 5000 V _pp , (xxi) 5000 - 5250 V _pp , (xiii) 5250 - 5500 V _pp , (xxiii) 5500 - 5750 V _pp , (xxiv) 5750 - 6000 V _pp , (xxv) 6000 - 6250 V _pp , (xxvi) 6250 - 6500 V _pp , (xxvii) 6500 - 6750 V _pp , (xxviii) 6750 - 7000 V _pp , (xxix) 7000 - 7250 V _pp , (xxx) 7250 - 7500 V _pp , (xxxi) 7500 - 7750 V _pp , (xxxii) 7750 - 8000 V _pp , ( xxxiii) 8000 - 8250 V _pp , (xxxiv) 8250 - 8500 V _pp , (xxx v) 8500 - 8750 V _pp , (xxxvi) 8750 - 9000 V _pp , (xxxvii) 9000 - 9250 V _pp , (xxxviii) 9250 - 9500 V _pp , (xxxix) 9500 - 9750 V _pp , (xl) 9750 - 10000 V _pp and (xli)> 10000 V _pp .

The fourth AC or RF voltage preferably has one within a range selected from the following group lying frequency: (i) <100 kHz, (ii) 100-200 kHz, (iii) 200-400 kHz, (iv) 400-600 kHz, (v) 600-800 kHz, (vi) 800 - 1000 kHz, (vii) 1.0-1.2 MHz, (viii) 1.2-1.4 MHz, (ix) 1.4-1.6 MHz, (x) 1.6-1.8 MHz, (xi) 1.8-2.0 MHz and (xii)> 2.0 MHz.

The third amplitude is preferred larger than the fourth amplitude.

According to other embodiments can five, six, seven, eight, nine, ten or more than ten ion traps in a row be provided.

It is preferably a continuous or pulsed ion source provided. The ion source can include: one Electrospray ion source, a chemical atmospheric pressure ionization ion source ("APCI ion source"), an atmospheric pressure MALDI ion source, an electron ionization ion source ("EI ion source"), an ion source with chemical ionization ("CI ion source"), a field desorption ionization ion source ("FI ion source"), a matrix-assisted laser desorption ionization ion source ("MALDI ion source"), a laser desorption ionization ion source ("LDI ion source"), a laser desorption / ionization-on-silicon ion source ("DIOS ion source"), a surface-enhanced laser desorption ionization ion source ("SELDI ion source") or an ion source with rapid atomic bombardment ("FAB ion source").

One ion detector can be downstream of the second Ion trap can be arranged. The ion detector can be an electron multiplier, have a photoelectron multiplier or a channeltron.

It can be a time-of-flight mass analyzer like an axial time-of-flight mass analyzer or more preferred of a lateral acceleration time-of-flight mass analyzer become.

In addition to the first, the second and optional to the third, fourth, etc. ion trap is preferred another ion trap is provided. The further ion trap preferably closes a quadrupole ion trap.

The further ion trap can be a 3D (Paul) quadrupole ion trap with a ring electrode and two end cap electrodes, where the ring electrode and the end cap electrodes are hyperbolic surface exhibit.

The further ion trap can be a or more cylindrical ring electrodes and two essentially have planar end cap electrodes.

Alternatively, the further ion trap one, two, three or more than three ring electrodes and two essentially have planar end cap electrodes.

According to one embodiment can one or more of the end cap electrodes of the further ion trap have a net or a grid.

According to another embodiment, can the other ion trap has a 2D (linear) quadrupole ion trap include multiple stick electrodes and two end electrodes.

According to less preferred embodiments the further ion trap can form a segmented ring set with several Electrodes in which there are openings from which ions are let through, or a Penning ion trap lock in.

Ions are preferably in one non-mass selective mode or a non-scanning mode pulsed taken from the further ion trap. For example, ions by applying a DC extraction pulse to the end cap electrodes the further ion trap pulsed from the further ion trap become. A DC voltage can also or alternatively be applied to the ring electrode (the ring electrodes) of the further ion trap, see above the existence more linear axial electrical field gradient is provided.

Additional ion traps can be used Storage of source ions in MS / MS operating modes provided become. The mass spectrometer can therefore be a first additional Have ion trap. The first additional ion trap preferably closes a quadrupole ion trap. The first additional ion trap can be one 3D (Paul) quadrupole ion trap with a ring electrode and two end cap electrodes, where the ring electrode and the end cap electrodes are hyperbolic surface exhibit.

Alternatively, the first additional Ion trap one or more cylindrical ring electrodes and two have essentially planar end cap electrodes.

The first additional ion trap can have one, two, three or more than three ring electrodes and two essentially have planar end cap electrodes. One or more end cap electrodes of the first additional Ion trap can have a net or a grid.

The first additional ion trap can be a 2D (linear) quadrupole ion trap with multiple stick electrodes and two end electrodes. alternative can be the first additional Ion trap a segmented ring set with several electrodes, in which there are openings from which ions are let through, or include a Penning ion trap.

A second additional ion trap can preferably be provided for storing starting ions in MS / MS operating modes. The second additional ion trap can include a quadrupole ion trap. The second additional ion trap can be a 3D (Paul) quadrupole ion trap with a ring electrode and two end cap electrodes include that, wherein the ring electrode and the end cap electrodes have a hyperbolic surface.

The second additional ion trap can be one or several cylindrical ring electrodes and two essentially planar Have end cap electrodes. Alternatively, the second additional Ion trap one, two, three or more than three ring electrodes and have two substantially planar end cap electrodes. A or more end cap electrodes of the second additional ion trap may be one Have mesh or a grid.

The second additional ion trap can be a 2D (linear) quadrupole ion trap with multiple stick electrodes and two end electrodes. alternative can the second additional Ion trap a segmented ring set with several electrodes, in which there are openings from which ions are let through, or include a Penning ion trap.

According to another aspect of the present invention, a method for mass spectrometry is provided, which has the following steps:
Providing a first ion trap with a first lower mass cut-off limit,
Providing a second ion trap with a second lower mass cut-off limit, the second lower mass cut-off limit being smaller than the first lower mass cut-off limit,
Trapping some ions in the first ion trap and trapping at least some ions in the second ion trap whose mass-to-charge ratios are less than the first lower mass cutoff limit and which are not trapped in the first ion trap.

If according to the different in the In the present application, embodiments provided a quadrupole ion trap with multiple internal electrodes (or ring electrodes) (which are easier to manufacture are used as electrodes with a hyperbolic surface) the quadrupole field can be created by applying different AC or RF voltage amplitudes with the same phase on each inner electrode. The inner electrodes should preferably be around the center of the ion trap be symmetrical. However, it is by choosing a particular opening or of a certain inner radius for the ring electrodes possible alternating electrical or HF field generate that comes close to a quadrupole field, with the same amplitude and phase of the AC or RF voltage applied to each ring electrode and with the opposite phase to the end cap electrodes is created.

If, for example, an ion trap with flat or thin Remove pulsed cylindrical electrodes from the ion trap (for example, the ions pulsed into an axial or lateral acceleration time-of-flight mass analyzer should bring in) those applied to the electrodes in such an ion extraction mode DC voltages are set up so that an essentially linear electric field is generated. This can be advantageous in terms of ion transfer efficiency his. Furthermore, a certain one can be carried out after the pulsed extraction Degree of spatial Flight time focus occur.

According to another aspect of the present invention, a mass spectrometer is provided which has:
a quadrupole ion trap,
another ion trap configured to receive ions ejected from the quadrupole ion trap, and
a time-of-flight mass analyzer which is set up to receive ions ejected from the further ion trap,
wherein the further ion trap, in a first mode of operation, receives a pulse of ions which have been mass-selectively ejected from or removed from the quadrupole ion trap, the ratio between the maximum mass-to-charge ratio of the ions in the ion pulse and the minimum The mass-to-charge ratio of the ions in the ion pulse is a maximum x, where x wobei 4.0 and the ions received by the quadrupole ion trap are cooled by collisions within the further ion trap.

Preferably x is from the following Group selected: (i) 3.9, (ii) 3.8, (iii) 3.7, (iv) 3.6, (v) 3.5, (vi) 3.4, (vii) 3.3, (viii) 3.2, (ix) 3.1, (x) 3.0, (xi) 2.9, (xii) 2.8, (xiii) 2.7, (xiv) 2.6, (xv) 2.5, (xvi) 2.4, (xvii) 2.3, (xviii) 2.2, (xix) 2.1, (xx) 2.0, (xxi) 1.9, (xxii) 1.8, (xxiii) 1.7, (xxiv) 1.6, (xxv) 1.5, (xxvi) 1.4, (xxvii) 1.3, (xxviii) 1.2 and (xxix) 1.1.

According to a first operating mode the further ion trap is preferably on one of the following Group selected Pressure held: (i) greater or equal to 0.0001 mbar, (ii) greater than or equal to 0.0005 mbar, (iii) greater or equal to 0.001 mbar, (iv) greater or equal to 0.005 mbar, (v) greater or equal to 0.01 mbar, (vi) greater than or equal to 0.05 mbar, (vii) greater or equal to 0.1 mbar, (viii) greater or equal to 0.5 mbar, (ix) greater or equal to 1 mbar, (x) greater or equal to 5 mbar and (xi) greater or equal 10 mbar.

According to a first operating mode the further ion trap is preferably on one of the following Group selected Pressure maintained: (i) less than or equal to 10 mbar, (ii) less than or equal to 5 mbar, (iii) less than or equal to 1 mbar, (iv) less than or equal to 0.5 mbar, (v) less than or equal to 0.1 mbar, (vi) less or equal to 0.05 mbar, (vii) less than or equal to 0.01 mbar, (viii) less than or equal to 0.005 mbar, (ix) less than or equal to 0.001 mbar, (x) less than or equal to 0.0005 mbar and (xi) less than or equal to 0.0001 mbar.

According to a first operating mode the further ion trap is preferably kept at a pressure selected from the following group: (i) between 0.0001 and 10 mbar, (ii) between 0.0001 and 1 mbar, (iii) between 0.0001 and 0.1 mbar, ( iv) between 0.0001 and 0.01 mbar, (v) between 0.0001 and 0.001 mbar, (vi) between 0.001 and 10 mbar, (vii) between 0.001 and 1 mbar, (viii) between 0.001 and 0.1 mbar, (ix) between 0.001 and 0.01 mbar, (x) between 0.01 and 10 mbar, (xi) between 0.01 and 1 mbar, (xii) between 0.01 and 0.1 mbar, (xiii ) between 0.1 and 10 mbar, (xiv) between 0.1 and 1 mbar and (xv) between 1 and 10 mbar.

Be in a second mode of operation Ions preferably in a non-mass selective or non-scanning Pulsed removed or ejected from the further ion trap, see above that ions can be extracted from the further ion trap in a non-resonantly excited manner and therefore the ions do not appear in a substantially excited state of the further ion trap. In the second operating mode can Ions by applying one or more DC voltage extraction pulses pulsed to the further ion trap taken from the further ion trap or ejected become. The one or more DC extraction voltages can also to one or more end electrodes or end cap electrodes further ion trap and / or to one or more central electrodes or ring electrodes of the further ion trap are applied. Preferably AC or RF voltages are not in the second operating mode to a considerable extent applied to the electrodes of the further ion trap.

According to a second operating mode, the further ion trap is preferably kept at a lower pressure than in the case in which it is operated in the first operating mode. The further ion trap is preferably kept at a pressure selected from the following group when it is operated in the second operating mode: (i) <5 x 10 ^-2 mbar, (ii) <10 ^-2 mbar, (iii) <5 × 10 ^-3 mbar, (iv) <10 ^-3 mbar, (v) <5 × 10 ^-4 mbar, (vi) <10 ^-4 mbar, (vii) <5 × 10 ^-5 mbar, (viii) <10 ^{- 5} mbar, (ix) <5 × 10 ^-6 mbar and (x) <10 ^-6 mbar.

In the first operating mode, a pulse of ions ejected from the quadrupole ion trap and received by the further ion trap preferably has a first energy range ΔE ₁ , with ions ejected from the further ion trap preferably having a second energy range ΔE ₂ , where ΔE ₂ <ΔE ₁ is. ΔE ₁ / ΔE ₂ is preferably at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100. ΔE ₁ is preferably at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 eV, and ΔE ₂ preferably takes a maximum of 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0, 02 or 0.01 eV.

According to another aspect of the present invention, a method for mass spectrometry is provided, which has the following steps:
Providing a quadrupole ion trap, a further ion trap which is set up to receive ions ejected from the quadrupole ion trap, and a time-of-flight mass analyzer which is set up to receive ions ejected from the further ion trap,
mass-selective ejection or scanning of an ion pulse in a first operating mode from the quadrupole ion trap, the further ion trap receiving the ion pulse and the ratio between the maximum mass-to-charge ratio of the ions in the ion pulse and the minimum mass-to-charge Ratio of ions in the ion pulse is a maximum x, where x ≤ 4.0, and
Collision cooling of the ions received by the quadrupole ion trap within the further ion trap.

According to another aspect of the present invention, a method for mass spectrometry is provided, which has the following steps:
Storing starting ions with a first mass-charge ratio in a first ion trap,
Storing at least some other starting ions with mass-charge ratios different from the first mass-charge ratio in one or more additional ion traps,
Fragmenting the initial ions with the first mass-charge ratio in the first ion trap to form fragment ions,
Trapping some of the fragment ions in the first ion trap with a first lower mass cutoff limit and
Trapping other fragment ions in a second ion trap with a second lower mass cutoff limit, the second lower mass cutoff limit being lower than the first lower mass cutoff limit.

According to another aspect of the present invention, a method for mass spectrometry is provided, which has the following steps:
Storing starting ions with a first mass-charge ratio in a first ion trap,
Storing at least some other starting ions with mass-charge ratios different from the first mass-charge ratio in one or more additional ion traps,
Fragmenting the starting ions with the first mass-charge ratio in a first ion trap to form fragment ions,
Trapping some of the fragment ions in the first ion trap with a first lower mass cutoff limit and
Trapping other fragment ions in a second ion trap with a second lower mass cutting limit, wherein the second lower mass cut-off limit is lower than the first lower mass cut-off limit.

According to another aspect of the present invention, a method for mass spectrometry is provided, which has the following steps:
Storing starting ions with a first mass-charge ratio in an ion trap,
Storing at least some other starting ions with mass-charge ratios different from the first mass-charge ratio in one or more additional ion traps,
Fragmenting the starting ions with the first mass-charge ratio to form fragment ions,
Trapping some of the fragment ions in a first ion trap with a first lower mass cutoff limit and trapping other fragment ions in a second ion trap with a second lower mass cutoff limit, the second lower mass cutoff limit being lower than the first lower mass cutoff limit.

The ion trap can be the same as the first ion trap.

Fragment ions are preferred within the first and / or the second ion trap due to collisions cooled. Some fragment ions are preferably scanned from the first and / or taken from the second ion trap or ejected from it mass-selectively, while others Fragment ions within the first and / or the second ion trap being held.

In a first operating mode, at least some fragment ions by scanning from the first ion trap and / or removed from the second ion trap or mass-selective therefrom pushed out received in another ion trap and cooled by collisions become.

An impulse from the further ion trap ejected or pulsed removed in a second operating mode Ions are preferably from a time of flight mass analyzer, for example an axial or lateral acceleration time-of-flight mass analyzer, receive.

According to another aspect of the present invention, a mass spectrometer is provided which has the following:
a first ion trap in which starting ions with a first mass-charge ratio are stored when used,
one or more additional ion traps storing at least some other starting ions with mass-to-charge ratios other than the first mass-to-charge ratio when used, and
a second ion trap,
wherein, in use, the parent ions having the first mass to charge ratio are fragmented in the first ion trap to form fragment ions, and some of the fragment ions in the first ion trap are captured with a first lower mass cutoff limit and others of the fragment ions in the second Ion trap are captured with a second lower mass cut-off limit, the second lower mass cut-off limit being lower than the first lower mass cut-off limit.

According to another aspect of the present invention, a mass spectrometer is provided which has the following:
an ion trap in which starting ions with a first mass-charge ratio are stored when used,
one or more additional ion traps, in which at least some other starting ions with mass-to-charge ratios other than the first mass-to-charge ratio are stored when used,
a first ion trap and
a second ion trap,
wherein, in use, the parent ions having the first mass to charge ratio are fragmented in the first ion trap to form fragment ions, and some of the fragment ions in the first ion trap are captured with a first lower mass cutoff limit and others of the fragment ions in the second Ion trap are captured with a second lower mass cut-off limit, the second lower mass cut-off limit being lower than the first lower mass cut-off limit.

According to another aspect of the present invention, a mass spectrometer is provided which has the following:
an ion trap in which starting ions with a first mass-charge ratio are stored when used,
one or more additional ion traps, in which at least some other starting ions with mass-to-charge ratios other than the first mass-to-charge ratio are stored when used,
a first ion trap and
a second ion trap,
wherein, in use, the parent ions are fragmented at the first mass to charge ratio to form fragment ions, and some of the fragment ions in the first ion trap are captured with a first lower mass cutoff limit and others of the fragment ions in the second ion trap with a second lower mass cut-off limit, the second lower mass cut-off limit being lower than the first lower mass cut-off limit.

According to another aspect of the present invention, a mass spectrometer is provided which has the following:
a first ion trap having an ion trap ion source with one or more central electrodes, a first end cap electrode and a second end cap electrode,
wherein a sample or target plate forms at least part of the first end cap electrode of the first ion trap.

The ion trap ion source can an ion source of a matrix-assisted laser desorption ionization ion trap ("MALDI ion source"), an ion source a laser desorption ionization trap ("LDI ion source"), an ion source, a laser desorption / ionization on silicon ion trap ("DIOS ion source"), an ion source a surface-reinforced laser desorption ionization ion trap ("SELDI ion source") and an ion trap ion source with rapid atomic bombardment ("FAB ion source").

According to another aspect of the present invention, a method for mass spectrometry is provided, which has the following steps:
Providing a first ion trap, the first ion trap having an ion trap ion source with one or more central electrodes, a first end cap electrode and a second end cap electrode, a sample or target plate forming at least part of the first end cap electrode,
Setting up a laser beam or an electron beam to hit the sample or target plate, and
Ionize samples or targets on the sample or target plate.

Various embodiments of the present Invention will now be given by way of example only with reference to the accompanying Drawing described. Show it:

1 an ion trap system according to an embodiment, which has two ion traps arranged in series with different lower mass cutting limits, so that ions not trapped in the first ion trap are trapped in the second ion trap,

2 a Mathieu stability diagram for a quadrupole ion trap,

3 an ion trap system according to the preferred embodiment, which has a further ion trap to support the coupling of the ion trap system with a lateral acceleration time-of-flight mass analyzer,

4 4 is a table showing the various stages that can be performed in mass analysis of ions having mass-to-charge ratios within the range of 100-3000 mass-to-charge ratio units, according to one embodiment of the present invention.

5 a less preferred embodiment in which a single mass-selective ion trap is coupled via a further ion trap to a lateral acceleration time-of-flight mass analyzer,

6 an ion trap system according to the preferred embodiment for carrying out MS / MS experiments, additional ion storage traps being provided for storing starting ions, and

7 an ion trap ion source according to an embodiment, wherein a microtitration sample plate or other target plate forms part of an end cap of an ion trap.

A preferred embodiment of the present invention will now be described with reference to FIG 1 described. 1 shows an embodiment in which two ion traps T1, T2, for example 3D (Paul) quadrupole ion traps, are arranged in series to provide an ion trapping system with an improved total mass range. The ion capture system is set up to receive ions from an ion source 1 to recieve. However, the ions are not necessarily generated outside of the first ion trap T1 and, according to another embodiment described in more detail below, they can be generated or formed within the first ion trap T1.

If ions are outside the first ion trap T1 generated, they are preferably using inhomogeneous confining RF fields from the ion source 1 into the first ion trap Transfer T1. For example, an HF ion guide can be provided and an axial electrical field gradient and / or running DC voltages or ongoing DC voltage waveforms (at which are moving axial capture areas along an ion guide can) to the HF ion guide be applied to force ions into the first ion trap T1. ions can also in a similar way Transferred from one ion trap to the other.

Ions can be less preferred under Use of DC focusing lenses or an ion guide at which is a central guide wire with a radially enclosing constant field or HF field with or without a collision gas is transferred into the first ion trap T1 or between ion traps become.

According to another embodiment can Ions axially or radially from one or more continuous or pulsed ion sources 1 into the first ion trap T1 and / or the second ion trap T2 can be initiated. According to a further embodiment can Ions switched from a continuous ion source and temporarily in a transmission area be stored before being transferred to the first ion trap T1 become.

The RF voltage supply for each ion trap T1, T2 can be from a single RF genera can be derived using different resistors to produce different amplitudes for each ion trap T1, T2.

wobei V_rf die Amplitude (von 0 bis zur Spitze) der an die zentrale Ringelektrode angelegten HF-Spannung (oder der zwischen die Ringelektrode und die Endkappenelektroden angelegten Spannung) ist, r₀ der eingeschriebene Radius der zentralen Ringelektrode ist, ω die Winkelfrequenz der angelegten HF-Spannung ist, U_dc die zwischen die Ringelektrode und die Endkappenelektroden angelegte Gleichspannung ist und m/z das Masse-Ladungs-Verhältnis eines Ions innerhalb der 3D-Quadrupol-Ionenfalle ist.Ions with certain mass-to-charge ratios are under operating conditions in the form of a 2 Mathieu stability diagram shown can be summarized and expressed by the Mathieu coordinates a _z and q _z , stable. The hatched area 2 represents ions that are both radially and axially stable. The Mathieu coordinates a _z and q _z are:

where V _{rf is} the amplitude (from 0 to the tip) of the RF voltage applied to the central ring electrode (or the voltage applied between the ring electrode and the end cap electrodes), r _{0 is} the inscribed radius of the central ring electrode, ω is the angular frequency of the applied RF voltage, U _{dc is} the DC voltage applied between the ring electrode and the end cap electrodes and m / z is the mass-to-charge ratio of an ion within the 3D quadrupole ion trap.

It is known that 3D (Paul) quadrupole ion traps do not store ions below a certain mass to charge ratio known as the lower mass cutoff limit ("LMCO"). If the central ring electrode is kept at the same DC voltage as the end cap electrodes (if U _dc is therefore set to zero volts and therefore a _z = 0), there is a maximum q _z value at which punctures become axially unstable. This maximum q _z value is g _zmax = 0.908. With this setting of q _z , LMCO can be calculated as follows:

As can be understood when considering the above equation, the LMCO value can be decreased either by decreasing V _rf or by increasing r ₀ or ω. Conversely, the LMCO value is increased by increasing V _rf .

According to the preferred embodiment to overcome that of a quadrupole ion trap has a mass range restriction of two (or more) ion traps T1, T2, for example 3D quadrupole ion traps, provided in series with a first ion trap T1, which is preferably for the Receiving ions from an ion source 1 is set up. Some ions of interest, their mass-to-charge ratios below the LMCO value of the first ion trap T1 are within the first ion trap T1 axially unstable. These ions become the first ion trap T1 ejected axially, however, the ions of interest are preferably not lost, because they are trapped in the second ion trap T2, which is preferred downstream the first ion trap T1. The second ion trap T2 is preferred configured to has a lower LMCO value than the first ion trap T1. Ions, their mass-to-charge ratios are lower than the LMCO value of the second ion trap T2 either no ions of interest, or alternatively additional additional ion traps can be used (not shown) in series with increasingly smaller LMCO values provided with the first ion trap T1 and the second ion trap T2 to capture these ions and to measure the mass range of the To further enlarge the overall ion capture system.

Ions whose mass-to-charge ratios are below the LMCO value of the first ion trap T1 are preferred by applying a small constant field (or alternating field) to the Transfer the end caps of the first ion trap T1 in the axial direction. Ions, their mass-to-charge ratio below the LMCO value of the first ion trap T1 are preferred in the second ion trap T2 downstream of the first ion trap T1 whose LMCO value is lower than the LMCO value of first ion trap T1. The captured and analyzed ions can either be positively or negatively charged.

According to the in 1 In the illustrated embodiment, an ion detector 2 is provided downstream of the first ion trap T1 and the second ion trap T2. According to further embodiments (not shown), three, four, five, six, seven, eight, nine, ten or more than ten ion traps can be provided in series to provide an ion trapping system that has an even further improved overall mass range. As will be understood, in these embodiments, the ion traps may have progressively lower LMCO values.

A particularly preferred feature of the preferred embodiment is that the amplitude of the alternating or RF voltage V _rf , which is applied, for example, to the ring electrode (or less preferably between the ring electrode and the end cap electrodes) of the first ion trap T1, can be considerably higher than the voltage that could otherwise be conventionally applied to a quadrupole ion trap in a comparable situation. Although by increasing the amplitude of the alternating or HF span applied to the electrode of the first ion trap T1 If the LMCO value of the first ion trap T1 is increased, ions of interest with mass-to-charge ratios below the LMCO value of the first ion trap T1 are not lost because they are caught in the second ion trap T2 downstream of the first ion trap T1.

As can be seen from the following equation for the depth D _{z of} the axial pseudopotential well, increasing the amplitude V _{rf of} the alternating or RF voltage applied to the ring electrode of the first ion trap T1 has the advantage that the depth of the axial pseudopotential well is within the first ion trap T1 is increased. Accordingly, ions with higher mass-to-charge ratios and / or ions with larger kinetic energies are advantageously captured more effectively in the first ion trap T1. Ions with larger kinetic energies are more effectively trapped in the first ion trap T1 because ions (in a first approximation) must have a greater kinetic energy than the depth of the axial pseudopotential well in order to escape from the trapped state in the ion trap. The depth of the axial pseudopotential well is given by the following equation:

It is clear from the above equation that increasing the amplitude of the applied AC or RF voltage Vrf increases the depth of the axial pseudopotential well. Similarly, the depth of the axial trough can be increased by reducing the frequency of the applied AC or RF voltage or by reducing the radius r _{0 of} the central ring electrode.

3 shows a particularly preferred embodiment for carrying out MS experiments, an ion trapping system with two ion traps T1, T2 being coupled via a further ion trap T0 to a lateral acceleration time-of-flight mass analyzer. The further ion trap T0 can include a 3D quadrupole ion trap, but in other embodiments it can also include other forms of ion trap.

In order to effectively transfer all of the output ions stored in the first ion trap T1 and the second ion trap T2 to a lateral acceleration time-of-flight mass analyzer, it is desirable to limit the mass range of the ions transferred to the time-of-flight mass analyzer at all times so that the ions in each individual ion pulse from Time-of-flight mass analyzer received ions have a limited range of mass-to-charge ratios. As explained in more detail below, it is desirable to have the range of mass-to-charge ratios in the range of extraction 3 of the time-of-flight mass analyzer to limit ions received so that all ions received by the mass analyzer are still in the extraction range at the time 3 are present, to which an electrostatic pulse on electrodes in the extraction area 3 is applied to pulsed ions from the extraction area 3 and take them to the drift or flight area of the time-of-flight mass analyzer. If the ions pulsed into a time-of-flight mass analyzer have a large range of mass-to-charge ratios, the ions are dispersed slightly in time according to their mass-to-charge ratios because the ions have essentially passed through a short drift or flight range, around the extraction area 3 to reach. Accordingly, some ions are beyond the end of the extraction range 3 run out while other ions are out of the extraction area 3 have not yet reached when ions are pulsed removed from the extraction area and introduced into the drift or flight area of the time-of-flight mass analyzer. Accordingly, if ions with a relatively high range of mass-to-charge ratios are pulsed into the time-of-flight mass analyzer, the duty cycle is reduced because some of these ions are not orthogonally accelerated into the drift or flight range of the time-of-flight mass analyzer. The further ion trap T0 is provided to address this problem and is described in more detail below.

Ions are also preferably ejected and led out of the first ion trap T1 and the second ion trap T2 by mass-selective instability. In the process, the amplitude of the AC or RF voltage applied to the ring electrodes is ramped up and ions with low mass-to-charge ratios above a q _z value of 0.908 are pushed. An alternative method for mass selection is resonant excitation, in which either a specific secular frequency or a broad band of secular frequencies are used to axially expel or hold ion groups with certain mass-to-charge ratios. A complementary electrical RF dipole field can be applied to the end cap electrodes and used in conjunction with a mass selective instability scan.

Ions that have been ejected mass-selectively from the first ion trap T1 and the second ion trap T2 are relatively energetic, and these ions are then preferably trapped within the further ion trap T0 and cooled (ie thermalized) by collisions. As soon as the ions have been cooled by collisions, the RF voltage applied to the further ion trap T0 is preferably switched off or significantly reduced in another way. The pressure of the collision cooling gas can also be significantly reduced at the same time. For example, it can be allowed that the pressure within the further ion trap T0 is reduced from, for example, 10 ^-3 mbar to <10 ^-4 mbar. If the further ion trap T0 is a quadrupole ion trap, an axial DC field can be applied to one or more of the end cap electrodes and / or ring electrodes of the further ion trap T0, so that pulsed ions are removed from the further ion trap T0. The constant axial field is used to move ions from the further ion trap T0 into the extraction area 3 to accelerate and transmit, for example, the lateral acceleration time-of-flight mass analyzer.

The width or distribution of the ion energies in the axial direction in the extraction area 3 The ions entering the time-of-flight mass analyzer depend on their thermal energy after the collision cooling, for example with helium gas at room temperature in the further ion trap T0. Ions that have been thermalized have an energy of approximately 0.05 eV. After applying an electrostatic extraction pulse of approximately 100 V to the end cap electrodes, the ions of the further ion trap T0 assume differential kinetic energies which depend on their location within the further ion trap T0 when the extraction pulse is applied. Ions taken from the further ion trap T0 in pulsed form therefore have an average kinetic energy of, for example, 50 eV and an energy width of ± 5 eV.

Without collision cooling the Ions in the further ion trap T0 would be the ion energy width of the ions ejected from the first and second ion traps significantly larger and she could have a negative effect on the time-of-flight mass analyzer, the tried a mass analysis of the ions. By reducing the energy width on some eV it is guaranteed that the Time of Flight mass not negatively affected becomes.

After the ions reach the extraction area 3 of the lateral acceleration time-of-flight mass analyzer, an electrostatic transverse pulse is preferably applied to the extraction area 3 designed to accelerate ions into the drift or flight area of the time-of-flight mass analyzer. The time-of-flight mass analyzer can have a reflectron. The above method for collision cooling of ions with the further ion trap T0 and the transfer of ions from the further ion trap T0 into the extraction area 3 in a pulsed, not mass-selective manner, has the important advantage of minimizing the energy width of the ions emerging from the further ion trap T0. This causes the sensitivity and resolution of the lateral acceleration time-of-flight mass analyzer to be optimized. Scanning a quadrupole ion trap, such as the first ion trap T1 and / or the second ion trap T2, for mass-selective ejection of ions causes these ions to be driven or excited in an unstable state. Therefore, by avoiding the mass-selective scanning of the ions from the further ion trap T0, the ions, once they have been cooled by collisions in the further ion trap T0, remain in a relatively non-energetic state, which is advantageous when the ions are transferred to a time-of-flight mass analyzer , Another important advantage of in 3 The embodiment shown is that ions can be ejected mass-selectively from the first and / or the second ion trap T1, T2 into the further ion trap T0 such that the ions in the further ion trap T0, which are then passed on to the time-of-flight mass analyzer, are one have a limited range of mass-to-charge ratios, which is desirable to optimize the duty cycle of the time-of-flight mass analyzer.

Despite the above, may according to one less preferred embodiment the AC or RF voltage applied to the further ion trap T0 nonetheless, and ions could be less preferably axially from the further ion trap T0, either by resonant expel (with an oscillating AC voltage between the end cap electrodes is created) or by mass-selective ejection (where the RF voltage elevated or the RF frequency is reduced or a DC voltage between some or all of the ring electrodes and the end cap electrodes is placed axially from the further ion trap T0 into the lateral acceleration time-of-flight mass analyzer pushed out become. The mass selective ejection of ions from the rest Ion trap T0 is less preferred because of the ion energy range increases, which is generally undesirable when a time-of-flight mass analyzer is used. However, the increased energy range is disadvantageous may be, the further ion trap T0 can emit ions that have a limited range of mass-to-charge ratios, whereby the duty cycle of the time-of-flight mass analyzer is improved. Such an arrangement can have some advantages over usual Offering arrangements is, however, compared to using DC extraction techniques less preferred for the reasons given above.

By the time the lateral acceleration time-of-flight mass analyzer extraction pulse is activated, it is desirable that the lowest ratio ions received by the further ion trap T0 not quite reach the end of the extraction range 3 have reached, while the ions with the highest mass-to-charge ratio are just in the extraction range 3 have occurred. Design constraints and other considerations significantly limit the physical position or length of the extraction area 3 , and thereby the mass range of the ions is considerably limited, which with a pulse duty factor of almost 100% in a pulse in cross direction can be accelerated. In order to address this problem, the AC or RF and / or DC voltage of the penultimate ion trap (i.e. the second ion trap T2 in the case of the in FIG 3 Embodiment shown) are preferably controlled so that only ions whose mass-to-charge ratios within a partial range or fraction of the total range of the mass-to-charge ratios of the ions stored in the (second) ion trap T2 into the last ion trap (i.e. the further ion trap T0) is transmitted axially. Ions are therefore preferably mass-selectively ejected from the (second) ion trap T2 into the further ion trap T0, so that all ions which are then subsequently pulsed out of the further ion trap T0 are within the extraction range 3 of the time-of-flight mass analyzer are accelerated essentially in the transverse direction.

After a group of ions go through mass-analyzed the lateral acceleration time-of-flight mass analyzer a different subrange or fraction of that in the second ion trap T2 stored ions in the further ion trap Transfer T0 to be cooled by collisions before being forwarded to the time-of-flight mass analyzer. A portion or fraction of that in the first ion trap Ions stored in T1 can also be transferred to the second ion trap T2 to be forwarded to the further ion trap T0 or to the process of mass selective ejection to repeat some ions from the second ion trap T2. This Process can Repeat a few times until all ions in the first ion trap T1 and the second ion trap T2 via the further ion trap Transfer T0 to the time-of-flight mass analyzer in a number of stages have been. The further ion trap T0 can be regarded as forming a collision cooling stage which reduces the energy width of the ions, which enables that the Time-of-flight mass analyzer works more effectively.

It can therefore be assumed that the in 3 Embodiment shown uses at least two ion traps T1, T2 to increase the total mass range of ions stored in the ion trapping system T1, T2 by ensuring that the LMCO value of the second ion trap T2 is lower than the LMCO value of the first ion trap T1. In the 3 The embodiment shown preferably also optimizes the mass-to-charge ratio range of the ions transmitted into the lateral acceleration time-of-flight mass analyzer by using a further ion trap T0. Collision cooling of ions is also effected in the further ion trap T0, as a result of which the energy width of the ions is reduced.

Now an MS mode of operation with reference to 3 described in more detail. The ion source 1 In one embodiment, may include a MALDI ion source that typically generates, for example, ions with mass-to-charge ratios in the range of 30-3,000. Ions of particular interest have mass-to-charge ratios in the range of 100-3000, so that ions with mass-to-charge ratios in the range of 30-100 may not be of particular interest and may have been lost. The ions from the ion source 1 are preferably transferred into the first ion trap T1, and the ions are preferably cooled within the first ion trap T1 by collisions.

The LMCO value of the first ion trap T1 can, for example, be set to m / z 300, so that ions with relatively high mass-to-charge ratios of, for example, up to m / z 3000 are more effectively captured within the first ion trap T1 than is otherwise the case would be because a higher AC or RF amplitude V _{rf can be applied} to the ring electrode (s) (or less preferably between the ring electrode (s) and the end cap electrodes) of the first ion trap T1. Preferably, the end cap electrode (s) of the first ion trap T1 is grounded. The higher alternating or RF voltage amplitude applied to the ring electrode (s) of the first ion trap T1 results in a greater depth of the axial pseudopotential well being provided within the first ion trap T1, thereby trapping ions with a high mass-to-charge ratio and energetic ions is improved.

It can be a slight DC bias are applied to the end cap electrodes of the first ion trap T1, so that ions with mass-to-charge ratios below the LMCO value the first ion trap T1 (ie with m / z <300), which is within the first Ion trap T1 are axially unstable, in the direction of the second ion trap T2 are ejected axially from the first ion trap T1. Which is a low one Mass-charge ratio Ions ejected from the first ion trap T1 are transferred while they are preferably undergo further collision cooling, and in the second Ion trap T2 captured, which is preferably downstream of the first ion trap T1.

The LMCO value for the second ion trap is T2 preferably set to a lower value than the LMCO value the first ion trap T1. For example, the LMCO value of second ion trap T2 are placed on m / z 100 (compared with m / z 300 for the first ion trap T1). Trapped in the first ion trap T1 Ions therefore have mass-to-charge ratios within the range m / z 300 - 3000 ions, and ions trapped within the second ion trap T2 have mass-to-charge ratios within the range m / z 100 - 300 on.

sein.If the distance from the origin of the further ion trap T0 to the beginning of the orthogonal extraction area 3 of the time-of-flight mass analyzer is 100 mm and the distance from the origin the further ion trap T0 to the end of the orthogonal extraction range 3 Is 141.4 mm, the maximum mass-to-charge ratio divided by the minimum mass-to-charge ratio of ions in an ion packet received by the time-of-flight mass analyzer should be less than for effective ion transfer

his.

According to one embodiment, ions are preferably transferred in two (or more) separate stages from the second ion trap T2 to the further ion trap T0. For example, ions with mass-to-charge ratios in the range m / z 100-200 can be transferred from the second ion trap T2 in a first stage and ions with mass-to-charge ratios in the range m / z 200-300 in a second stage from the second ion trap T2 are transmitted. After these two stages, the second ion trap T2 is essentially empty of ions. Ions from the first ion trap T1 can then via the second ion trap T2 and the further ion trap T0 to the extraction area 3 of the time-of-flight mass analyzer. For example, ions with mass-to-charge ratios in the range m / z 300-600 can be conveyed out of the first ion trap T1 in one stage, followed by ions with mass-to-charge ratios in the range m / z 600 - 1200 in the next stage. which are followed by ions with mass-to-charge ratios in the range m / z 1200 - 2400, which are finally followed in a last stage by ions with mass-to-charge ratios in the range m / z 2400 - 3000. It will be understood that at each stage in which ions are transferred, the ratio between the maximum mass to charge ratio and the minimum mass to charge ratio preferably does not exceed 2. According to this particular example, ions are transmitted to the time-of-flight mass analyzer in six discrete stages and a total of six orthogonal extraction pulses are required to effectively mass analyze ions over the entire desired m / z range of 100-3000. It will be understood that because the first ion trap T1 and the second ion trap T2 are preferably operated in mass selective (i.e. scanning) modes of operation, the order in which ions are transmitted can be changed as long as that in the extraction area 3 of the time-of-flight mass analyzer in each pulse received ions preferably have a limited range of mass-to-charge ratios. According to one embodiment, the ratio between the maximum mass-to-charge ratio and the minimum mass-to-charge ratio is less than or equal to 4, more preferably less than or equal to 3 and even more preferably less than or equal to 2.

In order to remove pulsed ions from the further ion trap T0, the cooling gas is preferably removed from the further ion trap T0 or allowed to disperse therefrom, so that the pressure within the further ion trap T0 decreases, for example, to <10 ^-4 mbar. The AC or RF voltage applied to the further ion trap T0 is also preferably switched off, and one or more DC voltage extraction pulses are preferably applied to the end cap electrodes of the further ion trap T0 in order to transfer ions from the further ion trap T0 into the extraction area 3 out of the lateral acceleration time-of-flight mass analyzer.

4 shows in more detail how the in 3 shown arrangement of ion traps can be operated to perform a typical MS experiment. The first ion trap T1, the second ion trap T2 and the further ion trap T0 are preferably similar 3D (Paul) quadrupole ion traps. The frequency of the RF voltage applied to all three ion traps T1, T2, T0 is preferably 0.8 MHz (5.0 rad / μs), and the radius of the central ring electrode r _{0 of} each ion trap T1, T2, T0 is preferably 0.707 cm , U _dc is preferably 0 V for all ion traps T1, T2, T0, and the ion traps T1, T2, T0 are preferably supplied with helium gas at a pressure of, for example, 0.001 mbar. As can be understood from the description below, the ion trap is used in a case where the low and high RF voltage in 4 are shown as being equal in one stage of operation, not scanned during that particular stage.

In a first stage S1, ions with mass-to-charge ratios in the range 300 - 3000 stored in the first ion trap T1, at which an RF voltage of 913.8 V to the ring electrode (the ring electrodes) of the first Ion trap T1 is created. Ions with mass-to-charge ratios in the range 100 - 300 are stored in the second ion trap T2, at which an RF voltage of 304.6 V to the ring electrode (the ring electrodes) of the second Ion trap T2 is created. The further ion trap T0 preferably contains initially no ions.

In the next stage S2, the amplitude of the to the ring electrode (s) of the second ion trap T2 applied RF voltage from 304.6 V to 609.2 V scanned what leads to that ions with mass-to-charge ratios in the range of 100-200 are expelled from the second ion trap T2 and into the further one Transfer ion trap T0 in which they are cooled by collisions.

In the next step S3, the cooling gas is allowed to disperse within the further ion trap T0, and the pressure within the further ion trap T0 is effectively dropped by turning off a valve pump that the further Io nenfalle T0 coolant gas. The RF voltage of 304.6 V applied to the ring electrode (s) of the further ion trap T0 is switched off, and ions are pulsed from the further ion trap T0 into the transverse acceleration range 3 of the time-of-flight mass analyzer. The cooling gas is then reintroduced into the further ion trap T0, and an RF voltage of 609.2 V is applied to the ring electrode (the ring electrodes) of the further ion trap T0, so that the further ion trap T0 is optimized to the next stage Receive ions with mass-to-charge ratios above 200 mass-to-charge ratio units.

In a fourth stage S4 RF voltage of 609.2 V to 913.8 applied to the second ion trap V scanned, which results in that the remaining ions with mass-to-charge ratios within the range of 200-300 are ejected from the second ion trap T2 and transferred into the further ion trap T0, where they are cooled by collisions become.

In a fifth stage S5, the cooling gas is allowed to disperse within the further ion trap T0 and the pressure within the further ion trap T0 is dropped by switching off a valve pump which supplies cooling gas to the further ion trap T0. The RF voltage of 609.2 V applied to the ring electrode (s) of the further ion trap T0 is switched off, and ions are pulsed out of the further ion trap T0 into the transverse acceleration range 3 of the time-of-flight mass analyzer. The cooling gas is then reintroduced into the further ion trap T0, and an RF voltage of 913.8 V is applied to the ring electrode (the ring electrodes) of the further ion trap T0, so that the further ion trap T0 is optimized to the next stage Receive ions with mass-to-charge ratios above 300 mass-to-charge ratio units.

In a sixth stage S6 RF voltage of 913.8 V to applied to the first ion trap T1 1827.6 V scanned which results in that the Ions with mass-to-charge ratios within the range of 300-600 Mass to charge ratio units ejected from the first ion trap T1 and into the second ion trap T2 will be transferred.

In the next seventh stage S7 will the amplitude of the to the ring electrode (the ring electrodes) second ion trap T2 applied RF voltage from 913.8 V to 1827.6 V scanned, which results in that the Ions with mass-to-charge ratios in the range of 300 - 600 ejected from the second ion trap T2 and into the further ion trap Be transferred to T0 where they are cooled by collisions.

In an eighth stage S8, the cooling gas is allowed to disperse within the further ion trap T0 and the pressure within the further ion trap T0 is dropped by switching off a valve pump which supplies cooling gas to the further ion trap T0. The RF voltage of 913.8 V applied to the ring electrode (s) of the further ion trap T0 is switched off, and ions are pulsed out of the further ion trap T0 into the transverse acceleration range 3 of the time-of-flight mass analyzer. The cooling gas is then reintroduced into the further ion trap T0, and an RF voltage of 1827.6 V is applied to the ring electrode (the ring electrodes) of the further ion trap T0, so that the further ion trap T0 is optimized to the next stage Receive ions with mass-to-charge ratios above 600 mass-to-charge ratio units.

In a ninth stage S9 RF voltage of 1827.6 V to applied to the first ion trap T1 3655.2 V scanned, which results in that the Ions with mass-to-charge ratios within the range of 600 - 1200 Mass to charge ratio units ejected from the first ion trap T1 and into the second ion trap T2 will be transferred.

In the next tenth stage S10 is the amplitude of the to the ring electrode (the ring electrodes) second ion trap T2 applied RF voltage from 1827.6 V to 3655.2 V scanned, which results in that the Ions with mass-to-charge ratios in the range of 600 - 1200 are ejected from the second ion trap T2 and transferred into the further ion trap T0, where they are cooled by collisions become.

In an eleventh stage S11, the cooling gas is allowed to disperse within the further ion trap T0 and the pressure within the further ion trap T0 is dropped by switching off a valve pump which supplies cooling gas to the further ion trap T0. The RF voltage of 1827.6 V applied to the ring electrode (s) of the further ion trap T0 is switched off, and ions are pulsed out of the further ion trap T0 into the transverse acceleration range 3 of the time-of-flight mass analyzer. The cooling gas is then reintroduced into the further ion trap T0, and an RF voltage of 3655.2 V is applied to the ring electrode (the ring electrodes) of the further ion trap T0, so that the further ion trap T0 is optimized to the next stage Receive ions with mass-to-charge ratios above 1200 mass-to-charge ratio units.

In a twelfth stage S12 the on the first ion trap T1 applied RF voltage from 3655.2 V to 7310.5 V scanned, which results in that the Ions with mass-to-charge ratios within the range of 1200-2400 mass-to-charge ratio units ejected from the first ion trap T1 and into the second ion trap T2 will be transferred.

In the next thirteenth stage S13, the amplitude of the RF voltage applied to the ring electrode (s) of the second ion trap T2 is scanned from 3655.2 V to 7310.5 V, which causes the ions with mass-to-charge ratios in the range of 1200-2400 to be expelled from the second ion trap T2 and transferred to the further ion trap T0, where they are cooled by collisions.

In a fourteenth stage S14, the cooling gas is dispersed within the further ion trap T0 and the pressure within the further ion trap T0 is dropped by switching off a valve pump that supplies cooling gas to the further ion trap T0. The RF voltage of 3655.2 v applied to the ring electrode (s) of the further ion trap T0 is switched off, and ions are pulsed out of the further ion trap T0 into the transverse acceleration range 3 of the time-of-flight mass analyzer. The cooling gas is then reintroduced into the further ion trap T0, and an RF voltage of 7310.5 V is applied to the ring electrode (the ring electrodes) of the further ion trap T0, so that the further ion trap T0 is optimized to the next stage Receive ions with mass-to-charge ratios above 2400 mass-to-charge ratio units.

In a fifteenth stage S15 the RF voltage of 7310.5 V to applied to the first ion trap T1 9138.1 V scanned, which results in that the Ions with mass-to-charge ratios within the range of 2400 - 3000 mass-to-charge ratio units ejected from the first ion trap T1 and into the second ion trap T2 are transferred whereby the first ion trap T1 is emptied of ions.

In the next sixteenth stage S16 the amplitude of the ring electrode (the ring electrodes) the second ion trap T2 applied RF voltage of 7310.5 V to 9138.1 V scanned, which results in that the Ions with mass-to-charge ratios in the range of 2400 - 3000 ejected from the second ion trap T2 and into the further ion trap Be transferred to T0 whereby the second ion trap is emptied. The ions are preferred cooled within the further ion trap T0 by collisions.

In a last seventeenth stage S17, the cooling gas is allowed to disperse within the further ion trap T0 and the pressure within the further ion trap T0 is dropped by switching off a valve pump which supplies cooling gas to the further ion trap T0. The RF voltage of 7310.5 V applied to the ring electrode (s) of the further ion trap T0 is switched off, and ions are pulsed out of the further ion trap T0 into the transverse acceleration range 3 of the time-of-flight mass analyzer. The cooling gas can then be introduced again into the further ion trap T0, and an HF voltage can be applied to the ring electrode (the ring electrodes) of the further ion trap T0 prepared for the next cycle.

To remove pulsed ions from the further ion trap T0 and into the extraction area 3 of a time-of-flight mass analyzer, a DC voltage, which is preferably in the range of 10-500 V, can be applied to the end cap electrodes of the further ion trap T0 in order to accelerate ions out of the further ion trap T0. The DC voltage can be applied, for example, for a minimum of 1 μs, and the extraction DC voltage can, according to other embodiments, be at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 , 80, 85, 90, 95 or 100 μs.

In one above regarding 4 In the example described, ions are removed by scanning either from the first ion trap T1 or from the second ion trap T2 ten times per cycle. Each scan of the RF voltage applied to the ion trap preferably takes 50 ms. The stage of collision cooling and pulsed extraction occurs in the further ion trap T0 in relation to 4 described example six times per cycle. The ions are preferably cooled in the further ion trap T0 by collisions for at least 30 ms. As soon as the ions in the further ion trap T0 have been cooled by collisions, the HF voltage applied to the further ion trap T0 is preferably switched off, if pulses are removed from the further ion trap T0, the HF voltage is reapplied and a gas is re-introduced the further ion trap T0 initiated. This process takes about 50 ms. The total cycle time is preferably approximately 1.1 seconds. The calculation of the cycle time does not include the time it takes to ionize the ions and transfer them to the first ion trap T1. The ion source is preferably pulsed and can be pulsed, for example, 10-100 times per second.

Referring again to 3 it should be noted that an MS / MS mode of operation can also be carried out in which the first ion trap T1 is controlled in such a way that selective exit ions with a certain mass-charge ratio of interest are retained, while all other exit ions preferably from the first ion trap T1 be expelled.

The initial ions held within the first ion trap T1 are then preferably fragmented in the first ion trap T1 by collisions, for example by setting the q _z value of the first ion trap T1 to about 0.3, which causes the starting ions to become energetic enough, so that when they collide with the background gas they fragment within the first ion trap T1. A resonance excitation is preferably applied to specific starting ions, which causes repeated collisions of higher energy, for example with helium gas, within the first ion trap T1, so that the starting ions gain sufficient internal energy so that a collision-induced dissociation (CID) occurs. The fragment ions with q _z > 0.908 are axially unstable within the first ion trap T1 and emerge from the first ion trap T1 along the z axis and are preferably captured within the second ion trap T2. Fragment ions can therefore be captured in both the first ion trap T1 and the second ion trap T2, and the fragment ions can be effectively transferred to the mass analyzer via the second ion trap T2 and the further ion trap T0 in a manner similar to that of the MS mode of operation has been described.

According to one in 5 The less preferred embodiment shown can be coupled to a lateral acceleration time-of-flight mass analyzer via a further ion trap T0, for example a mass-selective ion trap T1. Such an arrangement enables a limited mass range of ions to be cooled by collisions and then transferred to the time-of-flight mass analyzer so that the ions received by the time-of-flight mass analyzer in one pulse are all substantially accelerated transversely into the drift region. In the 5 However, the illustrated embodiment does not offer the advantage of an improved mass range capture system that requires two or more ion traps T1, T2 with different LMCO values.

Although in the 3 and 5 illustrated embodiments are able to perform MS / MS experiments, other starting ions than those initially captured in the first ion trap T1 can be effectively lost. To significantly increase the scanning efficiency of the starting ions, another is in 6 shown preferred embodiment is provided, in which additional ion traps TA, TB are provided to store ejected from the first ion trap T1 initial ions, which are not the subject of the present MS / MS analysis. A second additional ion trap TB may preferably be configured to have a lower LMCO than the first additional ion trap TA, so as to provide an improved ion trapping system for storing parent ions that are not yet the subject of the present mass analysis.

Once an MS / MS experiment has been run is, can the next initial ions of interest from the first additional Ion trap TA and / or the second additional ion trap TB in the first ion trap T1 transmitted in which the starting ions are then subjected to fragmentation become.

According to an alternative embodiment, all within the first and second additional ion trap TA and TB trapped ions, for example in a non-mass selective manner, in the first Transfer the ion trap T1 back and it can then the next starting ions of interest selectively in the first ion trap T1 be held while all other starting ions are mass-selective from the first ion trap T1 pushed out and into one or more of the additional ion traps TA, TB to be led back. More additional Ion traps (not shown) can be provided the effectiveness of capturing those waiting for further MS / MS analysis To improve starting ions.

Ions can be generated, for example, by a MALDI ion source 1 are generated and typically have mass-to-charge ratios in the range m / z 30-3000. That from the ion source 1 Emitted ions can be transferred to the first ion trap T1 and cooled there by collisions, although according to other embodiments, ions can be generated within the first ion trap T1.

An MS spectrum can be recorded beforehand and, for example, it may be desirable to have an MS / MS mass spectrum of the starting ions with a certain mass-charge ratio of, for example, 1500 to obtain. Starting ions with 1500 different mass-charge ratios can ejected from the first ion trap T1 and first into the first additional one Ion trap TA to be transferred. This can be done, for example, by applying a wobble frequency to the End cap electrodes of the first ion trap T1 can be reached, whereby a resonant excitation (axial modulation with an additional oscillating potential) of all ions except the desired one Starting ions is effected. The one applied to the first ion trap T1 RF voltage can also be temporary be decreased to increase the LMCO value.

According to another embodiment can all ions within the first ion trap T1 into the first additional one Transfer ion trap TA and the starting ions of interest with mass-to-charge ratios of 1500 can then using similar ones Methods like those described above from the first additional Ion trap TA can be transferred back into the first ion trap T1.

Starting ions with mass-to-charge ratios below the LMCO value of the first additional ion trap TA can in a second (or even more) additional ion trap TB be, preferably in series with the first additional Ion trap TA is provided and is preferred when used a lower LMCO value than the first additional Has ion trap TA.

After ions with a mass-to-charge ratio of 1500 have been isolated in the first ion trap T1 and have preferably been stored at another location (ie in additional ion traps TA, TB), the q _z value for the first ion trap T1 can be 0.3 (for m / z of 1500) in order to cause sufficient excitation for fragmentation of the parent ions to occur without axial or radial ejection. The LMCO value of the first ion trap T1 can be set to m / z 500. The LMCO value for the second ion trap T2 downstream of the first ion trap T1 can be set to m / z 100, that is to say a lower value than the LMCO value of the first ion trap T1. A background collision gas is preferably held in or introduced into the first ion trap T1, and a resonant excitation function is preferably applied to the end cap electrodes of the first ion trap T1 to increase the kinetic and internal energies of the starting ions so that they can then be used in the Collide with gas molecules within the first ion trap T1 fragment.

Fragment ions with mass-to-charge ratios in the m / z range from for example 100 - 1500 can be such a collision activation can be generated. fragment ions with mass-to-charge ratios below m / z 500, axially unstable in the first ion trap T1 and preferably ejected axially from the first ion trap T1, so that she be trapped in the second ion trap T2.

Fragment ions are now effectively extracted from the first ion trap T1 and the second ion trap T2 and in a number of discrete steps in a manner similar to that with respect to FIG 4 transferred MS operating mode described in the mass analyzer. In a first stage, ions in the m / z range of 100-200 can be transferred from the second ion trap T2 to the further ion trap T0, where they are cooled by collisions before they are passed on to the time-of-flight mass analyzer. In a second stage, ions in the m / z range of 200-400 can be transferred from the second ion trap T2 to the further ion trap T0, where they are cooled by collisions before they are passed on to the time-of-flight mass analyzer. In a third stage, ions in the m / z range of 400-500 can be transferred from the second ion trap T2 to the further ion trap T0, where they are cooled by collisions before they are passed on to the time-of-flight mass analyzer.

The three described above Lead steps that the second ion trap T2 is emptied of all fragment ions. fragment ions with mass-to-charge ratios in the m / z range from 500 - 1000 can then over the second ion trap T2 and over transfer the further ion trap T0 from the first ion trap T1 into the time-of-flight mass analyzer become. Below you can Fragment ions with mass-to-charge ratios in the range of 1000-2000 mass-to-charge ratio units over the second Ion trap T2 and the further ion trap T0 from the first ion trap T1 are transferred to the time-of-flight mass analyzer.

After all MS / MS data from one certain starting ion detected others can MS / MS acquisitions on some or preferably all of the remaining ones Starting ions run that are now in the first and the second additional Ion trap TA and TB have been saved. advantageously, no parent ions are lost and there can be for all parent ions of interest complete MS / MS data detected become.

According to a less preferred and not explained embodiment can the first additional Ion trap TA and the second additional Ion trap TB between the first ion trap T1 and the second Ion trap T2 may be arranged, or they can be located downstream of the first ion trap T1 and / or the second ion trap T2.

A particularly preferred ion trap system and a particularly preferred ion trap ion source will now be described with reference to 7 described. To reduce potential transmission losses between ion traps and to increase the homogeneity of the electric field when pulsing ions into the lateral acceleration time-of-flight mass analyzer, the electrodes of the different ion traps can be in the form of a plurality of cylindrical thin rings 10A . 10B . 10C being constructed. According to the in 7 In the illustrated embodiment, each ion trap has three such thin rings. Adjacent ion traps can continue through common end cap electrodes 11 be separated, the highly permeable grid 12 to reduce field penetration. Alternatively, some or all of the gridded end cap electrodes 11 can be replaced by circular plate electrodes with relatively small openings, which according to one embodiment can form differential pump openings between vacuum stages.

Ions can be taken from a sample or target plate within or near the first ion trap T1 by a laser 14 which is a laser beam 15 generated, generated. Shooting the laser 14 can with the phase of the ring electrodes 10A the first ion trap T1 applied RF voltage are synchronized so that the on or on the sample or target plate 13 generated ions immediately fly into or within the first ion trap T1. The electric field applied to the first ion trap T1 therefore preferably effectively extracts ions at the moment they are generated, preferably to exclude or minimize the risk of the ions reaching the sample or target plate 13 be reflected back, which could otherwise result in the ions being lost. The angle θ between the sample or target plate 13 and the ionizing pulsed laser beam 15 (or less preferably an electron beam) can be 90 °, in which case the pulsed laser beam 15 (or electron beam) through the extraction area 13 of the cross fitting can pass through time-of-flight mass analyzer. Angles smaller than 90 ° can also be used, and they are for example in the in 7 illustrated particular embodiment. In another embodiment, a mirror or other reflective element may be provided between the ion trap ion source and the mass analyzer. The mirror can for example be oriented at 45 °. A laser beam can be directed onto the mirror and then onto the target or sample plate 13 be reflected. Ions generated by the ion trap ion source can preferably be transmitted through a small opening provided in the mirror or other reflective element.

According to the preferred embodiment, the ring electrodes are attached 10A . 10B . 10C the first, the second and the further ion trap T1, T2, T0 RF voltages applied with a frequency of 800 kHz. The amplitudes of the RF voltages applied to each of the first, the second and the further ion trap T1, T2, T0 can vary. The DC voltage applied to all ion traps T1, T2, T0 is preferably set to zero. Helium gas is preferably fed to the first, the second and the further ion trap T1, T2, T0, and they are preferably kept at a pressure of 10 ^-3 mbar. Before ions are extracted from the further ion trap T0 and into the lateral acceleration range 3 of the time-of-flight mass analyzer, the pressure in the further ion trap T0 can be reduced to <10 ^-4 mbar. If the pressure in the further ion trap T0 is reduced according to one embodiment, the pressure in the first and / or the second ion trap T1, T2 can also be reduced to a pressure similar to that of the further ion trap T0.

In order to maintain an ion trap at a pressure such that collision cooling of ions occurs or collision activation occurs for MS / MS experiments, helium gas can be introduced into the ion trap to increase the pressure in the ion trap to about 10 ^-3 mbar. The helium or other gas may be introduced using a solenoid actuated needle valve or a pulsed supersonic valve (available from RM Jordan Inc., for example). The pulsed supersonic valve can be operated so that 50 μs gas pulses are provided at a repetition rate of 10 Hz. Once the collision or cooling gas has been introduced into an ion trap, it can be assumed that the gas remains within the ion trap for approximately 10 ms before it is dispersed or pumped out of the ion trap by the vacuum pump. The exact time over which it can be assumed that the collision gas remains effectively within the ion trap depends on the geometry of the ion trap and the vacuum chamber as well as the capacity of the vacuum pumps.

In all of the embodiments described above, between the first ion trap T1 and / or the second ion trap T2 and / or between the second ion trap T2 and the further ion trap T0 and / or between the further ion trap T0 and the mass analyzer, for example the time-of-flight mass analyzer, differential pump systems are used. According to one embodiment, the further ion trap T0 can be provided downstream of the first ion trap T1 and the second ion trap T2 in a vacuum chamber which is different from that of the first ion trap T1 and the second ion trap T2. If the further ion trap T0 is provided in a separate vacuum stage, the pressure of the gas in the further ion trap T0 is made easier between 10 ^-3 mbar (for collision cooling) and <10 ^-4 mbar (for the pulsed extraction of ions) can be changed, while the first ion trap T1 and the second ion trap T2 can, for example, be kept constant at, for example, 10 ^-3 mbar. According to a less preferred embodiment, the valves which supply gas to the first ion trap T1 and the second ion trap T2 can be switched off when the valve supplying gas to the further ion trap T0 is switched off.

According to the in 7 In the illustrated and described embodiment, the grid-shaped end cap electrode between the second ion trap T2 and the further ion trap T0 can be replaced by one provided with a differential pump opening.

The related to 7 The illustrated and described embodiment in which ions are generated directly inside an ion trap is particularly advantageous compared to conventional arrangements in which ions are generated outside an ion trap. If an ion pulse with a constant field is accelerated from a point outside an ion trap, ions with different mass-to-charge ratios have different flight times into the ion trap. The timing of the RF voltage applied to the ion trap must therefore be carefully optimized, or the voltage must even be turned off until all of the desired ions are within the ion trap, because otherwise they can be reflected back and lost. The acceptance and therefore the successful trapping of ions in a conventional ion trap depends on the position, the kinetic energy and the mass-charge ratio of the ions which are pulsed to the ion trap at the time when the RF voltage is applied to the Ion trap is created. Ions generated outside of the ion trap therefore usually have a considerable fluctuation in their position, which has an adverse effect on the acceptance of ions within the ion trap.

In addition to the ge Given constraints, geometric constraints also limit the acceptance of ions in a conventional ion trap. For example, some ions with a low mass-to-charge ratio may have entered the ion trap at the time and passed through the cap electrode of the output end of the ion trap at which an effective RF trapping voltage is applied to the ion trap, while other ions with a relative high mass to charge ratio the ion trap may not have reached at the time an effective RF capture voltage is applied to the ion trap. Conventional ion trap arrangements can therefore have discriminatory effects according to the mass-charge ratio. The ion trap ion source according to the preferred embodiment preferably does not have these problems and therefore represents a significantly improved ion trap and ion source system.

Although the present invention with respect to preferred embodiments Those skilled in the art will understand that various changes can be made to the shape and details without of that in the appended claims set out scope of the invention.

Claims (132)

Mass spectrometer, which has: a Quadrupole ion trap, another ion trap set up for this is out the quadrupole ion trap to receive ejected ions, and one Time-of-flight mass analyzer set up from the further ion trap ejected ions to recieve, the further ion trap in a first Operating mode receives a pulse or pulse of ions that mass-selective ejected from the quadrupole ion trap or have been removed from this by scanning, the ratio between the maximum mass-to-charge ratio of the Ions in the ion pulse and the minimum mass-to-charge ratio of the Ions in the ion pulse is a maximum x, where x ≤ 4.0 and the ions received by the quadrupole ion trap within the further ion trap are cooled by collisions. A mass spectrometer according to claim 1, wherein x is from the selected the following group is: (i) 3.9, (ii) 3.8, (iii) 3.7, (iv) 3.6, (v) 3.5, (vi) 3.4, (vii) 3.3, (viii) 3.2, (ix) 3.1, (x) 3.0, (xi) 2.9, (xii) 2.8, (xiii) 2.7, (xiv) 2.6, (xv) 2.5, (xvi) 2.4, (xvii) 2.3, (xviii) 2.2, (xix) 2.1, (xx) 2.0, (xxi) 1.9, (xxii) 1.8, (xxiii) 1.7, (xxiv) 1.6, (xxv) 1.5, (xxvi) 1.4, (xxvii) 1.3, (xxviii) 1.2 and (xxix) 1.1. A mass spectrometer according to claim 1 or 2, wherein the quadrupole ion trap includes a 3D (Paul) quadrupole ion trap a ring electrode and two end cap electrodes, wherein the ring electrode and the end cap electrodes are hyperbolic surface exhibit. A mass spectrometer according to claim 1 or 2, wherein the quadrupole ion trap has one or more cylindrical ring electrodes and has two substantially planar end cap electrodes. A mass spectrometer according to claim 1 or 2, wherein the quadrupole ion trap has one, two, three or more than three ring electrodes and has two substantially planar end cap electrodes. A mass spectrometer according to claim 4 or 5, wherein one or more of the end cap electrodes of the quadrupole ion trap form a network or have a grid. A mass spectrometer according to claim 1 or 2, wherein the quadrupole ion trap is a 2D (linear) quadrupole ion trap includes, which has a plurality of stick electrodes and two end electrodes. Mass spectrometer according to one of the preceding claims, wherein the further ion trap includes a quadrupole ion trap. A mass spectrometer according to claim 8, wherein the further Ion trap a 3D (Paul) quadrupole ion trap with a ring electrode and two end cap electrodes, the ring electrode and the end cap electrodes have a hyperbolic surface. A mass spectrometer according to claim 8, wherein the further Ion trap one or more cylindrical ring electrodes and two has essentially planar end cap electrodes. A mass spectrometer according to claim 8, wherein the further Ion trap one, two, three or more than three ring electrodes and has two substantially planar end cap electrodes. A mass spectrometer according to claim 10 or 11, wherein one or more end cap electrodes of the further ion trap Have mesh or a grid. A mass spectrometer according to claim 8, wherein the further Ion trap includes a 2D (linear) quadrupole ion trap that has a plurality of stick electrodes and two end electrodes. Mass spectrometer according to one of claims 1 to 7, wherein the further ion trap a segmented ring set with a plurality of electrodes has in which there are openings from which ions are let through. Mass spectrometer according to one of claims 1 to 13, wherein the time-of-flight mass analyzer has an axial acceleration or has a lateral acceleration time-of-flight mass analyzer. Mass spectrometer according to one of the preceding claims, wherein in the first operating mode, the further ion trap on one pressure which is selected from the following group: (i) larger or equal to 0.0001 mbar, (ii) greater than or equal to 0.0005 mbar, (iii) greater or equal to 0.001 mbar, (iv) greater or equal to 0.005 mbar, (v) greater or equal to 0.01 mbar, (vi) greater than or equal to 0.05 mbar, (vii) greater or equal to 0.1 mbar, (viii) greater or equal to 0.5 mbar, (ix) greater or equal to 1 mbar, (x) greater or equal to 5 mbar and (xi) greater or equal 10 mbar. Mass spectrometer according to one of the preceding claims, wherein in the first operating mode, the further ion trap on one pressure which is selected from the following group: (i) less than or equal to 10 mbar, (ii) less than or equal to 5 mbar, (iii) less than or equal to 1 mbar, (iv) less than or equal to 0.5 mbar, (v) less than or equal to 0.1 mbar, (vi) less than or equal to 0.05 mbar, (vii) less than or equal to 0.01 mbar, (viii) less than or equal to 0.005 mbar, (ix) less than or equal to 0.001 mbar, (x) less than or equal to 0.0005 mbar and (xi) less than or equal to 0.0001 mbar. Mass spectrometer according to one of the preceding claims, wherein in the first operating mode, the further ion trap on one pressure which is selected from the following group: (i) between 0.0001 and 10 mbar, (ii) between 0.0001 and 1 mbar, (iii) between 0.0001 and 0.1 mbar, (iv) between 0.0001 and 0.01 mbar, (v) between 0.0001 and 0.001 mbar, (vi) between 0.001 and 10 mbar, (vii) between 0.001 and 1 mbar, (viii) between 0.001 and 0.1 mbar, (ix) between 0.001 and 0.01 mbar, (x) between 0.01 and 10 mbar, (xi) between 0.01 and 1 mbar, (xii) between 0.01 and 0.1 mbar, (xiii) between 0.1 and 10 mbar, (xiv) between 0.1 and 1 mbar and (xv) between 1 and 10 mbar. Mass spectrometer according to one of the preceding claims, wherein in a second operating mode ions in a non-mass selective or not scanned in a pulsed manner from the further ion trap removed or ejected become. A mass spectrometer according to claim 19, wherein in the second operating mode ions by applying one or more DC extraction pulses pulsed out to the further ion trap removed or ejected become. A mass spectrometer according to claim 20, wherein in the second operating mode, the one or more DC extraction voltages to the one or more end or end cap electrodes of the another ion trap. A mass spectrometer according to claim 20 or 21, wherein in the second operating mode, the one or more DC extraction voltages to the one or more central electrodes or ring electrodes of the further ion trap. Mass spectrometer according to one of claims 19 to 22, with AC or RF voltages not in the second operating mode to a considerable extent be applied to the electrodes of the further ion trap. Mass spectrometer according to one of claims 19 to 23, the further ion trap being opened in the second operating mode a lower pressure is maintained than if the further ion trap in the first operating mode is operated. The mass spectrometer of claim 24, wherein the further ion trap is maintained at a pressure selected from the following group when operating in the second mode of operation: (i) <5 × 10 ^-2 mbar, (ii) <10 ^-2 mbar, (iii ) <5 × 10 ^-3 mbar, (iv) <10 ^-3 mbar, (v) <5 × 10 ^-4 mbar, (vi) <10 ^-4 mbar, (vii) <5 × 10 ^-5 mbar, ( viii) <10 ^-5 mbar, (ix) <5 × 10 ^-6 mbar and (x) <10 ^-6 mbar. A mass spectrometer according to any one of claims 19 to 25, wherein in the first mode of operation a pulse of ions ejected from the quadrupole ion trap and received by the further ion trap has a first energy range ΔE ₁ and wherein in the second mode of operation ions ejected from the further ion trap have a second energy range Have ΔE ₂ , where ΔE ₂ <ΔE ₁ . The mass spectrometer of claim 26, wherein ΔE ₁ / ΔE _{2 is} at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100 is. A mass spectrometer according to claim 26 or 27, wherein ΔE _{1 is} at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 eV. Mass spectrometer according to one of claims 26, 27 or 28, wherein ΔE ₂ at most 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0 , 1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02 or 0.01 eV. A mass spectrometer according to any one of the preceding claims, which further comprises a continuous or pulsed ion source. The mass spectrometer of claim 30, wherein the ion source selected from the following group is: (i) an electrospray ion source, (ii) an atmospheric pressure ionization chemical ion source ("APCI ion source"), (iii) an atmospheric pressure MALDI ion source, (iv) an electron ionization ion source ("EI ion source"), (v) an ion source with chemical Ionization ("CI ion source") and (vi) one Field desorption ionization ion source ("FI ion source"). The mass spectrometer of claim 30, wherein the ion source selected from the following group is: (i) a matrix supported Laser desorption ion source ("MALDI ion source"), (ii) a laser desorption ionization ion source ("LDI ion source"), (iii) a laser desorption / ionization-on-silicon ion source ("DIOS ion source"), (iv) a surface-enhanced laser desorption ionization ion source ("SELDI ion source") and (v) an ion source with rapid atomic bombardment ("FAB ion source"). A method of mass spectrometry which comprises the following Steps comprises: Providing a quadrupole ion trap, another ion trap, which is set up from the Quadrupole ion trap expelled Ions and a time-of-flight mass analyzer set up for this purpose is to receive ejected ions from the further ion trap, mass selective expel or by scanning an ion pulse or pulse ions in a first operating mode from the quadrupole ion trap, the further ion trap receiving the ion pulse and being the ratio between the maximum mass-to-charge ratio of the ions in the ion pulse and the minimum mass to charge ratio Ions in the ion pulse is a maximum x, where x ≤ 4.0, and collision cooling of the ions received by the quadrupole ion trap within the another ion trap. The method of claim 33, further comprising in the first mode of operation the further ion trap on one of the following Group selected pressure is held: (i) larger or equal to 0.0001 mbar, (ii) greater or equal to 0.0005 mbar, (iii) greater or equal to 0.001 mbar, (iv) greater or equal to 0.005 mbar, (v) greater or equal to 0.01 mbar, (vi) greater than or equal to 0.05 mbar, (vii) greater or equal to 0.1 mbar, (viii) greater or equal to 0.5 mbar, (ix) greater or equal to 1 mbar, (x) greater or equal to 5 mbar and (xi) greater or equal to 10 mbar. The method of claim 33 or 34, further comprising in the first operating mode, the further ion trap on one off selected from the following group Pressure is maintained: (i) less than or equal to 10 mbar, (ii) less or equal to 5 mbar, (iii) less than or equal to 1 mbar, (iv) less or equal to 0.5 mbar, (v) less than or equal to 0.1 mbar, (vi) less or equal to 0.05 mbar, (vii) less than or equal to 0.01 mbar, (viii) less than or equal to 0.005 mbar, (ix) less than or equal to 0.001 mbar, (x) less than or equal to 0.0005 mbar and (xi) less than or equal to 0.0001 mbar. The method of claim 33, 34 or 35, wherein further in the first operating mode, the further ion trap on a selected from the following group Pressure is maintained: (i) between 0.0001 and 10 mbar, (ii) between 0.0001 and 1 mbar, (iii) between 0.0001 and 0.1 mbar, (iv) between 0.0001 and 0.01 mbar, (v) between 0.0001 and 0.001 mbar, (vi) between 0.001 and 10 mbar, (vii) between 0.001 and 1 mbar, (viii) between 0.001 and 0.1 mbar, (ix) between 0.001 and 0.01 mbar, (x) between 0.01 and 10 mbar, (xi) between 0.01 and 1 mbar, (xii) between 0.01 and 0.1 mbar, (xiii) between 0.1 and 10 mbar, (xiv) between 0.1 and 1 mbar and (xv) between 1 and 10 mbar. A method according to any one of claims 33 to 36, the further in a second operating mode ions in non-mass selective or ejected from the further ion trap in a non-scanning manner or pulsed can be removed. The method of claim 37, wherein in the second Ion operating mode by applying one or more DC voltage extraction pulses pulsed to the other ion trap are removed from it or ejected. 39. The method of claim 38, wherein in the second Operating mode the one or more extraction DC voltages to the one or more end or end cap electrodes of the another ion trap. A method according to claim 38 or 39, wherein in the second operating mode the one or more DC extraction voltages to the one or more central electrodes or ring electrodes of the further ion trap. Method according to one of claims 37 to 40, wherein in the second mode of operation AC or RF voltages are not significant Dimensions to the Electrodes of the further ion trap are applied. 42. The method according to any one of claims 37 to 41, wherein the further Ion trap in the second mode of operation at a lower pressure than is held in the first mode of operation. The method of claim 42, wherein the further ion trap is on one of the following group selected pressure is maintained when operating in the second operating mode: (i) <5 × 10 ^-2 mbar, (ii) <10 ^-2 mbar, (iii) <5 × 10 ^-3 mbar, (iv) <10 ^{- 3} mbar, (v) <5 × 10 ^-4 mbar, (vi) <10 ^-4 mbar, (vii) <5 × 10 ^-5 mbar, (viii) <10 ^-5 mbar, (ix) <5 × 10 ^-6 mbar and (x) <10 ^-6 mbar. A method according to any one of claims 37 to 43, wherein in the first operating mode a pulse of ions ejected from the quadrupole ion trap and received by the further ion trap has a first energy range ΔE ₁ and wherein in the second operating mode ions ejected from the further ion trap have a second energy range Have ΔE ₂ , where ΔE ₂ <ΔE ₁ . The method of claim 44, wherein ΔE ₁ / ΔE _{2 is} at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100 is. The method of claim 44 or 45, wherein ΔE _{1 is} at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 eV. Method according to one of claims 44, 45 or 46, wherein ΔE ₂ at most 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0 , 1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02 or 0.01 eV. A method of mass spectrometry which comprises the following Steps comprises: Storage of initial ions with a first mass to charge ratio in a first ion trap, Save at least some others Starting ions with different from the first mass-charge ratio Mass-to-charge ratios in one or more additional Ion traps, Fragment the starting ions with the first mass to charge ratio in the first ion trap to form fragment ions capture some of the fragment ions in the first ion trap with a first one lower cutoff limit and Capture other fragment ions in a second ion trap with a second lower mass cutoff limit, where the second lower cutoff limit is less than the first lower mass cutoff limit. A method of mass spectrometry which comprises the following Steps comprises: Storage of initial ions with a first mass to charge ratio in a first ion trap, Save at least some others Starting ions with different from the first mass-charge ratio Mass-to-charge ratios in one or more additional Ion traps, Fragment the starting ions with the first mass to charge ratio in a first ion trap to form fragment ions capture some of the fragment ions in the first ion trap with a first one lower mass cutoff limit and trapping other of the fragment ions in a second ion trap with a second lower mass cut-off limit, where the second lower cutoff limit is less than the first lower mass cutoff limit. A method of mass spectrometry which comprises the following Steps comprises: Storage of initial ions with a first mass to charge ratio in an ion trap, Storing at least some other parent ions with mass-to-charge ratios different from the first mass-to-charge ratio in one or more additional Ion traps, Fragment the starting ions with the first mass to charge ratio to To form fragment ions Trapping some of the fragment ions in a first ion trap with a first lower mass cutoff limit and Trapping other fragment ions in a second ion trap with a second lower mass cutoff limit, the second lower mass cutoff limit is lower than the first lower mass cutoff limit. 51. The method of claim 50, wherein the ion trap includes the first ion trap. A method according to any one of claims 48 to 51, which further collision cooling of fragment ions within the first ion trap. A method according to any one of claims 48 to 52, which further collision cooling of fragment ions within the second ion trap. A method according to any one of claims 48 to 53, which further the removal by scanning or mass-selective ejection of some fragment ions from the first ion trap while other fragment ions be kept within the first ion trap. A method according to any one of claims 48 to 54, which further the removal by scanning or mass-selective ejection of some fragment ions from the second ion trap while other fragment ions be kept within the second ion trap. 56. The method of claim 54 or 55, further comprising in a first operating mode at least some fragment ions that removed from the first ion trap and / or the second ion trap by scanning or were ejected from it mass-selectively, in another Ion trap can be received, captured and cooled by collisions. The method of claim 56, wherein the further ion trap maintained at a pressure selected from the following group in the first operating mode becomes: (i) larger or equal to 0.0001 mbar, (ii) greater or equal to 0.0005 mbar, (iii) greater than or equal to 0.001 mbar, (iv) greater or equal to 0.005 mbar, (v) greater or equal to 0.01 mbar, (vi) greater than or equal to 0.05 mbar, (vii) greater or equal to 0.1 mbar, (viii) greater or equal to 0.5 mbar, (ix) greater or equal 1 mbar, (x) larger or equal to 5 mbar and (xi) greater or equal to 10 mbar. The method of claim 56 or 57, wherein the further Ion trap in the first mode of operation on one of the following Group selected pressure is held: (i) less than or equal to 10 mbar, (ii) less than or equal to 5 mbar, (iii) less than or equal to 1 mbar, (iv) less than or equal to 0.5 mbar, (v) less than or equal to 0.1 mbar, (vi) less or equal to 0.05 mbar, (vii) less than or equal to 0.01 mbar, (viii) less than or equal to 0.005 mbar, (ix) less than or equal to 0.001 mbar, (x) less than or equal to 0.0005 mbar and (xi) less than or equal to 0.0001 mbar. The method of claim 56, 57 or 58, wherein the further ion trap in the first operating mode on one of the following group selected Pressure is maintained: (i) between 0.0001 and 10 mbar, (ii) between 0.0001 and 1 mbar, (iii) between 0.0001 and 0.1 mbar, (iv) between 0.0001 and 0.01 mbar, (v) between 0.0001 and 0.001 mbar, (vi) between 0.001 and 10 mbar, (vii) between 0.001 and 1 mbar, (viii) between 0.001 and 0.1 mbar, (ix) between 0.001 and 0.01 mbar, (x) between 0.01 and 10 mbar, (xi) between 0.01 and 1 mbar, (xii) between 0.01 and 0.1 mbar, (xiii) between 0.1 and 10 mbar, (xiv) between 0.1 and 1 mbar and (xv) between 1 and 10 mbar. A method according to any one of claims 56 to 59, the further in a second operating mode ions in non-mass selective or ejected from the further ion trap in a non-scanning manner or pulsed can be removed. The method of claim 60, wherein in the second Ion operating mode by applying one or more DC voltage extraction pulses pulsed to the other ion trap are removed from it or ejected. The method of claim 61, wherein in the second Operating mode the one or more extraction DC voltages to the one or more end or end cap electrodes of the another ion trap. A method according to claim 61 or 62, wherein in the second operating mode the one or more DC extraction voltages to the one or more central electrodes or ring electrodes of the further ion trap. 63. The method according to any one of claims 60 to 63, wherein in the second mode of operation AC or RF voltages are not significant Dimensions to the Electrodes of the further ion trap are applied. A method according to any one of claims 60 to 64, wherein the further Ion trap in the second mode of operation at a lower pressure than is held in the first mode of operation. 67. The method of claim 65, wherein the further ion trap is maintained at a pressure selected from the following group when operating in the second mode of operation: (i) <5 × 10 ^-2 mbar, (ii) <10 ^-2 mbar, (iii ) <5 × 10 ^-3 mbar, (iv) <10 ^-3 mbar, (v) <5 × 10 ^-4 mbar, (vi) <10 ^-4 mbar, (vii) <5 × 10 ^-5 mbar, ( viii) <10 ^-5 mbar, (ix) <5 × 10 ^-6 mbar and (x) <10 ^-6 mbar. A method according to any one of claims 60 to 66, wherein in the first operating mode a pulse of ions ejected from the quadrupole ion trap and received by the further ion trap has a first energy range ΔE ₁ and wherein in the second operating mode ions ejected from the further ion trap have a second energy range Have ΔE ₂ , where ΔE ₂ <ΔE ₁ . The method of claim 67, wherein ΔΈ ₁ / ΔE _{2 is} at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100 is. The method of claim 67 or 68, wherein ΔE1 at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 eV. Method according to one of claims 67, 68 or 69, wherein ΔE ₂ at most 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0 , 1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02 or 0.01 eV. A method according to any one of claims 60 to 70, wherein an im second mode of operation ejected from the further ion trap or pulsed ion pulse from a time-of-flight mass analyzer Will be received. The method of claim 71, wherein the time of flight mass analyzer includes an axial time-of-flight mass analyzer. The method of claim 71, wherein the time of flight mass analyzer includes a lateral acceleration time-of-flight mass analyzer. Mass spectrometer, which comprises: a first ion trap, in which when used Aus ion ions with a first mass-charge ratio are stored, one or more additional ion traps in which, when used, at least some other starting ions with mass-charge ratios other than the first mass-charge ratio are stored, and a second ion trap, wherein, in use, the parent ions having the first mass to charge ratio are fragmented in the first ion trap to form fragment ions, and some of the fragment ions in the first ion trap are captured with a first lower mass cutoff limit and others of the fragment ions in the second Ion trap are captured with a second lower mass cut-off limit, the second lower mass cut-off limit being lower than the first lower mass cut-off limit. Mass spectrometer, which has: a Ion trap in which when using starting ions with a first Mass-charge ratio saved become, one or more additional ion traps, in which at using at least some other parent ions with others Mass-to-charge ratios stored as the first mass-to-charge ratio become, a first ion trap and a second ion trap, in which when used, the starting ions with the first mass-to-charge ratio in the first ion trap are fragmented so that fragment ions are formed and with some of the fragment ions in the first ion trap be captured with a first lower mass cutoff limit and others of the fragment ions in the second ion trap with one second lower mass cut-off limit are captured, wherein the second lower cut-off limit is lower than the first lower cutoff limit. Mass spectrometer, which has: a Ion trap in which when using starting ions with a first Mass-charge ratio saved become, one or more additional ion traps, in which at using at least some other parent ions with others Mass-to-charge ratios stored as the first mass-to-charge ratio become, a first ion trap and a second ion trap, in which in use the starting ions are fragmented with the first mass-charge ratio, so that fragment ions are formed, and with some of the fragment ions in the first Ion trap captured with a first lower mass cutoff limit and other fragment ions in the second ion trap a second lower mass cut-off limit are captured, where the second lower cutoff limit is less than the first lower mass cutoff limit. 76. The mass spectrometer of claim 76, wherein the ion trap includes the first ion trap. Mass spectrometer according to one of claims 74 to 77, the first ion trap including a quadrupole ion trap. 79. The mass spectrometer of claim 78, wherein the first Ion trap a 3D (Paul) quadrupole ion trap with a ring electrode and two end cap electrodes, the ring electrode and the end cap electrodes have a hyperbolic surface. 79. The mass spectrometer of claim 78, wherein the first Ion trap one or more cylindrical ring electrodes and two has essentially planar end cap electrodes. 79. The mass spectrometer of claim 78, wherein the first Ion trap one, two, three or more than three ring electrodes and has two substantially planar end cap electrodes. 81. The mass spectrometer of claim 80 or 81, wherein an end cap electrode of the first ion trap a sample or Has target plate. The mass spectrometer of claim 82, wherein the samples or Target plate has a substrate with several sample areas. A mass spectrometer according to claim 82 or 83, wherein the sample or target plate is arranged in a microtitration format is. Mass spectrometer according to claim 82, 83 or 84, where the distance between samples on the sample or target plate is approximately or is exactly 18 mm, 9 mm, 4.5 mm, 2.25 mm or 1.125 mm. Mass spectrometer according to one of claims 82 to 85, taking up to or at least 48, 96, 384, 1536 or 6144 samples can be received on the sample or target plate. Mass spectrometer according to one of claims 82 to 86, using a laser beam or electron beam is directed onto the sample or target plate. A mass spectrometer according to any one of claims 80 to 87, wherein an end cap electrode the first ion trap has a mesh or grid. 79. The mass spectrometer of claim 78, wherein the first Ion trap includes a 2D (linear) quadrupole ion trap that has a plurality of stick electrodes and two end electrodes. Mass spectrometer according to one of claims 74 to 77, the first ion trap being selected from the following group: (i) a segmented ring set with multiple electrodes, which openings from which ions are transmitted, and (ii) one Penning ion trap. Mass spectrometer according to one of claims 74 to 90, wherein a first AC or RF voltage with a first Amplitude is applied to the first ion trap. 91. The mass spectrometer of claim 91, wherein the first amplitude is selected from the following group: (i) 0-250 V _pp , (ii) 250-500 V _pp , (iii) 500-750 V _pp , (iv) 750-1000 V _pp , (v) 1000 - 1250 V _pp , (vi) 1250 - 1500 V _pp , (vii) 1500 - 1750 V _pp , (viii) 1750 - 2000 V _pp , (ix) 2000 - 2250 V _pp , (x) 2250 - 2500 V _pp , (xi) 2500 - 2750 V _pp , (xii) 2750 - 3000 V _pp , (xiii) 3000 - 3250 V _pp , (xiv) 3250 - 3500 V _pp , (xv) 3500 - 3750 V _pp , (xvi) 3750 - 4000 V _pp , (xvii) 4000 - 4250 V _pp , (xviii) 4250 - 4500 V _pp , (xix) 4500 - 4750 V _pp , (xx) 4750 - 5000 V _pp , (xxi) 5000 - 5250 V _pp , (xxii) 5250 - 5500 V _pp , (xxiii) 5500 - 5750 V _pp , (xxiv) 5750 - 6000 V _pp , (xxv) 6000 - 6250 V _pp , (xxvi) 6250 - 6500 V _pp , (xxvii) 6500 - 6750 V _pp , (xxviii) 6750 - 7000 V _pp , (xxix) 7000 - 7250 V _pp , (xxx) 7250 - 7500 V _pp , (xxxi) 7500 - 7750 V _pp , (xxxii) 7750 - 8000 Vp _p , (xxxiii) 8000 - 8250 V _pp , (xxx iv) 8250 - 8500 V _pp , (xxxv) 8500 - 8750 V _pp , (xxxvi) 8750 - 9000 V _pp , (xxxvii) 9000 - 9250 V _pp , (xxxviii) 9250 - 9500 V _pp , (xxxix) 9500 - 9750 V _pp , (xl) 9750 - 10000 V _pp and (xli)> 10000 V _pp . A mass spectrometer according to claim 91 or 92, wherein the first AC or RF voltage is a frequency within one selected from the following group Has range: (i) <100 kHz, (ii) 100-200 kHz, (iii) 200-400 kHz, (iv) 400-600 kHz, (v) 600-800 kHz, (vi) 800-1000 kHz, (vii) 1.0-1.2 MHz, (viii) 1.2-1.4 MHz, (ix) 1.4-1.6 MHz, (x) 1.6-1.8 MHz, (xi) 1.8-2.0 MHz and (xii)> 2.0 MHz. Mass spectrometer according to one of claims 74 to 93, the second ion trap including a quadrupole ion trap. 94. The mass spectrometer of claim 94, wherein the second Ion trap a 3D (Paul) quadrupole ion trap with a ring electrode and includes two end cap electrodes, the ring electrode and the end cap electrodes have a hyperbolic surface. 94. The mass spectrometer of claim 94, wherein the second Ion trap one or more cylindrical ring electrodes and two has essentially planar end cap electrodes. 94. The mass spectrometer of claim 94, wherein the second Ion trap one, two, three or more than three ring electrodes and has two substantially planar end cap electrodes. The mass spectrometer of claim 96 or 97, wherein one or more end cap electrodes of the second ion trap Have mesh or grid. 94. The mass spectrometer of claim 94, wherein the second Ion trap includes a 2D (linear) quadrupole ion trap that has a plurality of stick electrodes and two end electrodes. Mass spectrometer according to one of claims 74 to 93, the second ion trap being selected from the following group: (i) a segmented ring set with multiple electrodes, which openings from which ions are transmitted, and (ii) one Penning ion trap. Mass spectrometer according to one of claims 74 to 100, wherein a second AC or RF voltage with a second Amplitude is applied to the second ion trap. 101. The mass spectrometer of claim 101, wherein the second amplitude is selected from the following group: (i) 0-250 V _pp , (ii) 250-500 V _pp , (iii) 500-750 V _{p p} , (iv) 750-1000 V _pp , (v) 1000 - 1250 V _pp , (vi) 1250 - 1500 V _pp , (vii) 1500 - 1750 V _pp , (viii) 1750 - 2000 V _pp , (ix) 2000 - 2250 V _pp , (x) 2250 - 2500 V _pp , (xi) 2500 - 2750 V _pp , (xii) 2750 - 3000 V _pp , (xiii) 3000 - 3250 V _pp , (xiv) 3250 - 3500 V _pp , (xv) 3500 - 3750 V _pp , (xvi) 3750 - 4000 V _pp , (xvii) 4000 - 4250 V _pp , (xviii) 4250 - 4500 V _pp , (xix) 4500 - 4750 V _pp , (xx) 4750 - 5000 V _pp , (xxi) 5000 - 5250 V _pp , (xxii) 5250 - 5500 V _pp , (xxiii) 5500 - 5750 V _pp , (xxiv) 5750 - 6000 V _pp , (xxv) 6000 - 6250 V _pp , (xxvi) 6250 - 6500 V _pp , (xxvii) 6500 - 6750 V _pp , (xxviii) 6750 - 7000 V _pp , (xxix) 7000 - 7250 V _pp , (xxx) 7250 - 7500 V _pp , (xxxi) 7500 - 7750 V _pp , (xxxii) 7750 - 8000 V _pp , (xxxiii) 8000 - 8250 V _pp , (x xxiv) 8250 - 8500 V _pp , (xxxv) 8500 - 8750 V _pp , (xxxvi) 8750 - 9000 V _pp , (xxxvii) 9000 - 9250 V _pp , (xxxviii) 9250 - 9500 V _pp , (xxxix) 9500 - 9750 V _pp , (xl) 9750 - 10000 V _pp and (xli)> 10000 V _pp . A mass spectrometer according to claim 101 or 102, wherein the second AC or RF voltage has a frequency within a range selected from the following group: (i) <100 kHz, (ii) 100-200 kHz, (iii) 200-400 kHz , (iv) 400 - 600 kHz, (v) 600 - 800 kHz, (vi) 800 - 1000 kHz, (vii) 1.0 - 1.2 MHz, (viii) 1.2 - 1.4 MHz, ( ix) 1.4 - 1.6 MHz, (x) 1.6 - 1.8 MHz, (xi) 1.8 - 2.0 MHz and (xii) > 2.0 MHz. Mass spectrometer according to one of claims 74 to 103, the amplitude of one applied to the first ion trap AC or RF voltage is greater as the amplitude of an alternating applied to the second ion trap or RF voltage. 104. The mass spectrometer of claim 104, wherein the amplitude of an AC or RF voltage applied to the first ion trap is at least x V _pp greater than the amplitude of an AC or RF voltage applied to the second ion trap, where x is selected from the following group is: (i) 5, (ii) 10, (iii) 20, (iv) 30, (v) 40, (vi) 50, (vii) 60, (viii) 70, (ix) 80, (x) 90, (xi) 100, (xii) 110, (xiii) 120, (xiv) 130, (xv) 140, (xvi) 150, (xvii) 160, (xviii) 170, (xix) 180, (xx) 190, (xxi) 200, (xxii) 250, (xxiii) 300, (xxiv) 350, (xxv) 400, (xxvi) 450, (xxvii) 500, (xxviii) 550, (xxix) 600, (xxx) 650, (xxxi) 700, (xxxii) 750, (xxxiii) 800, (xxxiv) 850, (xxxv) 900, (xxxvi) 950 and (xxxvii) 1000. Mass spectrometer according to one of claims 74 to 105, wherein the first ion trap and / or the second ion trap a pressure selected from the following group is held: (i) bigger or equal to 0.0001 mbar, (ii) greater than or equal to 0.0005 mbar, (iii) greater or equal to 0.001 mbar, (iv) greater or equal to 0.005 mbar, (v) greater or equal to 0.01 mbar, (vi) greater than or equal to 0.05 mbar, (vii) greater or equal to 0.1 mbar, (viii) greater or equal to 0.5 mbar, (ix) greater or equal to 1 mbar, (x) greater or equal to 5 mbar and (xi) greater or equal 10 mbar. Mass spectrometer according to one of claims 74 to 106, wherein the first ion trap and / or the second ion trap a pressure selected from the following group is held: (i) less than or equal to 10 mbar, (ii) less than or equal to 5 mbar, (iii) less than or equal to 1 mbar, (iv) less than or equal to 0.5 mbar, (v) less than or equal to 0.1 mbar, (vi) less than or equal to 0.05 mbar, (vii) less than or equal to 0.01 mbar, (viii) less than or equal to 0.005 mbar, (ix) less than or equal to 0.001 mbar, (x) less than or equal to 0.0005 mbar and (xi) less than or equal to 0.0001 mbar. Mass spectrometer according to one of claims 74 to 107, the first ion trap and / or the second ion trap at use on a print selected from the following group is maintained: (i) between 0.0001 and 10 mbar, (ii) between 0.0001 and 1 mbar, (iii) between 0.0001 and 0.1 mbar, (iv) between 0.0001 and 0.01 mbar, (v) between 0.0001 and 0.001 mbar, (vi) between 0.001 and 10 mbar, (vii) between 0.001 and 1 mbar, (viii) between 0.001 and 0.1 mbar, (ix) between 0.001 and 0.01 mbar, (x) between 0.01 and 10 mbar, (xi) between 0.01 and 1 mbar, (xii) between 0.01 and 0.1 mbar, (xiii) between 0.1 and 10 mbar, (xiv) between 0.1 and 1 mbar and (xv) between 1 and 10 mbar. Mass spectrometer according to one of claims 74 to 108, which is a continuous or pulsed ion source having. The mass spectrometer of claim 109, wherein the Ion source is selected from the following group: (i) an electrospray ion source, (ii) an atmospheric pressure ionization chemical source ("APCI ion source"), (iii) an atmospheric pressure MALDI ion source, (iv) an electron ionization ion source ("EI ion source"), (v) an ion source with chemical Ionization ("CI ion source") and (vi) one Field desorption ionization ion source ("FI ion source"). The mass spectrometer of claim 109, wherein the Ion source is selected from the following group: (i) a matrix-assisted laser desorption ionization ion source ("MALDI ion source"), (ii) a laser desorption ionization ion source ("LDI ion source"), (iii) a laser desorption / ionization-on-silicon ion source ("DIOS ion source"), (iv) a surface-enhanced laser desorption ionization ion source ("SELDI ion source") and (v) an ion source with rapid atomic bombardment ("FAB ion source"). Mass spectrometer according to one of claims 74 to 111, which is further downstream of the second ion trap arranged ion detector. The mass spectrometer of claim 112, wherein the Ion detector an electron multiplier, a photo electron multiplier or has a channeltron. Mass spectrometer according to one of claims 74 to 113, which further comprises a time of flight mass analyzer. The mass spectrometer of claim 114, wherein the Time-of-flight mass analyzer an axial acceleration or one Has lateral acceleration time-of-flight mass analyzer. Mass spectrometer according to one of claims 74 to 115, which further has another ion trap. The mass spectrometer of claim 116, wherein the another ion trap includes a quadrupole ion trap. Mass spectrometer according to claim 117, wherein the further ion trap includes a 3D (Paul) quadrupole ion trap which has a ring electrode and two end cap electrodes, the ring electrode and the end cap electrodes having a hyperbolic surface. The mass spectrometer of claim 117, wherein the further ion trap one or more cylindrical ring electrodes and has two substantially planar end cap electrodes. The mass spectrometer of claim 117, wherein the further ion trap one, two, three or more than three ring electrodes and has two substantially planar end cap electrodes. Mass spectrometer according to claim 119 or 120, one or more end cap electrodes of the further ion trap has a mesh or grid. The mass spectrometer of claim 117, wherein the another ion trap includes a 2D (linear) quadrupole ion trap that has a plurality of stick electrodes and two end electrodes. The mass spectrometer of claim 116, wherein the further ion trap is selected from the following group: (i) a segmented ring set with multiple electrodes, which openings from which ions are transmitted, and (ii) one Penning ion trap. Mass spectrometer according to one of claims 116 to 123, with ions in a non-mass selective or not scanning mode pulsed from the further ion trap or pushed out become. The mass spectrometer of claim 124, wherein ions by applying a DC voltage extraction pulse to the others Ion trap can be removed or ejected in a pulsed manner. Mass spectrometer according to one of claims 74 to 125, wherein the one or more additional ion traps include a quadrupole ion trap. 126. The mass spectrometer of claim 126, wherein the one or more additional A 3D (Paul) quadrupole ion trap with a ring electrode and two end cap electrodes, wherein the ring electrode and the end cap electrodes are hyperbolic surface exhibit. 126. The mass spectrometer of claim 126, wherein the one or more additional Ion traps one or more cylindrical ring electrodes and two have essentially planar end cap electrodes. 126. The mass spectrometer of claim 126, wherein the one or more additional Ion traps one, two, three or more than three ring electrodes and have two substantially planar end cap electrodes. Mass spectrometer according to claim 128 or 129, wherein the one or more end cap electrodes of the one or of the several additional ones Ion traps have a network or a grid. 126. The mass spectrometer of claim 126, wherein the one or more additional Ion traps a 2D (linear) quadrupole ion trap includes, which have several rod electrodes and two end electrodes. Mass spectrometer according to one of claims 74 to 115, the one or more additional ion traps from the selected the following group are: (i) a segmented ring set with several electrodes, what openings from which ions are transmitted, and (ii) one Penning ion trap.