CN102651301A - Mass spectrometer with linear ion storage and time-of-flight mass analyzer connected in series - Google Patents
Mass spectrometer with linear ion storage and time-of-flight mass analyzer connected in series Download PDFInfo
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- CN102651301A CN102651301A CN2012101614730A CN201210161473A CN102651301A CN 102651301 A CN102651301 A CN 102651301A CN 2012101614730 A CN2012101614730 A CN 2012101614730A CN 201210161473 A CN201210161473 A CN 201210161473A CN 102651301 A CN102651301 A CN 102651301A
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Abstract
The invention belongs to the technical field of mass spectrometric analysis, in particular to a mass spectrometer with a linear ion storage and a time-of-flight mass analyzer which are connected in series. The mass spectrometer comprises an ion source, an ion optical system, the linear ion storage, the time-of-flight mass analyzer, an ion detector and a signal detecting, controlling and recording system, wherein the linear ion storage and the time-of-flight mass analyzer are directly connected; an accelerated electric field inlet of the time-of-flight mass analyzer is directly opposite to a lead electrode of the linear ion storage; and a conducting grid net is loaded on the ion lead electrode. After being collected and stored for certain time in the linear ion storage, ions are dispelled through a grid net electrode under the action of pulse voltage applied to the grid net electrode of the linear ion storage, and are led to an ion free flying area of the time-of-flight mass analyzer by the subsequent ion accelerating voltage, and then time-of-flight mass spectrometric analysis is finished. The combined instrument is good in performance and convenient to use, and the limitations and defects of the current combined instrument are overcome.
Description
Technical field
The invention belongs to the analytical technique of mass spectrum field, be specifically related to the mass spectrometer of a kind of linear ion stores and time of flight mass analyzer series connection.
Background technology
Mass spectrometer is that a kind of charged particle movement locus in electromagnetic field according to different quality is different, thus the separation of atom, molecule or the molecular fragment of realization different material and the analytical instrument of detection.Mass spectrometer has qualitative, quantitative analysis, structure to unknown compound and forms ability such as confirm, is widely used in fields such as environment measuring, food security, geological exploration, biomedicine.Since first mass spectrometer appearance in 1919, mass spectrometric kind is varied: magnetic mass spectrometer, quadrupole mass spectrometer, ion trap mass spectrometer, time-of-flight mass spectrometer, orbitrap analyzer, ICR etc.
The principle of time-of-flight mass spectrometer is that sample ions at first gets into the ion modulator zone, under the dc pulse voltage effect, gets into successively in accelerating lens and the condenser lens, advances to quicken and focused on the back to get into the field-free flight district, finally arrives detector.According to the difference of ion in the flight time of field-free region, mass of ion is big more, and it is long more to arrive the used time of detector, and mass of ion is more little, and it is short more to arrive the used time of detector, according to this principle, realizes separation and detection that different quality is counted ion.Reflection time-of-flight mass has increased mirror lens, and in order to the initial space dispersion of correcting sample ion, resolution improves the quality.Flight time mass spectrum have mass range in theory no maximum, analysis speed is fast and advantage such as sensitivity height, has been widely used in the for example mass spectral analysis of peptide section, albumen, nucleic acid etc. of large biological molecule.But; Time-of-flight mass spectrometer has the defective of himself; Sample ions gets into tof tube from the ion modulator zone and adopts the pulse input mode; Sample ions in the ion modulator zone has only sub-fraction to be introduced into tof tube to carry out mass separation, make that the duty ratio (duty cycle) of instrument is very low, caused the loss of a large amount of sample ions simultaneously; In addition, flight time mass spectrum self does not possess the cascade mass spectrometry ability, is difficult to obtain the information of the fragment ion of sample.
In order to improve the analytical performance of flight time mass spectrum, the mass spectrum insider has adopted the method for ion trap and the coupling of time of flight mass analyzer, and sample ions gets into before the time of flight mass analyzer, earlier through an ion trap.After current a collection of sample ions gets into the time of flight mass analyzer; The sample ions of its back is stored in ion trap immediately; Ion before treating gets into the ion modulator zone after accomplishing quality analysis again, is connected through the ion transfer system between ion trap and the ion modulator zone.Ion in the modulator zone gets into tof tube under the effect of pulse voltage, effectively improve the duty ratio of instrument, has reduced the loss of ion.
The ion trap of the GC-MS original adoption of ion trap and time of flight mass analyzer is a three-dimensional ion trap.The structure of three-dimensional ion trap causes its ion storage quantity very limited, can provide the nA level other ionic current than contemporary ion source, can't satisfy the requirement of ion storage and analysis far away.Simultaneously, the state after the three-dimensional ion trap intermediate ion is in bond generally is near the motion of central point that converges at trap, receives the influence of space charge effect very obvious, and is final, causes the performance of three-dimensional ion trap and flight time mass spectrum coupling instrument to improve very limited.2002, after linear ion hydrazine occurred, the GC-MS of ion trap and time of flight mass analyzer began to adopt linear ion hydrazine.The state of linear ion hydrazine intermediate ion generally is to converge on the axial line of z of linear ion hydrazine to move, and the quantity that can hold ion in the trap increases substantially.Than traditional three-dimensional ion trap, linear ion hydrazine has higher ion storage ability and lower space charge effect.
A kind of series connection linear ion hydrazine-time-of-flight mass spectrometer has been described among the patent WO 99/30350.Ion gets in the linear ion hydrazine vertically, discharges vertically then, gets into the ion modulator zone of Time-of flight analyzer through the ion transfer system.The direction of ion operation and the direction of tof tube are perpendicular quadrature and distribute.Linear ion hydrazine is made up of four round bar electrodes, and ion moves along the central shaft that round bar surrounds the zone, gets into Time-of flight analyzer.The technical scheme that this patent proposes; Can receive the influence of ion mass number; And the more important thing is that in the ion modulator zone, it is limited that pulsatile once is incorporated into the mass number of the ion in the time of flight mass analyzer; Only be the part of all-mass scope ion in the ion trap, this causes the sample analysis flux to be restricted.
A kind of method that makes the linear ion hydrazine intermediate ion get into time-of-flight mass spectrometer has been described in patent US 5763878.According to this method, linear ion hydrazine adopts the round bar electrode to form, and ion gets in the linear ion hydrazine vertically; Through cooling off with the collision of buffer gas, under the effect of rf electric field, will be along the axial gathering of trap; Then; Ion ejects the direction of edge with the axial direction quadrature of trap, and concrete is to pass from the space between the round bar electrode, gets into Time-of flight analyzer.This patent proposes when ion is drawn, and the rf electric field on the trap will break off, and through applying dc pulse voltage ion ejected, and how not to realize but describe this, and the voltage on the electrode is disposed and draws sequential does not have description yet.In addition; During the ion trap operation; The electric field that applies on four round bar electrodes is a high-voltage radio-frequency electric field with timing variations, and amplitude is generally at several kilovolts (zero peak values), and the method that this patent proposes will require the high-voltage radio-frequency electric field moment on the round bar electrode to break off simultaneously in a short period of time (several millisecond) to apply a very high dc pulse voltage and be used for ion and draw; This is difficult to realize in reality, the also not relevant as yet at present report of realizing this technology.
A kind of series connection linear ion hydrazine-time-of-flight mass spectrometer has been described in patent CN 200950429Y.In this equipment, modulating pulse is penetrated the lower end slit of object ion property along the line ion trap, upwards directly gets into Time-of flight analyzer from the footpath.Concrete, ion is to eject through the slit of opening on the electrode, slit width is that 1 mm is to 2 mm.Linear ion trap is made up of four identical cylinders or plate.This patent is not described modulating pulse and where and how to be applied to and to apply, and how to realize that the high speed of radio-frequency voltage and modulating pulse changes.SECO to configuration of the voltage on the electrode and voltage does not have description simultaneously yet.The more important thing is that the quantity that ion is drawn will be subject to the size of slit on the electrode, this will lose the strong advantage of linear ion hydrazine ion storage ability.
In patent CN 1926657A, a kind of tandem ion-trap time-of-flight mass spectrometer has been described.In this equipment, adopt digital voltage to drive ion trap, digitial controller is accurately controlled the high-speed electronic switch of one group of direct voltage and some, being connected and disconnection of the electrode of quick control direct voltage and ion trap.Four inner section of linear ion hydrazine are that bi-curved bar electrode is formed, and are being used for the electrode upper shed that ion is drawn simultaneously, and ion upwards ejects through opening from the footpath, gets into Time-of flight analyzer.The performance of this equipment mainly depends on digitial controller to the waveform of digital wave and the accurate control of sequential, and the TT&C system of instrument is had very high requirement.In addition, the digital RF voltage on the linear ion hydrazine is to be provided by electronic switch set, and the withstand voltage degree of electronic switch can limit the magnitude of voltage that applies on the trap, and the amplitude of digital RF voltage is very limited, and this will directly influence the storage and the ejection of ion.
The above shows that the technical scheme that the ion trap that existing patent proposes is connected with time-of-flight mass spectrometer exists many restrictions and shortcoming, and the performance of coupling instrument improves very limited, and simultaneously, the feasibility of instrument is lower.
Summary of the invention
The object of the present invention is to provide the spectrometer system of good, easy to use linear ion stores of a kind of coupling instrument performance and time of flight mass analyzer series connection, to overcome the many restrictions and the shortcoming of existing coupling instrument.
The spectrometer system of linear ion stores provided by the invention and the series connection of time of flight mass analyzer, its part comprises ion source, ion-optic system (transmission system), linear ion stores, time of flight mass analyzer, ion detector and signal observing and controlling and register system.Wherein:
Described linear ion stores directly links to each other with said time of flight mass analyzer, and the accelerating field inlet of time of flight mass analyzer is directly relative with the extraction electrode of linear ion memory.There is not other interface equipment between linear ion memory and the time of flight mass analyzer, like electrodes such as lens;
Said linear ion stores is by x in the three dimensions, the enclosed construction that y, the electrode pair of three directions of z surround.Pair of electrodes in the linear ion stores is used for ion draws, and applies direct voltage on it, and direct voltage has timing variations.Ion extraction electrode device has the conductive grid structure, is designated hereinafter simply as grid electrode.Ion in the linear ion stores directly ejects from memory through aperture plate, and grid electrode directly enters the mouth over against the accelerating field of time of flight mass analyzer.
Among the present invention, the direction that the setting ion is drawn is the x direction.The electrode pair of y direction applies radio-frequency voltage, and radio-frequency voltage has timing variations.Z direction electrode pair applies direct voltage, and direct voltage has timing variations.
In the Instrumental Analysis process, the ion that ion source produces gets into the linear ion stores from the z direction of principal axis earlier and stores, and gets in the time of flight mass analyzer again.Ion in the linear ion stores is under the effect of pulsed dc voltage; Eject through grid electrode; Get into immediately in the accelerating field of Time-of flight analyzer; Through getting into the field-free flight district after acceleration, focusing, the deflection, finally arrive ion detector, realize the analysis of connecting of linear ion stores and time of flight mass analyzer.
Make up the x of linear ion stores, y, each electrode in the electrode pair of three directions of z can be electrodes, also can be by two, or the discrete electrodes more than two constitutes.
The size and the specification of said grid electrode are unrestricted.The shape and size of the electrode of contraposition are unrestricted mutually with grid electrode.
The ion extraction electrode is right on the x direction, and one of them is a grid electrode, and another electrode can be a plate electrode, also can be grid electrode, also can be the electrode of other structure, must satisfy the requirement that can make up zero potential surface.
Z direction electrode pair is a plate electrode, wherein is used for having ion on the electrode that ion introduces and introduces aperture, and the shape and size of aperture are unrestricted, everyly can satisfy all small structures that ion is introduced linear ion stores and all can adopt.Be that the right shape and size of Z direction top electrode are unrestricted in the linear ion stores.
Y direction electrode pair, electrode structure can make plate electrode, also can be the hyperboloid electrode, also can be the round bar electrode, also can make the square bar electrode, and every electrode structure that fetters ion of can realizing all can adopt.Be that the right shape and size of y direction top electrode are unrestricted in the linear ion stores.
The structure of time of flight mass analyzer is unrestricted, and existing various structures all can adopt at present.
Feed neutral gas in the linear ion stores as cold gas, the mass number of neutral gas requires the mass number less than analyte.Neutral gas feeds the not restriction of position in the linear ion stores, can feed from any direction, as long as can gassy in the memory all can.
Voltage distribution characteristics on each electrode of linear ion stores that proposes among the present invention is following, and linear ion stores has the different operating stage in time, and the voltage of each electrode distributes different, and adopting cation with sample ions is the example explanation.
Introduce the stage at ion, the DC potential on the z direction electrode pair reduces, and has a potential difference between the ion-optic system at the linear ion stores and the upper reaches, makes sample ions get in the linear ion stores.Apply the radio-frequency voltage of certain amplitude at this moment on the electrode pair of y direction, the ion extraction electrode of x direction is to remaining on zero potential, and the time that ion is introduced the stage is some milliseconds.
In the ion storage stage, the DC potential of the electrode pair of z direction raises, and forms a potential difference, the ion at the upper reaches is kept off outside memory, with the ion binding in the memory on the z direction.The ion extraction electrode of x direction is to keeping zero potential, and the electrode pair of y direction applies the rf electric field of certain amplitude; Ion and neutral gas bump and consume self kinetic energy.Ion is being stored in linear ion stores under the acting in conjunction of DC potential and rf electric field.
Eject the stage at ion, apply direct voltage on the electrode pair of z direction and remain unchanged.Extraction electrode on the x direction on apply the dc pulse voltage of special parameter, amplitude is (high-voltage dc pulse) up to several kilovolts, moment forms the repulsion electric field that a direction is pointed to grid electrode on the x direction.Ion receives the repulsive force of a high strength, direction sensing grid electrode in moment.Parameters such as the positive negativity of pulsed dc voltage, cycle, width, amplitude do not have concrete restriction, according to the kind concrete configuration of being drawn ion, can realize that voltage that memory intermediate ion moment draws grid electrode distributes all to be suitable for.Under the effect of pulse voltage, the ion that fetters in the memory will eject from linear ion stores through aperture plate, directly get into Time-of flight analyzer, accomplish quality analysis.
After ion got into the time of flight mass analyzer, x direction ion extraction electrode was to getting back to zero potential rapidly.Linear ion stores begins next ion introducing-storage-spill process immediately, and whether the ion analysis process in the time of flight mass analyzer does not influence that the ion of linear ion stores is drawn, storing process.
The structure of the linear ion stores that adopts among the present invention and voltage distribute, and rf electric field separates with high-voltage dc pulse voltage fully, and is independent separately.High-voltage dc pulse voltage and radio-frequency voltage can not influence each other between the two, and Energy distribution when ion is drawn and spatial distribution can not receive the influence of rf electric field.
The grid electrode that proposes among the present invention has good ion trafficability characteristic; Under the effect of high-voltage dc pulse; When drawing, passes in the ion in the memory from whole grid electrode face; Almost the whole ions in the memory all can eject moment, even there is certain decentralization in the ion in the memory, the ejection of ion can not be affected yet.The interface of tandem mass spectrum has been simplified in the use of grid electrode, and can not receive the restriction of drawing the size of slit or opening such as ion, can to greatest extent the ion that fetters in the linear ion stores be incorporated in the Time-of flight analyzer.It is thus clear that coupling instrument performance of the present invention is good, easy to use, overcome the many restrictions and the shortcoming of existing coupling instrument.
Description of drawings
Fig. 1: the mass spectrometric block diagram of the embodiment of the invention 1.
The voltage distribution map of the linear ion stores that Fig. 2: embodiment 1 adopts.Wherein, (A) being the two-dimensional cross-sectional view of xy face, (B) is the two-dimensional cross-sectional view of yz face.
The structure chart that the linear ion stores that Fig. 3: embodiment 1 adopts is connected with the time of flight mass analyzer
Fig. 4: the embodiment of the invention 1 mass spectrometric integrally-built cross sectional view.
Fig. 5: linear ion stores intermediate ion simulation of movement track.Wherein, (A) being the two-dimensional cross-sectional view of xy face, (B) is the two-dimensional cross-sectional view of yz face.
Fig. 6: the mode that the applies sketch map of pulse voltage on the ion extraction electrode in the linear ion stores.
Fig. 7: the integrally-built cross sectional view of the embodiment of the invention 2 mass spectrometers.
Embodiment
Hereinafter is through embodiment and combine accompanying drawing, further describes the present invention, can better understand advantage of the present invention.
Specific embodiment 1 is the block diagram of the linear ion stores-time-of-flight mass spectrometer of connecting with reference to shown in Figure 1.Instrument mainly contains ion source, ion-optic system (transmission system), linear ion stores, Time-of flight analyzer, detector and TT&C system and forms.Ionogenic kind and structure are unrestricted, and any disclosed method and apparatus of sample ionsization of can realizing all can adopt in the prior art.
The structure of the linear ion stores that adopts among the embodiment 1 is as shown in Figure 2, is made up of six cube electrodes, is respectively the electrode 205 and 206 of axially going up (z direction), and perforate on the electrode 205 is used for ion and introduces; Pair of electrodes 202 and 203 on the x direction, the pair of electrodes 201 and 204 on the y direction, the direction that the definition ion ejects is the x direction.Wherein, apply direct voltage on the z direction electrode 205 and 206, be used for axially going up the constraint ion.Electrode 201 and 204 applies radio-frequency voltage, and electrode 202 and 203 all is in zero potential in the non-ejection of the ion stage, and the acting in conjunction of electrode 201,202,203,204,205,206 realizes the constraint of ion.
Shown in Figure 3 is accelerating field cascaded structure distribution map in linear ion stores and the Time-of flight analyzer among the embodiment 1.Electrode 301 and symmetrical with it another electrode (not drawing among Fig. 3) are formed y direction electrode pair, and electrode 302 and 305 is formed x direction electrode pairs, and electrode 303 and 304 is formed z direction electrode pairs.Ion axially gets into the linear ion stores from the electrode 304 with aperture along z, cools off through the direct voltage of the radio-frequency voltage on the y direction electrode pair, z direction electrode pair and with the collision of buffer gas and realizes the constraint of ion in memory.Pair of electrodes on the x direction keeps zero potential; Wherein electrode 305 is as the ion extraction electrode, and device has the conductive grid structure, and electrode 302 is that plate electrode also can be a grid electrode; Its purpose is; When applying pulsed dc voltage on the electrode 302, can make up an equally distributed DC electric field between the electrode 302 and 305, be used for ion is drawn linear ion stores.The ion of drawing gets into accelerating field, is made up of electrode 306,307,308, and the number of electrodes and the structure of accelerating field are unrestricted.Get into tof tube through quickening the back, carry out quality analysis analysis time.Ion ejects the stage, and the ion in the linear ion stores can pass through the grid electrode face in moment, and almost the whole ions in the memory all can eject.
Shown in Figure 4 is the integrally-built cross sectional view of the linear ion stores-time-of-flight mass spectrometer of series connection of embodiment 1.
The analytic process of embodiment 1 is: the ion that ion source 401 produces gets in the linear ion stores and stores through the transmission of ion-optic system 402, gets in the time of flight mass analyzer through the ion extraction electrode again.
The linear ion stores that adopts among the embodiment 1 is made up of three pairs of electrodes, and electrode 404 and 406 is the pair of electrodes on the linear ion stores x direction, and wherein electrode 406 is ion extraction electrodes, and device has the conductive grid structure.Do not show among pair of electrodes Fig. 4 on the y direction.Electrode 403 and 405 is the pair of electrodes on the z direction, has aperture on the electrode 403.Ion gets in the linear ion stores through the aperture from z direction top electrode 403.
407 is the conduit of neutral gas, is used for neutral gas is imported linear ion stores.Comprise accelerating field electrode group 408 in the time of flight mass analyzer, focus lens group 409, mirror lens group 410, and ion detector 411,412 expression sample ions.
The change in voltage of each electrode of the linear ion stores among the embodiment 1 is following:
Introduce the stage at ion, suppose that sample ions is a cation, the DC potential on the z direction electrode 403 and 405 reduces, and has potential difference between ion stores and ion-optic system before 401 and 402, orders about ion and gets in the linear ion stores.The pair of electrodes of y direction applies the rf electric field of certain amplitude, and the electrode 404 and 406 of x direction remains on zero potential, and the time of introducing the stage is Millisecond.
After ion was introduced in the linear ion stores, the DC potential on the electrode 403 and 405 raise, and forms a potential difference, and ion 412 is strapped in the memory, simultaneously the ion in the upstream ion optical system was kept off outside memory.Electrode 404 in the memory and 406 keeps zero potentials, and the pair of electrodes of y direction applies rf electric field, and 405 wireways for example feed that mass number such as helium, argon gas maintains 10 less than the neutral gas of analyte as cold gas air pressure
-1-10
-3Between the Pa.Ion 412 bumps with cold gas and consumes self kinetic energy, under the acting in conjunction of DC potential and rf electric field, is bound in the linear ion stores.
Eject the stage at ion, apply the dc pulse voltage of some cycles and amplitude on electrode 404 and the grid electrode 406, make ion receive a repulsive force powerful, direction sensing grid electrode 406 in moment.Under the effect of pulse voltage; Ion 412 in the linear ion stores will eject from memory through grid electrode 406, apply direct voltage on the accelerating field 408,408 of entering Time-of flight analyzer; Ion 412 is through after quickening; Get into condenser lens 409, apply direct voltage on it, ion 412 is focused on or deflection.Ion 412 gets into the field-free flight district after leaving condenser lens; After one section field-free flight; Get into reflected field district 410, through the final ion detector microchannel plate (MCP) 411 that arrives in reflection back, through the data acquisition system record with after amplifying; Handle and output through follow-up instrument again, finally obtain the mass spectrogram of needed sample ions 412.
After ion got into Time-of flight analyzer, x direction ion extraction electrode was to getting back to zero potential rapidly.Linear ion stores begins next ion introducing-storage-spill process immediately, and whether the ion analysis process in the time of flight mass analyzer does not influence that the ion of linear ion stores is drawn, storing process.
Generally speaking, ion-optic system, linear ion stores, time of flight mass analyzer and ion detector all must operate under the vacuum condition.Ion source is also inequality according to the different desired vacuum condition of its kind.
When studying the linear ion stores work that proposes in this patent in great detail to the constraint ability of ion, through use temperature 300 k, neutral buffered gas as the helium condition under memory intermediate ion motion state carry out emulation.Simulation result is as shown in Figure 5.501 and 502 is pair of electrodes on the linear ion stores y direction, applies radio-frequency voltage on it; 503 and 504 is x direction pair of electrodes, and 503 and 504 all adopt grid electrode, and current potential remains on zero potential on it.505 and 506 is z direction pair of electrodes, applies certain DC potential on it.Fig. 5 (A) shows that ion center in the xy plane in linear ion stores is reciprocating, reciprocating motion on the center line on Fig. 5 B demonstration ion yz plane in linear ion stores.In conjunction with Fig. 5 (A) and Fig. 5 (B), the linear ion stores structure that the present invention proposes can be successfully with ion binding therein.
The mode that applies for pulse voltage on the ion extraction electrode in the linear ion stores that adopts among the embodiment 1 shown in Figure 6.601 and 602 represent the pair of electrodes of x direction respectively, and wherein 602 is grid electrode.Applying of pulse signal can be passed through several different methods; For example: add on the electrode 601 on the pulse voltage, electrode 602 of plus or minus direction and keep zero potential; Perhaps apply pulse voltage in the opposite direction respectively on the electrode 601 and 602, it is little perhaps to apply identical pulse voltage of direction and the pulse voltage value on the grid electrode on the electrode 601 and 602 respectively.The concrete direction of pulse signal can be according to the kind concrete configuration of being drawn ion on 601 and 602 electrodes, and its result satisfies moment ion is evicted to grid electrode motion and through grid electrode.
Shown in Figure 7 is the integrally-built cross sectional view of linear ion stores-time-of-flight mass spectrometer that embodiment 2 adopts.
The analytic process of embodiment 2 is: the ion that ion source 701 produces gets in the linear ion stores and stores through the transmission of ion-optic system 702, gets in the time of flight mass analyzer through the ion extraction electrode again.
The linear ion stores that adopts among the embodiment 2 is made up of electrode many, and x direction top electrode has 704,705,706,707,708,709, and y direction electrode has 717,718,719,720,721,722 (see figure 7)s, and z direction electrode has 703 and 710.Its intermediate ion extraction electrode is 707, and device has the conductive grid structure, hereinafter to be referred as grid electrode.Ion extraction electrode 707 directly enters the mouth over against the accelerating field 713 of time of flight mass analyzer.
711 is the conduit of neutral gas, is used for neutral gas is imported linear ion stores.Comprise accelerating field electrode group 713 in the time of flight mass analyzer, focus lens group 714, mirror lens group 715, and ion detector 716,712 expression sample ions.
Voltage on each electrode of linear ion stores among the embodiment 2 distributes as follows: x direction electrode 704,705,708,709 applies radio-frequency voltage and direct voltage simultaneously, and direct voltage is as the direct current biasing of radio-frequency voltage, and has timing variations; Electrode 706,707 only applies direct voltage, and has timing variations.Y direction electrode 717,718,719,720,721,722 applies radio-frequency voltage and direct voltage simultaneously, and direct voltage is as the direct current biasing of radio-frequency voltage, and has timing variations. Z direction electrode 703 and 710 applies direct voltage.
The change in voltage of electrode is following in the linear ion stores that embodiment 2 proposes:
Introduce the stage at ion; Suppose that sample ions is a cation; Direct voltage on x, y, three direction electrodes of z forms one from the ion transfer system to electrode 710, and the potential difference that each electrode potential distributes is from high to low ordered about ion and got in the linear ion stores.X direction electrode 704,705,708,709, three pairs of electrodes of y direction apply radio-frequency voltage simultaneously, and electrode 706 and 707 remains on zero potential, and the time of introducing the stage is several milliseconds.
After ion is introduced in the linear ion stores; X direction electrode 704,705,708,709; The direct voltage on the electrode 717,718,721,722 of y direction and the electrode 719,720 of x direction electrode 706,707 and y direction form the DC potential difference on the z direction between each electrode pair.The electrode 704,705,708,709 and the DC potential on the electrode 717,718,721,722 that are positioned at z direction two ends are high, and the electrode 706,707 and the DC potential on the electrode 719,720 that are positioned at z direction mid portion are low.Three pairs of electrodes of x direction electrode 704,705,708,709 and y direction apply radio-frequency voltage simultaneously.711 wireways feed the neutral gas of certain air pressure as cold gas gas.Ion 712 bumps with cold gas and consumes self kinetic energy, under the acting in conjunction of DC potential and rf electric field, will get into ion binding in the memory in the space that the electrode 719,720 of x direction electrode 706,707 and y direction is surrounded.
Draw the stage at ion, apply the dc pulse voltage of some cycles and amplitude on electrode 706 and the grid electrode 707, ion receives the repulsive force high-intensity, that direction is pointed to grid electrode 707 in moment.Under the effect of pulse voltage; Ion 712 in the linear ion stores will eject from memory through grid electrode 707, apply direct voltage on the accelerating field 713,713 of entering Time-of flight analyzer; Ion 712 is through after quickening; Get into condenser lens 714, apply direct voltage on it, ion 712 is focused on or deflection.Ion 712 gets into the field-free flight district after leaving condenser lens; After one section field-free flight; Get into reflected field district 715, through the final ion detector microchannel plate (MCP) 716 that arrives in reflection back, through the data acquisition system record with after amplifying; Handle and output through follow-up instrument again, finally obtain the mass spectrogram of needed sample ions 712.
After ion got into Time-of flight analyzer, x direction ion extraction electrode was to getting back to zero potential rapidly.Linear ion stores begins next ion introducing-storage-spill process immediately, and whether the ion analysis process in the time of flight mass analyzer does not influence that the ion of linear ion stores is drawn, storing process.
Generally speaking, ion-optic system, linear ion stores, time of flight mass analyzer and ion detector all must operate under the vacuum condition.Ion source is also inequality according to the different desired vacuum condition of its kind.
Claims (5)
1. the mass spectrometer of linear ion stores and time of flight mass analyzer series connection; It is characterized in that its part comprises ion source, ion-optic system, linear ion stores, time of flight mass analyzer, ion detector and signal observing and controlling and register system; Wherein:
Described linear ion stores directly links to each other with described time of flight mass analyzer, and the accelerating field inlet of time of flight mass analyzer is directly relative with the extraction electrode of linear ion memory;
Said linear ion stores is by x in the three dimensions, the enclosed construction that y, the electrode pair of three directions of z surround, and the pair of electrodes in the linear ion stores is used for ion draws, and applies direct voltage on it, and direct voltage has timing variations; The ion extraction electrode is provided with the conductive grid structure; Be designated hereinafter simply as grid electrode; Ion in the linear ion stores directly ejects from linear ion stores through grid electrode, and grid electrode directly enters the mouth over against the accelerating field of time of flight mass analyzer.
2. the mass spectrometer of linear ion stores according to claim 1 and the series connection of time of flight mass analyzer is characterized in that, the direction that the setting ion is drawn is the x direction, and the electrode pair of y direction applies radio-frequency voltage, and radio-frequency voltage has timing variations; Z direction electrode pair applies direct voltage, and direct voltage has timing variations;
In the Instrumental Analysis process, the ion that ion source produces gets into the linear ion stores from the z direction of principal axis earlier and stores, and gets in the time of flight mass analyzer again; Ion in the linear ion stores is under the effect of pulsed dc voltage; Eject through grid electrode, get into immediately in the accelerating field of Time-of flight analyzer, through getting into the field-free flight district after acceleration, focusing, the deflection; The final ion detector that arrives is realized the analysis of connecting of linear ion stores and time of flight mass analyzer.
3. the mass spectrometer of linear ion stores according to claim 1 and the series connection of time of flight mass analyzer; It is characterized in that; Constitute the x of linear ion stores, y, each electrode in the electrode pair of three directions of z are electrodes; Perhaps by two, or the discrete electrodes more than two constitutes.
4. the mass spectrometer of linear ion stores according to claim 1 and the series connection of time of flight mass analyzer is characterized in that the ion extraction electrode is right on the x direction, and one of them is a grid electrode, and another electrode is plate electrode or is grid electrode;
Z direction electrode pair is a plate electrode, wherein is used for having ion on the electrode that ion introduces and introduces aperture;
Y direction electrode pair is a plate electrode, perhaps is the hyperboloid electrode, perhaps is the round bar electrode, perhaps is the square bar electrode.
5. the mass spectrometer of linear ion stores according to claim 1 and the series connection of time of flight mass analyzer is characterized in that the voltage distribution characteristics on said each electrode of linear ion stores is following:
Introduce the stage at ion, the DC potential on the z direction electrode pair reduces, and has a potential difference between the ion-optic system at the linear ion stores and the upper reaches, makes sample ions get in the linear ion stores; Apply the radio-frequency voltage of certain amplitude at this moment on the electrode pair of y direction, the ion extraction electrode of x direction is to remaining on zero potential, and the time that ion is introduced the stage is some milliseconds;
In the ion storage stage, the DC potential of the electrode pair of z direction raises, and forms a potential difference, the ion at the upper reaches is kept off outside linear ion stores, with the ion binding in the linear ion stores on the z direction; The ion extraction electrode of x direction is to keeping zero potential, and the electrode pair of y direction applies the rf electric field of certain amplitude; Ion and neutral gas bump and consume self kinetic energy; Ion is being stored in linear ion stores under the acting in conjunction of DC potential and rf electric field;
Eject the stage at ion, apply direct voltage on the electrode pair of z direction and remain unchanged; Extraction electrode on the x direction on apply the pulse voltage of special parameter, amplitude is up to several kilovolts, moment forms the repulsion electric field that a direction is pointed to grid electrode on the x direction, ion receives the repulsive force that a high strength, direction are pointed to grid electrode in moment; Under the effect of pulse voltage, the ion that fetters in the linear ion stores ejects from linear ion stores through grid electrode, directly gets into the time of flight mass analyzer, accomplishes quality analysis;
After ion gets into the time of flight mass analyzer; X direction ion extraction electrode is to getting back to zero potential rapidly; Linear ion stores begins next ion introducing-storage-spill process immediately, and whether the ion analysis process in the time of flight mass analyzer does not influence that the ion of linear ion stores is drawn, storing process.
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