CN101320016A - Method for cascade mass spectrometry by using multiple ion traps - Google Patents

Method for cascade mass spectrometry by using multiple ion traps Download PDF

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Publication number
CN101320016A
CN101320016A CNA2008100331992A CN200810033199A CN101320016A CN 101320016 A CN101320016 A CN 101320016A CN A2008100331992 A CNA2008100331992 A CN A2008100331992A CN 200810033199 A CN200810033199 A CN 200810033199A CN 101320016 A CN101320016 A CN 101320016A
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China
Prior art keywords
ion
ion trap
trap
electric field
mass
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CNA2008100331992A
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Chinese (zh)
Inventor
蒋公羽
罗婵
丁传凡
丁力
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Fudan University
Shimadzu Corp
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Fudan University
Shimadzu Corp
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Priority to CNA2008100331992A priority Critical patent/CN101320016A/en
Publication of CN101320016A publication Critical patent/CN101320016A/en
Priority to PCT/CN2009/071048 priority patent/WO2009094954A1/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/4205—Device types
    • H01J49/422—Two-dimensional RF ion traps
    • H01J49/423—Two-dimensional RF ion traps with radial ejection
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/426—Methods for controlling ions
    • H01J49/427—Ejection and selection methods

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)

Abstract

The invention belongs to the quality analysis technology field and in particular relates to a method of using a plurality of ion traps for the tandem mass spectrometric analysis, including that a high frequency capturing electric field based on a quadrupole field is produced in the first ion trap for capturing ions with various mass-to-charge ratios. A dipolar excitation alternating electric field with certain frequency along the direction of a straight line for connecting the center of the first ion trap center with the center of a second ion trap center is produced in the first ion trap. Thus, the ions with a mass-to-charge ratio oscillate along the direction to reach to the large amplitude under the resonance excitation. Furthermore, a discharged pulse electric field generates in a specific phase of the first ion trap. The ions reaching to the large moving amplitude are discharged and enter the second ion trap. And the ions with other mass-to-charge ratios are still left in the first ion trap. Through a deceleration field added in the second ion trap or the gas collision, the entering ions or byproduct ions are captured and the researching analysis is further made in the second ion trap.

Description

The a plurality of ion traps of a kind of usefulness are carried out the method for cascade mass spectrometry
Technical field
The invention belongs to the quality analysis technical field, be specifically related to a kind of method of using two or more ion traps ion to be carried out quality analysis.
Technical background
Mass spectrometer is a kind of scientific instrument that can be used for the various compositions of amalyzing substances sample, content and molecular structure.Ion trap mass spectrometer is one of mass spectrometer that is widely used at present.Characteristics such as it has simple in structure, and is easy to operate, and price is more cheap.Be widely used in chemistry, life science, geological sciences, petrochemical complex, medical and health, environmental protection, every field such as food security.
Traditional ion trap can be divided into three-dimensional ion trap according to the difference of its structure, linear ion trap.The electrode shape that constitutes ion trap has hyperboloid shape electrode, cylindrical electrode, or rectangular electrode etc.
Fig. 1 has provided the structural representation (not showing among two termination electrode figure of linear ion trap) of four hyperboloid electrodes of a traditional linear ion trap.In actual use, two electrode of opposite 11 and 13,12 and 14 are linked together, form two end points 15 and 16, on each end points, add opposite polarity radio-frequency power supply then.Be shown below:
Ф 1(t)＝+(U+Vcosωt)
Ф 2(t)＝-(U+Vcosωt)
In the formula, U represents DC voltage, and V represents alternating voltage, and ω=2 π f represent the angular frequency of radio-frequency power supply, and f is the frequency of radio-frequency power supply.
The quadrupole ion trap system in by four zones that electrode surrounded, produces the Electric Field Distribution based on quadripolar electric field under the effect of radio-frequency power supply.It can be so that enter the intrasystem positive ion of this quadrupole rod or negative ion under quadripolar electric field is main electric field action, is bound in the zone that four electrodes etc. are surrounded, and promptly ion is stored.
When need be to being stored in ion in the ion trap when carrying out quality analysis, can be added in ac voltage on four utmost point electrodes by variation, allow the ion of different mass-to-charge ratioes be evicted from by the slit on the electrode stem 17 successively.Detection and record are evicted from the signal of ion, promptly obtain the result of mass spectrophotometry.
The patent No. is that 200410024946.8 Chinese invention patent has provided a kind of method that makes up linear ion trap with printed-wiring board (PWB).Fig. 2 has provided the cross section structure synoptic diagram of a printed-wiring board (PWB) ion trap.In Fig. 2,21,22,23 and 24 are respectively four bar printing wiring boards makes.Each printed-wiring board (PWB) is made up of five strip electrodes that apply on the surface again.As wiring board 21 by five littler strip electrodes 201,202,203,204 and 205 compositions; Wiring board 22 is by five littler strip electrodes 206,207,208,209 and 210 compositions; Wiring board 23 is by five littler strip electrodes 211,212,213,214 and 215 compositions; Wiring board 24 is by five littler strip electrodes 216,217,218,219 and 220 compositions.
When above-mentioned ion trap is in running order, its power supply connected mode is: electrode 201 and 206 links together, electrode 210 and 211 links together, electrode 215 and 220 links together, electrode 205 and 216 links together, and the above-mentioned electrode of respectively organizing is loaded an identical DC voltage according to the experiment needs at last.Electrode 202 and 204 links together, and electrode 212 and 214 is joined together.Electrode 207 and 209 links together, and electrode 217 and 219 links together.The load mode of ion trap operating voltage is: electrode 203 and 213 is joined together and loads radio-frequency power supply+RF1, and electrode 208 and 218 is joined together, and loads radio-frequency power supply-RF1.Electrode 202 and 204, electrode 212 and 214 are loaded radio-frequency power supply+α RF1 (0＜α＜1), and electrode 207 and 209, electrode 217 and 219 are loaded radio-frequency power supply-α RF1 (0＜α＜1).Under the effect of above-mentioned electrode connection mode and power supply, in the central area of ion trap, will produce, and contain the ion binding electric field of a small amount of other high-order electric field compositions based on quadripolar electric field.Enter ion 221 in the ion trap under these effect of electric field, will be stored in the ion trap.
Utilize auxiliary AC electric field, can excite successively by the size of their mass-to-charge ratioes and evict from, can receive and make signal and amplify by ion detector 223 by the ion of evicting from the slit 222 to being stored in ion 221 in the ion trap.Further signal record and processing will provide needed mass-spectrometer measurement result.
International monopoly WO0129875A, PCT/GB00/03964 have proposed to produce on the electrode of a square-wave voltage output ion trap with one group of switch, also can reach the purpose of quality analysis.Facts have proved that above-mentioned PCB ion trap can replace sinusoidal wave RF voltage by square-wave voltage too,, realize the linear ion trap quality analysis of digital P CB as driving voltage.In the preceding like this formula,
Ф 1(t)＝-Ф 2(t)＝(-1) nV
n＝int(2t/T)
Be that t experiences every half period T/2, constraint driving voltage is become-V by+V, or-V becomes+V.
The mass-spectrometry method of analyzing molecules structure commonly used is so-called cascade mass spectrometry method.It is by at first analyzed sample ions being cracked into fragmention, and then further fragmention is carried out mass spectrophotometry, obtains forming the fragmention product of sample ions.Infer the molecular composition of original analyzed ion and structure etc. by fragmention again.
When with tandem mass spectrometry methods analyst molecular structure, common experimental analysis process comprises three parts: (1) parent ion is selected, and (2) parent ion dissociates, (3) daughter ion analysis.That is, earlier with the sample ions that ion gun produced, promptly so-called usually " parent ion " separated from other various ions, and then the parent ion of separating is dissociated into fragmention with certain method, promptly so-called " daughter ion ".The last composition of measuring the daughter ion again.Can go out the The Nomenclature Composition and Structure of Complexes of parent ion according to the constituent analysis of daughter ion.
Traditionally, having several method can be used for parent ion selects.A kind of method is to realize the parent ion selection with quadrupole ion trap.Its detailed process is, the sample ions that ion gun is produced is introduced and is stored in the ion trap earlier, the AC field that superposes specific then wherein unwanted ion is all evicted ion trap from, and the parent ion that will need further to do cascade mass spectrometry is retained in the ion trap.Next, adopt the method for physics or chemistry to make to continue to keep and be stored in parent ion generation dissociation reaction in the ion trap, generate fragmention, or be called the daughter ion.Analyze the mass spectrum result of daughter ion, can obtain the composition of daughter ion.Can further infer the The Nomenclature Composition and Structure of Complexes of parent ion at last according to the composition of daughter ion.
The method that another kind is used for the parent ion selection is to carry out with the quadrupole rod massenfilter.Its detailed process is, the central area of the sample ions introducing quadrupole rod massenfilter that earlier ion gun is produced, then the operating voltage of quadrupole mass filter is arranged to certain numerical value, make the parent ion have only chosen mass-to-charge ratio can be stably by quadrupole rod ion massenfilter and arrive next reaction unit, and remaining ion is all because under the condition of setting in advance, and its motion state is unstable and can not pass through quadrupole rod ion massenfilter.The parent ion selected through the quadrupole rod massenfilter generally is introduced in the follow-up ion reaction chamber, in the quadrupole ion collision cell, carries out the ionic dissociation reaction and generates fragmention, or be called the daughter ion.Analyze the mass spectrum result of daughter ion, obtain the composition of daughter ion, can further infer the The Nomenclature Composition and Structure of Complexes of parent ion.
Can see from above-mentioned two kinds of parent ion systems of selection commonly used: no matter be to use ion trap, still select parent ion, all can only select and keep a parent ion, and remaining ion all must be wasted at every turn with the quadrupole rod massenfilter.That is to say, in experimentation, can only carry out cascade mass spectrometry to a parent ion, and remaining ion can only slattern all at every turn.Therefore, if will carry out cascade mass spectrometry, must constantly repeat above-mentioned experimentation to a plurality of compositions in the sample.Seldom the material composition analysis of sample will be very difficult for having only for this.
The analytical approach that also has some other research tandem mass spectrometry is as realizing the dissociating of parent ion and the composition of further assay products daughter ion in flight time mass spectrum.But similarly, also can only obtain the daughter ion result of a material composition at every turn.
In the patent No. was 200410024946.8 Chinese invention patent, the inventor gave the method that a kind of many linear ion traps arranged side by side that make up with printed-wiring board (PWB) realize the ion cascade mass spectrometries.The method that provides according to this invention, in the multistage linear ion trap systems that makes up with printed-wiring board (PWB), the all samples ion that ion gun is produced is all introduced and is stored in first ion trap earlier, then, select an interested parent ion, from the slit of processing on an electrode of ion trap, evict this ion from first ion trap, and introduce in second ion trap and store.Then, adopt physics or chemical method to make and be stored in second parent ion generation dissociation reaction in the ion trap, generate fragmention.Analyze the mass spectrum result of daughter ion, can obtain the composition of daughter ion.There is not ion chosen and that evicted from first ion trap to be retained in first ion trap with continuing.If desired, can from continue to be stored in the ion first ion trap, select next interested parent ion, and this ion is transferred to from first trap in second ion trap stores.Then, make with physics or chemical method equally and be stored in second parent ion generation dissociation reaction in the ion trap this moment, generate fragmention.Can analyze the mass spectrum result of the daughter ion of parent ion production thus equally, obtain their composition.Similarly, there are not all the other chosen ions to be retained in first ion trap with continuing.In the experimentation, can repeatedly repeat above-mentioned parent ion selectivity transmission-parent ion as required and dissociate-the daughter ion analytic process, up to obtaining needed full detail.According to this invention, can also from second ion trap, select interested certain daughter ion.This ion evicted from second ion trap and introduce in the 3rd ion trap store.Then, adopt physics or chemical method to make and be stored in the 3rd the daughter ion generation dissociation reaction in the ion trap, generate littler fragmention.Analyze the mass spectrum result of these littler fragmentions, can obtain their composition.There is not ion chosen and that evicted from second ion trap to be retained in second ion trap with continuing.Similarly, can use the same method and step the interested daughter ion of the next one is made cascade mass spectrometry.Can and connect together a plurality of linear ion traps, utilize this a plurality of linear ion trap systems, can realize the multiple tracks of ion, multiple cascade mass spectrometry.Though having provided, this patent utilize a plurality of ion traps that link together to carry out the method for cascade mass spectrometry, but do not provide the specific implementation method of the quality selectivity transmission of ion between the adjacent ions trap, particularly do not have to provide and make the ion of certain mass-to-charge ratio from an ion trap, be evicted from, and be stored in concrete voltage conditions and parameter change procedure in the next ion trap effectively by selectivity.
In the patent No. is in the United States Patent (USP) of US6483109B1, and the inventor has provided the method that realizes the tandem ion mass spectrometry with the linear ion trap array of resonance.According to this invention, several linear ion traps are axial along they, link together.In experimentation, the ion that is produced by a pulsed ion source is introduced in the ion trap array, and is stored in one of them ion trap.Then can from the numerous ions that are stored in this ion trap, select a kind of parent ion of mass-to-charge ratio as required, from then on ion trap axially evict this ion trap from, and from axially be incorporated into second ion trap, store.Do not use for follow-up experiment and there is chosen and dispossessed ion still to be continued to be stored in the original ion trap.Owing to a plurality of linear ion traps can be linked together as stated above, make ion transmit and take place dissociation reaction in different linear ion traps.Though having proposed a kind of utilization, this patent carries out the ion transfer between the different ions trap and the method for tandem ion analysis by the linear ion trap of a plurality of resonance that axially links together, but, because the method that this patent proposes to utilize axial resonance is transferred to the ion of extra fine quality the next ion trap from an ion trap, and linear ion trap is if make its internal electric field prolong axial formation resonance field, and then the length of this ion trap must be suitable with its width dimensions radially.That is to say that the length of a harmonic ions trap will be very limited, so its ion storage amount can not satisfy the requirement of big flux cascade mass spectrometry also with smaller.
Summary of the invention
The objective of the invention is to propose a kind ofly utilize a plurality of ion traps to carry out the cascade mass spectrometry method, to solve in the above-mentioned multi-stage ms analysis a kind of ion of mass-to-charge ratio is expelled to problem the next linear ion trap from a linear ion trap selectively, and solve in the above-mentioned multi-stage ms analysis ion with a kind of mass-to-charge ratio and be expelled to the next linear ion trap and in this linear ion trap from a linear ion trap selectively and caught effectively, thereby realize the problem of multi-stage mses such as follow-up cracking, scanning.
The mass spectrometric analysis method that the present invention proposes is a kind of cascade mass spectrometry method that has quality optionally to carry out ion transfer between a plurality of ion traps, comprises the following steps:
(1) in first ion trap, produces radio frequency capture electric field, in order to catch the ion of multiple mass-to-charge ratio based on quadrupole field;
(2) in first ion trap, produce, make the ion of a certain mass-to-charge ratio be subjected to reaching bigger motional amplitude in direction in resonance excitation along the dipole excitation alternating electric field of the certain frequency of the rectilinear direction that connects an ion trap center, first ion trap center to the second;
(3) further in dipole excitation alternating electric field particular phases, in first ion trap, produce and discharge impulse electric field, make the above-mentioned ion that reaches a certain mass-to-charge ratio of bigger motional amplitude discharge and enter in second ion trap, and the ion of other mass-to-charge ratioes is still stayed in first ion trap;
(4) in second ion trap, produce the radio frequency capture electric field, above-mentioned ion or its product ion that enters second ion trap is hunted down at second ion trap electric field.
Among the present invention, the described generation radio frequency capture of step (4) electric field, also can further adopt the mode of superimposed pulse retarding field, specifically, be included in the ion of the multiple mass-to-charge ratio of first ion trap IT, produce the dipole excitation alternating electric field, make the ion of a certain mass-to-charge ratio be subjected to resonance excitation and reach bigger motional amplitude, further certain particular phases in first ion trap, produce and discharge impulse electric field, the above-mentioned ion that reaches a certain mass-to-charge ratio of bigger motional amplitude is discharged in second ion trap, and in second ion trap, the superimposed pulse retarding field reduces the above-mentioned ion kinetic energy that enters second ion trap, is caught by the electric field of second ion trap.
Among the present invention, in described second ion trap, also can further adopt the mode of injecting collision gas, specifically, be included in the ion of the multiple mass-to-charge ratio of first ion trap IT, produce the dipole excitation alternating electric field, make the ion of a certain mass-to-charge ratio be subjected to resonance excitation and reach bigger motional amplitude, and then in first ion trap certain particular phases, produce and discharge impulse electric field, the above-mentioned ion that reaches a certain mass-to-charge ratio of bigger motional amplitude is discharged in second ion trap, and further, in second ion trap, inject collision gas, make the above-mentioned ion that enters second ion trap reduce kinetic energy, caught by the electric field of second ion trap because of collision.
Among the present invention, in described second ion trap, also can further adopt the mode of injecting collision gas, with the ion cracking that causes entering through above-mentioned steps.Specifically, be included in the ion of the multiple mass-to-charge ratio of first ion trap IT, produce the dipole excitation alternating electric field, make the ion of a certain mass-to-charge ratio be subjected to resonance excitation and reach bigger motional amplitude, and then in first ion trap certain particular phases, produce and discharge impulse electric field, the above-mentioned ion that reaches a certain mass-to-charge ratio of bigger motional amplitude is discharged in second ion trap, and further, in second ion trap, inject collision gas, make the above-mentioned ion that enters second ion trap because of collision cracking take place, at least a product ion is caught by the electric field of second ion trap after the cracking.
Among the present invention, described first ion trap and second ion trap can be the linear ion traps, and the substantially parallel placement of the axis of two traps has groove between two traps, can make ion transfer arrive the other side.Particularly, the present invention proposes two linear ion traps side by side of a kind of usefulness are optionally transmitted ion between ion trap method, be included in the alternating electric field that excites that produces certain frequency in first ion trap, make the ion of a certain mass-to-charge ratio be subjected to resonance excitation and reach bigger motional amplitude, exciting the alternating electric field particular phases, produce and discharge impulse electric field, the above-mentioned ion that reaches a certain mass-to-charge ratio of bigger motional amplitude is discharged in second ion trap by the groove between ion trap, and the ion of other mass-to-charge ratioes is still stayed in first ion trap; In second ion trap, produce the radio frequency capture electric field simultaneously, above-mentioned ion or its product ion that enters second ion trap is hunted down second ion trap.
Among the present invention, the described alternating electric field that excites can be dipole recurrent pulses alternating electric fields, and it can make a certain specific mass-to-charge ratio ion of transmission effectively be excited on the direction of transmission.
In the method for above-mentioned whole cascade mass spectrometries, wherein the electric field intensity of dipole excitation is enough to make the ion of above-mentioned selected mass-to-charge ratio to be subjected to resonance excitation, its motional amplitude generally should surpass ion trap field radius half so that utilize non-linear characteristics and other ion isolation of evicting the high-speed pulse electric field from, the details of each method sees embodiment and application example for details.
Another aspect of the present invention proposes a kind of ion storage and the device that separates, and comprises:
The linear ion trap memory block of at least two lateral communications placed side by side;
Make in the ion storage district voltage source device that produces the radio frequency capture electric field that is used to catch ion;
Be used to be superimposed upon voltage source and the coupling device of first ion storage district generation to the dipole alternating electric field of the selective resonance excitation of mass-to-charge ratio, and
Be used for being expelled to direction the pulse voltage generating means of the high-speed pulse electric field in second ion storage district perpendicular to ion storage district axis at the ion that first ion storage district generation will be excited.
Last the present invention also proposes further to comprise in order to produce a kind of like this ion storage of pulse voltage generating means of the high-speed pulse electric field that makes ion retardation and the device of analysis second memory block.
The present invention provides carries out with two or more ion strap mass analyzers that link together that sample ions is separated and the apparatus and method of cascade mass spectrometry, its biggest advantage is, the first, a kind of new material composition separation method and specific implementation process are provided.Make in this way, can be more efficient, more accurate and more quickly sample is carried out component separating; The second, can improve the sensitivity and the analysis efficiency of cascade mass spectrometry.It is different from and existingly can only keeps a kind of parent ion and make cascade mass spectrometry, and the method that other losses of ions must be fallen.Make cascade mass spectrometry but select a kind of ion earlier, and other is continued to be stored in the ion trap, use in the follow-up cascade mass spectrometry treating.The 3rd, because the ion trap mass spectrometer that can use printed-wiring board (PWB) to make, its instrument production cost also will greatly reduce.
Description of drawings
Fig. 1: four utmost point trap mass analyzer synoptic diagram of being formed by four bar type electrodes (prior art).
Fig. 2: four utmost point trap mass analyzer synoptic diagram of being formed with the printed wire plate electrode (prior art).
Fig. 3: with two experimental system schematic diagrams that are used for ion isolation and cascade mass spectrometry that linear ion trap mass spectrometer is formed of printed-wiring board (PWB) structure.
Fig. 4: the ion that obtains by computer simulation draws (4A) and ion is caught (4B) energy needed-phase diagram by second trap.Wherein, be the ion energy distribution that ejects from ion trap and the graph of a relation of At time of eject ion trap radio frequency constraint field phase (4A), (4B) for can by ion trap catch optimum outside when injecting kinetic energy and injecting the ion trap radio frequency fetter the graph of a relation of field phase.
Fig. 5: with the electric signal systematic schematic diagram of ion selectivity transmission between two linear ion traps of printed-wiring board (PWB) structure.
Fig. 6: pulse voltage Pulse1, the variation relation figure of Pulse2 and Pulse3 and time.
Fig. 7: the four polar curve shape ion strap mass analyzer system schematic that provide with the present invention.
Fig. 8: the mass analyzer system synoptic diagram that the four polar curve shape ion traps that provide with the present invention are connected with time of-flight mass spectrometer and formed.
Fig. 9: the mass analyzer system synoptic diagram that the four polar curve shape ion traps that provide with the present invention are connected with time of-flight mass spectrometer and formed.
Number in the figure:
11 be in the hyperbola ion trap non-ejection to wherein one of two hyperboloid electrodes, 12 is wherein one that ejects in the hyperbola ion trap to two hyperboloid electrodes, 13 be in the hyperbola ion trap non-ejection to two hyperboloid electrodes its in addition in one, 14 is wherein another root that ejects in the hyperbola ion trap to two hyperboloid electrodes, 15 be in the hyperbola ion trap non-ejection to the working power of two hyperboloid electrodes, 16 is the working power that ejects in the hyperbola ion trap to two hyperboloid electrodes, and 17 is to eject in the hyperbola ion trap to draw slit to the ion of hyperboloid electrode.
21 for forming the non-ejection of printed-wiring board (PWB) ion trap wherein to two bar printing wiring boards, 22 for forming printed-wiring board (PWB) ion trap ejection wherein to two bar printing wiring boards, 23 for forming the non-ejection of printed-wiring board (PWB) ion trap wherein another piece to two bar printing wiring boards, 24 for forming printed-wiring board (PWB) ion trap ejection wherein another piece to two bar printing wiring boards, 201 for forming the corner strip electrode of the non-ejection of printed-wiring board (PWB) ion trap to a wherein last side of two bar printing wiring boards, 202 for forming the avris strip electrode of the non-ejection of printed-wiring board (PWB) ion trap to a wherein last side of two bar printing wiring boards, 203 for forming wherein the central strip electrode one piece on of the non-ejection of printed-wiring board (PWB) ion trap to two bar printing wiring boards, 204 for forming the non-ejection of printed-wiring board (PWB) ion trap wherein avris strip electrode of going up opposite side to two bar printing wiring boards, 205 for forming the non-ejection of printed-wiring board (PWB) ion trap wherein corner strip electrode of going up opposite side to two bar printing wiring boards, 206 for forming the corner strip electrode of printed-wiring board (PWB) ion trap ejection to a wherein last side of two bar printing wiring boards, 207 for forming the avris strip electrode of printed-wiring board (PWB) ion trap ejection to a wherein last side of two bar printing wiring boards, 208 eject the wherein central strip electrode on to two bar printing wiring boards for forming the printed-wiring board (PWB) ion trap, 209 for forming printed-wiring board (PWB) ion trap ejection wherein avris strip electrode of going up opposite side to two bar printing wiring boards, 210 for forming printed-wiring board (PWB) ion trap ejection wherein corner strip electrode of going up opposite side to two bar printing wiring boards, 211 for forming the corner strip electrode of the non-ejection of printed-wiring board (PWB) ion trap side on wherein another piece of two bar printing wiring boards, 212 for forming the avris strip electrode of the non-ejection of printed-wiring board (PWB) ion trap side on wherein another piece of two bar printing wiring boards, 213 for forming the central strip electrode of the non-ejection of printed-wiring board (PWB) ion trap on wherein another piece of two bar printing wiring boards, 214 for forming the avris strip electrode of the non-ejection of printed-wiring board (PWB) ion trap opposite side on wherein another piece of two bar printing wiring boards, 215 for forming the corner strip electrode of the non-ejection of printed-wiring board (PWB) ion trap opposite side on wherein another piece of two bar printing wiring boards, 216 for forming the corner strip electrode that the printed-wiring board (PWB) ion trap ejects a side on wherein another piece of two bar printing wiring boards, 217 for forming the avris strip electrode that the printed-wiring board (PWB) ion trap ejects a side on wherein another piece of two bar printing wiring boards, 218 for forming the central strip electrode of printed-wiring board (PWB) ion trap ejection on wherein another piece of two bar printing wiring boards, 219 for forming the avris strip electrode that the printed-wiring board (PWB) ion trap ejects opposite side on wherein another piece of two bar printing wiring boards, 220 for forming the corner strip electrode that the printed-wiring board (PWB) ion trap ejects opposite side on wherein another piece of two bar printing wiring boards, 221 for being stored in the ion in the printed-wiring board (PWB) ion trap, 222 draw slit for the ion on the central strip electrode of printed-wiring board (PWB) ion trap one side, and 223 is ion detector.
31 are one of them of two linear ion traps that make up with printed-wiring board (PWB) of connecting together, 32 for two linear ion traps that make up with printed-wiring board (PWB) of connecting together wherein another, 301 produce and are stored in sample ions in one of them linear ion trap for ion gun, 302 are the sample ions that is stimulated and pulse selects quality to evict from from linear ion trap, 303 are the transmission slit between two the linear ion traps that make up with printed-wiring board (PWB) that connect together, 304 for being stored in second ion the linear ion trap from first ion trap ejaculation, 305 for being stored in the selected ion of evicting from that excites of quality in second linear ion trap, 306 for to draw the slit of ion outside trap from second linear ion trap, 307 is ion detector.
501 are to two bar printing wiring boards wherein one of the non-ejection of forming first ion trap in two printed-wiring board (PWB) ion traps connecting together, 502 are to two bar printing wiring boards wherein one of the ejection of forming first ion trap in two printed-wiring board (PWB) ion traps connecting together, 503 is to form the non-ejection of first ion trap in two printed-wiring board (PWB) ion traps that connect together wherein another piece to two bar printing wiring boards, 504 is to form the ejection of first ion trap in two printed-wiring board (PWB) ion traps that connect together wherein another piece to two bar printing wiring boards, shared with second ion trap, 505 are to two bar printing wiring boards wherein one of the non-ejection of forming second ion trap in two printed-wiring board (PWB) ion traps connecting together, 506 is to form the ejection of second ion trap in two printed-wiring board (PWB) ion traps that connect together wherein another piece to two bar printing wiring boards, 507 is to form the non-ejection of second ion trap in two printed-wiring board (PWB) ion traps that connect together wherein another piece to two bar printing wiring boards, 5001 is to form the non-ejection of first ion trap in two printed-wiring board (PWB) ion traps that connect together wherein corner strip electrode of going up non-common side to two bar printing wiring boards, 5002 is to form the non-ejection of first ion trap in two printed-wiring board (PWB) ion traps that connect together wherein avris strip electrode of going up non-common side to two bar printing wiring boards, 5003 are the non-ejection of forming first ion trap in two printed-wiring board (PWB) ion traps connecting together the wherein central strip electrode on to two bar printing wiring boards, 5004 is to form the non-ejection of first ion trap in two printed-wiring board (PWB) ion traps that connect together wherein avris strip electrode of going up common side to two bar printing wiring boards, 5005 is to form the non-ejection of first ion trap in two printed-wiring board (PWB) ion traps that connect together wherein corner strip electrode of going up common side to two bar printing wiring boards, 5006 is to form the corner strip electrode of the ejection of first ion trap in two printed-wiring board (PWB) ion traps that connect together to a wherein last side of two bar printing wiring boards, 5007 is to form the avris strip electrode of the ejection of first ion trap in two printed-wiring board (PWB) ion traps that connect together to a wherein last side of two bar printing wiring boards, 5008 are the ejection of forming first ion trap in two printed-wiring board (PWB) ion traps connecting together the wherein central strip electrode on to two bar printing wiring boards, 5009 is to form the ejection of first ion trap in two printed-wiring board (PWB) ion traps that connect together wherein avris strip electrode of going up opposite side to two bar printing wiring boards, 5010 is to form the ejection of first ion trap in two printed-wiring board (PWB) ion traps that connect together wherein corner strip electrode of going up opposite side to two bar printing wiring boards, 5011 for forming the corner strip electrode of non-ejection non-common side on wherein another piece of two bar printing wiring boards of first ion trap in two printed-wiring board (PWB) ion traps that connect together, 5012 for forming the avris strip electrode of non-ejection non-common side on wherein another piece of two bar printing wiring boards of first ion trap in two printed-wiring board (PWB) ion traps that connect together, 5013 for forming the central strip electrode of non-ejection on wherein another piece of two bar printing wiring boards of first ion trap in two printed-wiring board (PWB) ion traps that connect together, 5014 for forming the avris strip electrode of non-ejection common side on wherein another piece of two bar printing wiring boards of first ion trap in two printed-wiring board (PWB) ion traps that connect together, 5015 for forming the corner strip electrode of non-ejection common side on wherein another piece of two bar printing wiring boards of first ion trap in two printed-wiring board (PWB) ion traps that connect together, 5016 for forming in two printed-wiring board (PWB) ion traps connecting together the corner strip electrode of the shared ejection of two ion traps to a side of printed-wiring board (PWB), 5017 for forming in two printed-wiring board (PWB) ion traps connecting together the avris strip electrode of the shared ejection of two ion traps to a side of printed-wiring board (PWB), 5018 for forming in two printed-wiring board (PWB) ion traps connecting together the central strip electrode of the shared ejection of two ion traps to printed-wiring board (PWB), 5019 for forming in two printed-wiring board (PWB) ion traps connecting together the avris strip electrode of the shared ejection of two ion traps to the opposite side of printed-wiring board (PWB), 5020 for forming in two printed-wiring board (PWB) ion traps connecting together the shared ejection of two ion traps to the corner of the opposite side of printed-wiring board (PWB) strip electrode, 5021 is to form the non-ejection of second ion trap in two printed-wiring board (PWB) ion traps that connect together wherein corner strip electrode of going up common side to two bar printing wiring boards, 5022 is to form the non-ejection of second ion trap in two printed-wiring board (PWB) ion traps that connect together wherein avris strip electrode of going up common side to two bar printing wiring boards, 5023 are the non-ejection of forming second ion trap in two printed-wiring board (PWB) ion traps connecting together the wherein central strip electrode on to two bar printing wiring boards, 5024 is to form the non-ejection of second ion trap in two printed-wiring board (PWB) ion traps that connect together wherein avris strip electrode of going up non-common side to two bar printing wiring boards, 5025 is to form the non-ejection of second ion trap in two printed-wiring board (PWB) ion traps that connect together wherein corner strip electrode of going up non-common side to two bar printing wiring boards, 5026 for forming the corner strip electrode of ejection side on wherein another piece of two bar printing wiring boards of second ion trap in two printed-wiring board (PWB) ion traps that connect together, 5027 for forming the avris strip electrode of ejection side on wherein another piece of two bar printing wiring boards of second ion trap in two printed-wiring board (PWB) ion traps that connect together, 5028 for forming the central strip electrode of ejection on wherein another piece of two bar printing wiring boards of second ion trap in two printed-wiring board (PWB) ion traps that connect together, 5029 for forming the avris strip electrode of ejection opposite side on wherein another piece of two bar printing wiring boards of second ion trap in two printed-wiring board (PWB) ion traps that connect together, 5030 for forming the corner strip electrode of ejection opposite side on wherein another piece of two bar printing wiring boards of second ion trap in two printed-wiring board (PWB) ion traps that connect together, 5031 for forming the corner strip electrode of non-ejection common side on wherein another piece of two bar printing wiring boards of second ion trap in two printed-wiring board (PWB) ion traps that connect together, 5032 for forming the avris strip electrode of non-ejection common side on wherein another piece of two bar printing wiring boards of second ion trap in two printed-wiring board (PWB) ion traps that connect together, 5033 for forming the central strip electrode of non-ejection on wherein another piece of two bar printing wiring boards of second ion trap in two printed-wiring board (PWB) ion traps that connect together, 5034 for forming the avris strip electrode of non-ejection non-common side on wherein another piece of two bar printing wiring boards of second ion trap in two printed-wiring board (PWB) ion traps that connect together, 5035 for forming the corner strip electrode of non-ejection non-common side on wherein another piece of two bar printing wiring boards of second ion trap in two printed-wiring board (PWB) ion traps that connect together, 5036 are the transmission slit between two the linear ion traps that make up with printed-wiring board (PWB) that connect together, 5037 for drawing the slit of ion outside trap in two the linear ion traps with the printed-wiring board (PWB) structure that connect together from second linear ion trap, 5038 produce and are stored in the sample ions in first ion trap in two printed-wiring board (PWB) ion traps that connect together for ion gun, 5039 is to be evicted and be stored in from second ion in the linear ion trap by quality selective excitation to reach by its ion that dissociates from first ion trap, 5040 is ion detector, 550 is the high voltage pulse signal generator, and 551 for selecting the high-pressure electronic switch of also isolated high-voltage pulse and radio frequency.
61 pull out the sequential that is added in the shared pulse voltage of ejection on the central strip electrode of printed-wiring board (PWB) of two ion traps when impulse method is drawn ion for adopting, 62 for adopting the sequential of pulling out the pulse voltage of two non-ejections on the central strip electrode of printed-wiring board (PWB) that is added in second ion trap when impulse method is drawn ion, and 63 for adopting the sequential of pulling out the pulse voltage of another piece ejection on the central strip electrode of printed-wiring board (PWB) that is added in second ion trap when impulse method is drawn ion.
71 is the forvacuum chamber, 72 is level quality analysis chamber, back vacuum chamber, 701 is the sample ions source, 702 is the working power in sample ions source, 703 primary sample ions for the generation of sample ions source, 704 is the vacuum sample intake, 705 is the ion optics of forevacuum cylinder, 706 is the working power of the ion optics of forevacuum cylinder, 707 for connecting the osculum in prime chamber and quality analysis chamber, 708 axial ion intakes for first ion trap in two linear ion traps that connect together, 709 are first ion trap in two linear ion traps that connect together, 710 are second ion trap in two linear ion traps that connect together, 711 working power combinations for two linear ion traps connecting together, 712 for injecting and be stored in the ion flow of first ion trap, 713 are the transmission slit between two linear ion traps that connect together, 714 is to be evicted and be stored in from second ion in the linear ion trap by quality selective excitation to reach by its ion that dissociates from first ion trap, 715 for drawing the slit of ion outside trap from second linear ion trap, 716 is ion detector, 717 for extracting the vacuum pump system of forvacuum chamber, and 718 for extracting the vacuum pump system of level quality analysis chamber, back vacuum chamber.
81 is the forvacuum chamber, 82 is level quality analysis chamber, back vacuum chamber, 801 is the sample ions source, 802 is the working power in sample ions source, 803 primary sample ions for the generation of sample ions source, 804 is the vacuum sample intake, 805 is the ion optics of forevacuum cylinder, 806 is the working power of the ion optics of forevacuum cylinder, 807 for connecting the osculum in prime chamber and quality analysis chamber, 808 axial ion intakes for first ion trap in three linear ion traps that connect together, 809 are first ion trap in three linear ion traps that connect together, 810 working power combinations for first ion trap in three linear ion traps that connect together, 811 working power combinations for second ion trap in three linear ion traps that connect together, 812 for injecting and be stored in the ion flow of first ion trap, 813 are the transmission slit between the second ion trap in three linear ion traps that connect together, 814 are second ion trap in three linear ion traps that connect together, 815 is to be evicted and be stored in from second ion in the linear ion trap by quality selective excitation to reach by its ion that dissociates from first ion trap, 816 are the transmission slit between the two or three ion trap in three linear ion traps that connect together, 817 are the 3rd ion trap in three linear ion traps that connect together, 818 is to be evicted and be stored in from the 3rd ion in the linear ion trap by quality selective excitation to reach by its ion that dissociates from second ion trap, 819 for evicting the slit of ion from outside trap from the 3rd ion trap, 820 is ion detector, 821 for extracting the vacuum pump system of forvacuum chamber, and 822 for extracting the vacuum pump system of level quality analysis chamber, back vacuum chamber.
91 is first ion trap in the linear ion trap of rectangle in parallel, 92 is second ion trap in the linear ion trap of rectangle in parallel, 93 is reflection type flight time mass spectrometer, 901 for injecting and be stored in the ion flow of first ion trap, 902 is the ion of being evicted from by quality selective excitation from first ion trap, 903 are the transmission slit between two linear ion traps that connect together, 904 is that the ion of evicting from that is stored in second linear ion trap reaches by its daughter ion that dissociates, 905 for evicting the slit of ion from outside trap from second ion trap, 906 for arriving the ion in time of-flight mass spectrometer ion repulsion district, 907 is the ion repulsion district of time of-flight mass spectrometer, and 908 is the plane ion detector.
Embodiment
As one of embodiments of the present invention, Fig. 3 has provided two experimental system schematic diagrams that are used for cascade mass spectrometry that linear ion trap mass spectrometer is formed that make up with printed-wiring board (PWB).Wherein 31 and 32 be respectively two the linear ion traps that connect together, the xsect that one of them has or two all have rectangle with the printed-wiring board (PWB) structure.The sample ions 301 that ion gun produces is introduced in the ion trap 31 and is stored in.The 302nd, chosen mass-to-charge ratio is certain parent ion of m/z, they are excited under the effect of one group of specific AC power supplies, when the intrinsic motion frequency of the parent ion of the frequency of AC power supplies and this mass-to-charge ratio is close, the amplitude of ion can increase sharply, and can evict ion trap 31 from from the aperture groove 303 on the two trap partition walls and enter in the ion trap 32.
But can be subjected to sufficient acceleration at this process intermediate ion of evicting from, the ion that arrives at ion trap 32 has very big kinetic energy, can't be caught effectively by trap 32.Fig. 4 A provided the kinetic energy and the relation of HF voltage phase place when entering when ion enters ion trap 32, and Fig. 4 B has provided that ion might be caught desired kinetic energy by ion trap 32 and the relation of the HF voltage phase place when entering.As seen reality differs greatly with requirement, and ion can't be caught by trap 32.Moreover because discharge process has certain randomness, the ion that mass-to-charge ratio is all m/z also not necessarily is discharged from the cycle of same eigenvibration, has further increased the complicacy of effectively catching in trap 32.
In order to address this problem, the present invention has introduced high-voltage pulse power source, shown among Fig. 5 550.Usually it can cooperate the function that realizes so-called high-voltage pulse by high-voltage power supply with high-voltage switch gear.Its output is added at least one electrode of ion trap 31, in the particular phases of RF electric field, selected and resonance excitation suddenly is discharged in second trap 32 with impulse form to the ion of certain amplitude.Because being the same phase place of ion in the cycle of same eigenvibration of m/z, all mass-to-charge ratioes promoted by brute force, time and phase place that they arrive trap 32 also differ less, its kinetic energy that carries just can be reduced by a reverse Pulse Electric place retardance, and these ions just can be caught by the radio frequency capture electric field of trap 32.
Below be example just with two digital line shape PCB ion traps, specifically describe this transmission course.Fig. 5 has provided the experimentation synoptic diagram of forming with two linear ion trap mass spectrometers that is used for ion isolation and cascade mass spectrometry.51 and 52 represent the cross section structure figure of two linear ion traps that link to each other respectively, are X-axis with the straight line at an ion trap 52 centers, center to the second that connect ion trap 51.501,502,503 and 504 for constituting four printed wire plate electrodes of ion trap 51; 504,505,506 and 507 for constituting four printed wire plate electrodes of ion trap 52.Obviously, electrode 504 is shared by two ion traps, and the purpose of doing like this has two: the one, and can be so that the structure of ion trap becomes simpler; The 2nd, make that the move distance of ion between two ion traps is shorter, can improve ion transmission efficiency.Each printed wire plate electrode is made up of five littler strip electrodes again.As electrode 501 by five littler strip electrodes 5001,5002,5003,5004 and 5005 compositions; Electrode 502 is by five littler strip electrodes 5006,5007,5008,5009 and 5010 compositions; Electrode 503 is by five littler strip electrodes 5011,5012,5013,5014 and 5015 compositions; Electrode 504 is by five littler strip electrodes 5016,5017,5018,5019 and 5020 compositions.Electrode 505 is by five littler strip electrodes 5021,5022,5023,5024 and 5025 compositions; Electrode 506 is by five littler strip electrodes 5026,5027,5028,5029 and 5030 compositions; Electrode 507 is by five littler strip electrodes 5031,5032,5033,5034 and 5035 compositions.
When above-mentioned two ion traps were in running order, its power supply connected mode was: electrode 5001,5006, and 5010,5011,5025,5026,5030,5035,5005,5016,5021,5015,5020 and 5031 link together ground connection.Electrode 5003,5013,5023 and 5033 are joined together, and load positive HF voltage+V, and electrode 5018 and 5028 is joined together, and loads negative HF voltage-V.Electrode 5002,5004,5012 and 5014 are joined together, and load positive high frequency dividing potential drop+α V (0＜α＜1), electrode 5022,5024,5032 and 5034 are joined together, and also load positive high frequency dividing potential drop+α V (0＜α＜1), electrode 5017,5019 is joined together, and loads negative high frequency dividing potential drop-α V (0＜α＜1).Electrode 5008 is except loading negative HF voltage-V, and also will superpose is used for the auxiliary AC voltage of resonance excitation, and this can be come in by transformer 560 couplings, and electrode 5008 also will be linked on the pulsed high voltage generator 550.And electrode 5007 and 5009 will also be got certain proportion (the negative HF voltage of (0＜α＜1), auxiliary AC voltage and high voltage pulse by the capacitance-resistance dividing potential drop.
Before high voltage pulse arrives, in the central area of ion trap 51 and 52, will produce, and contain the ion binding electric field of a small amount of other high-order electric field compositions based on quadripolar electric field.The ion 5038 that enters ion trap will be stored in the ion trap under these effect of electric field.
In addition, can also on above-mentioned all electrodes, promptly load a direct current voltage up to electrode 5035, escape vertically to avoid ion according to the needs of experiment situation from electrode 5001.
In experimentation, when the ion that need be m/e, when evicting ion trap 51 from, on electrode 5008, load an auxiliary alternating voltage AC as 5039 with certain selected mass-to-charge ratio, obtain the auxiliary alternating voltage α AC (0＜α＜1) that decays on 5007 and 5009 naturally.The effect of auxiliary alternating voltage AC and α AC be the ion 5040 that certain selected mass-to-charge ratio is m/e is excited in ion trap and along directions X away from the ion trap central area, and keep other not have chosen ion not to be subjected to the influence of this auxiliary alternating voltage substantially, or only be subjected to less influence and keep the ion trap central area.The purpose of doing so obviously is to wish with chosen mass-to-charge ratio to be that the ion of m/e and other do not have chosen ion isolation to open.
Next will carry out the process that ion is drawn, when ion chosen and be excited after, on electrode 5008, load one prior seclected time width pulse voltage Pulse1.Simultaneously, it is identical to obtain time response on electrode 5007 and 5009, but the pulse voltage α Pulse1 that decayed (0＜α＜1).The effect of above-mentioned voltage causes generating in the ion trap 51 direction and points to X, and size is the non-linear release impulse electric field that successively decreases along directions X, ion selected and that be excited " is pushed away " by the slit on the electrode 504 5036 go out ion trap 51.Because this impulse electric field is non-linear, unawakened ion receives that its effect is very little, is not enough to be evicted from ion trap 51 by it.In order to prevent high-voltage pulse signal damage RF power supply, available high-voltage switch gear 551 is isolated in the said process.
Also can evict ion trap 51 from another kind of pulse voltage ion that will select and that be excited, promptly on electrode 5018, load one prior seclected time width pulse voltage-Pulse1.Simultaneously, on electrode 5017 and 5019, load identical time response, but the pulse voltage that decayed-α Pulse1 (0＜α＜1).At this moment, above-mentioned pulse voltage-Pulse1 and-effect of α Pulse1 is to draw impulse electric field ion 5039 that will select and that be excited and " drawn " by the slit on the electrode 504 5036 and go out ion trap 51 in order to produce one.
Also can evict ion trap 51 from the auxiliary ion that will select and that be excited of another kind of pulse voltage, promptly on electrode 5003 and 5013, load one prior seclected time width satellite pulse voltage-Pulse AuxSimultaneously, on electrode 5002,5004,5012 and 5014, load identical time response, but the satellite pulse of decaying voltage-α Pulse Aux(0＜α＜1).At this moment, above-mentioned satellite pulse voltage-Pulse AuxWith-α Pulse AuxEffect be in order to produce satellite pulse quadripolar electric field and above-mentioned release or to draw that will select and that be excited the in the lump ion 5039 of impulse electric field and evict ion trap 51 from by the slit on the electrode 504 5036, this pulse quadripolar electric field can effectively improve the direction homogeneity of evicting ion from, and promote and to evict the non-linear of electric field from so that evict the voltage amplitude of pulse from and descend, to reduce to influence of retaining ion and manufacture difficulty and the cost that reduces the pulse power.
After ion is evicted from ion trap 51, on electrode 5023 and 5033, load another pulse voltage Pulse2, simultaneously at electrode 5022,5024, load identical time response on 5032 and 5034, but the pulse voltage α Pulse2 that decayed (0＜α＜1).On electrode 5028, load the pulse voltage Pulse3 with the identical time response of pulse voltage Pulse2, with the identical time response of loading on electrode 5027 and 5029, but the pulse voltage α Pulse3 that decayed (0＜α＜1).Above-mentioned pulse voltage Pulse2, α Pulse2, the effect of Pulse3 and α Pulse3 is in order to reduce kinetic energy selected and that evicted from the ion 5039 of ion trap 51, so that they can be held onto by the electric field in the trap 52 and be stored in the ion trap 52.
After ion is stored in the ion trap 52, can do further analysis and research to ion, as the method with physics or chemistry, as so-called collision induced dissociation, photodissociation or electron capture dissociate etc., make it to dissociate, and generate fragmention, or are called the daughter ion.Also can study chemical reaction of they and other material etc.
At last, can be by on electrode 5028, loading an auxiliary AC power AC2, with simultaneously identical with 5029 characteristics of last load time at electrode 5027, but the auxiliary AC power α AC2 (0＜α＜1) that decayed, realization is excited successively according to the difference of its mass-to-charge ratio product ion in the ion trap 52 and is evicted from ion trap 52 by the slit on the electrode 506 5037.5040 is one to be placed near the ion detector the slit 5039, and its effect is to receive and amplify the ion signal of being evicted from by slit 5039, the quality analysis process of the final ion of realizing.
By ion-optical emulation, we can find needed voltage of above-mentioned ion transfer process and sequential relationship.Push away the pulse example with one below and illustrate that ion is stored in ion trap 51, quality selective excitation and by being evicted from 51, ion is decelerated in ion trap 52 and ion is stored in process in 52.
Suppose to be under the thermal equilibrium state, and mass-to-charge ratio is m/e=117 that 119,121 ion is introduced in the ion trap 51 and is stored.
Be carried in electrode 5003,5013, the ion trap driving switch voltage amplitude on 5023 and 5033 is fixed as 150V (peak-to-peak value), and be 0.87us square wave V start cycle, and promptly frequency is 1.154MHz.Next step makes V begin to do the cycle incremental scan, and sweep velocity is that the cycle of per 21 all after date power supplys increases 0.5ns.The frequency that is carried in the auxiliary alternating voltage AC on the electrode 5008 remains 1/3 of ion trap driving frequency, and amplitude is 0.8V (peak-to-peak value).When 9950.00us, mass-to-charge ratio is that the ion of m/e=119 has reached bigger amplitude, and is positioned at trap by electrode 5,008 one sides, and additional Pulse1 obtains α Pulse1 by attenuator circuit simultaneously on 5007,5009 on electrode 5008.The pulse height of Pulse1 is 130V, and width is 300ns, and the rise time is 36ns.Simultaneously Pulse2 also when 9950.00ns, is attached on the electrode 5023,5033, and 5022,5024,5032 and 5034 enclose α Pulse2 by attenuator circuit, and the pulse height of Pulse2 is 500V, and width is 1150ns, and the rise time is 36ns.Pulse3 also when 9950.00ns, is attached on the electrode 5028, and by the additional α Pulse3 of attenuator circuit, the pulse height of Pulse3 is 500 on the while 5027,5029, and width is 1500ns, and the rise time is 36ns.Above-mentioned used radio frequency exchanges dividing potential drop α value and is 66.9%.
Through top step, about 80% the mass-to-charge ratio mass-to-charge ratio that to be 119 ion enter trap about 2,75% from trap 1 is that 119 ion is stored in trap 52.And being 117 and 121 ion, mass-to-charge ratio still is retained in the trap 51.
Can draw the pulse example to illustrate that ion is stored in ion trap 51 with one equally, quality selective excitation and evicted from 51, ion is decelerated in ion trap 52 and ion is stored in process in 52.
To last similar, be carried in electrode 5003,5013, the ion trap driving switch voltage amplitude on 5023 and 5033 is fixed as 150V (peak-to-peak value), and be 0.87us square wave V start cycle, and promptly frequency is 1.154MHz.Next step makes V begin to do the cycle incremental scan, and sweep velocity is that the cycle of per 21 all after date power supplys increases 0.5ns.The frequency that is carried in the auxiliary alternating voltage AC on the electrode 5008 remains 1/3 of ion trap driving frequency, and amplitude is 0.8V (peak-to-peak value).When 9951.06us, mass-to-charge ratio is that the ion of m/e=119 has reached bigger amplitude, and is positioned at trap by electrode 5,018 one sides, additional Pulse1 on electrode 5018 at this moment, and the pulse height of Pulse1 is-100V, and width is 300ns, and the rise time is 36ns.On 5017,5019, obtain α Pulse1 by attenuator circuit.Simultaneously Pulse2 also when 9951.06ns, is attached on the electrode 5023,5033, and 5022,5024,5032 and 5034 enclose α Pulse2 by attenuator circuit, and the pulse height of Pulse2 is 420V, and width is 1200ns, and the rise time is 36ns.Pulse3 also when 9951.06ns, is attached on the electrode 5028, and by the additional α Pulse3 of attenuator circuit, the pulse height of Pulse3 is 500V on the while 5027,5029, and width is 1500ns, and the rise time is 36ns.
The voltage method that is loaded on all the other each electrodes as previously described.In this example, used ion trap drives the HF voltage dividing potential drop, the auxiliary dividing potential drop that exchanges, and the attenuation coefficient α value of pulse voltage dividing potential drop is 66.9%.
Fig. 6 has provided respectively and has drawn pulse voltage Pulse1, the variation relation of deceleration pulse Pulse2 and Pulse3 and time.
After top experimentation was finished, the mass-to-charge ratio that the ion that about mass-to-charge ratio of about 80% is m/e=119 enters ion trap about 52,50% from ion trap 51 was that 119 ion is bound in the ion trap 52 and is stored.And being the ion of m/e=117 and 121, mass-to-charge ratio still is retained in the ion trap 51.
After parent ion 5039 enters ion trap 52 and is stored down, can be with the method for physics or chemistry, as so-called collision induced dissociation, photodissociation or electron capture dissociate etc., make parent ion generation dissociation reaction generate the daughter ion.After the dissociation reaction process is finished, the daughter ion can fetter under the effect of voltage and auxiliary AC voltage (not showing out among the figure) at high frequency, is the ion detectors that are placed in aperture 5037 outsides according to the difference of its mass-to-charge ratio by evict ion trap 52.5040 from from aperture (or notch) 5037.It can write down and amplify the ion signal of evicting from from aperture.Further follow-up data is handled record and is promptly obtained needed mass spectrogram.
Application example
Fig. 7 is one of application example of the present invention.Concrete experimentation is: sample ions source 701 produces ion flow 703 under the effect of its working power 702.The ion flow that produces is introduced hole 704 by ion and is introduced in the vacuum chamber 71.705 for being placed in the ion optics in the vacuum chamber, is the quadrupole ion guide bar here.706 is 705 working power.Ion flow is introduced hole 707 by another ion and is entered in the vacuum chamber 72 after ion-optic system 705 effects.
709 and 710 for being placed in two in the vacuum chamber 72 linear ion traps that link together.Promptly be introduced in the ion trap 709 subsequently through 707 ion flows that enter in 72.Ion flow 712 is in bond and store owing to be subjected to the effect of ion trap operating voltage 710 in ion trap 709.
After 709 storage regular hours, can be selected the ion that a kind of mass-to-charge ratio is m/e by ion trap as required at ion flow 712.This kind ion is excited and evicts ion trap 709 under the effect of above-mentioned particular power source combination, and is entered in the next ion trap 710 by slit 713.Similarly, entering ion flow 714 in 710 can be in bond and be stored in this ion trap.And be not excited and all the other ions of evicting from still are retained in the ion trap 709.That is to say that chosen mass-to-charge ratio is that the ion of m/e is by separating in other ion flow.
Next, can make further experimental study, study as tandem mass spectrometry to the ion that is pursued and be stored in the ion trap 710.Promptly the method with physics or chemistry makes its littler ion of generation that dissociates, or is called the daughter ion.The daughter ion that produces can be evicted from from ion trap 710 according to the size of its mass-to-charge ratio under the effect of power supply 711 successively, and arrives ion detector 716 by slit 715.Ion is handled and output by follow-up instrument through 716 records with after amplifying, and promptly obtains needed tandem mass spectrometry research information.
Also can carry out chemical reaction research to the ion 714 that is stored in the ion trap 710.The reaction product that obtains can be evicted from from ion trap 710 successively according to the size of its mass-to-charge ratio equally, and arrives ion detector 716 by slit 715.Ion is handled and output by follow-up instrument through 716 records with after amplifying, and promptly obtains needed tandem mass spectrometry research information.
The vacuum tightness of vacuum chamber 71 is obtained by vacuum pump system 717.The vacuum tightness of vacuum chamber 72 is obtained by vacuum pump system 718.
Generally speaking, ion-optic system, mass of ion analyzer and ion detector all must operate under the vacuum condition.Ion gun is also inequality according to the different desired vacuum condition of its kind.
Fig. 8 is the another application of the invention example.Its ion isolation and cascade mass spectrometry system are made up of three and the linear ion trap that connects together.Its concrete experimentation is: sample ions source 801 produces ion flow 803 under the effect of its working power 802.The ion flow that produces is introduced hole 804 by ion and is introduced in the vacuum chamber 81.805 for being placed in the ion optics in the vacuum chamber, is the quadrupole ion guide bar here.806 is 805 working power.Ion flow is introduced hole 807 by another ion and is entered in the vacuum chamber 82 after ion-optic system 805 effects.
809,814 and 817 for being placed in three in the vacuum chamber 82 linear ion traps that link together.Enter ion flow in 82 with after the ion of ion trap 809 is introduced the hole is introduced in the ion trap 809 through 807.Ion flow 812 is in bond and store owing to be subjected to the effect of ion trap operating voltage 810 in ion trap 809.
After 809 storage regular hours, can be selected the ion that a kind of mass-to-charge ratio is m/e by ion trap as required at ion flow 812.This kind ion is excited and evicts ion trap 809 under the effect of one group of particular power source, and is entered in the next ion trap 814 by slit 813.Similarly, entering ion flow 812 in 809 can be in bond and be stored in this ion trap.And be not excited and all the other ions of evicting from still are retained in the ion trap 809.That is to say that chosen mass-to-charge ratio is that the ion of m/e is by separating in other ion flow.
Next, can make further experimental study, study as tandem mass spectrometry to the ion that is pursued and be stored in the ion trap 814.Promptly the method with physics or chemistry makes its littler ion of generation that dissociates, or is called the daughter ion.
Can further from the daughter ion that produces, select the ion of certain mass-to-charge ratio, and by one group of specific power supply effect, make the daughter ion be selected be excited and evict ion trap 814 from that these are advanced the ion of evicting from 814 and can enter ion by slit 816 and advance in 817 from ion.Similarly, entering ion flow 818 in 817 can be in bond and be stored in this ion trap 817.And be not excited and all the other daughter ions of evicting from still are retained in the ion trap 814.That is to say that chosen mass-to-charge ratio is that the daughter ion of m/e is by separating in other daughter ion flow.
Can make further experimental study to the daughter ion that is stored in the ion trap 817, study as tandem mass spectrometry.Promptly the method with physics or chemistry makes its littler daughter ion of generation that dissociates.
The more boy body ion that generates in ion trap 817 can add under the effect of work power supply outside, is evicted from from ion trap 817 successively according to the size of its mass-to-charge ratio, and arrives ion detector 820 by slit 819.Ion is handled and output by follow-up instrument through 820 records with after amplifying, and promptly obtains needed tandem mass spectrometry research information.
Similarly, also can carry out chemical reaction research to the daughter ion 818 that is stored in the ion trap 817.The reaction product that obtains can be evicted from from ion trap 817 successively according to the size of its mass-to-charge ratio equally, and arrives ion detector 820 by slit 819.Ion is handled and output by follow-up instrument through 820 records with after amplifying, and promptly obtains needed tandem mass spectrometry research information.
The vacuum tightness of vacuum chamber 81 is obtained by vacuum pump system 821.The vacuum tightness of vacuum chamber 82 is obtained by vacuum pump system 822.
Generally speaking, ion-optic system, mass of ion analyzer and ion detector all must operate under the vacuum condition.Ion gun is also inequality according to the different desired vacuum condition of its kind.
Fig. 9 is three of an application example of the present invention.It is by two linear ion traps 91 that are connected in parallel and 92 and reflection type flight time mass spectrometers 93 be cascaded constitute.Concrete experimentation is: the ion flow 901 that is produced by the sample ions source is introduced in the linear ion trap 91 and stores.
After ion flow 901 was stored the regular hours by ion trap 91, can select a kind of mass-to-charge ratio as required was the ion 902 of m/e.This kind ion is excited and evicts ion trap 91 under the effect of aforementioned particular power source, and is entered in the next ion trap 92 by slit 903.Ion stores after being decelerated in 92.And be not excited and all the other ions of evicting from still are retained in the ion trap 91.That is to say that chosen mass-to-charge ratio is that the ion 902 of m/e is by separating in other ion flow.
Next, can make further experimental study, study as tandem mass spectrometry to the ion that is stored in the ion trap 92.Promptly the method with physics or chemistry makes its littler ion of generation that dissociates, or is called the daughter ion.All daughter ions 904 that produce can be evicted from from ion trap 92 under the effect of pulse voltage, and are arrived in the ion repulsion electrode zone 907 of time of-flight mass spectrometer 93 by slit 905.Arrive that ion 906 in 907 is accelerated in time of-flight mass spectrometer and compartment analysis after arrive in the ion detector 908 and be detected.By the ion signal of ion detector 908 record through further amplify and record after, handle and export by follow-up instrument, promptly obtain needed tandem mass spectrometry research information.
Can see from above-described experimental technique and process: use the given technology of the present invention, method and apparatus can be realized the high-level efficiency of ion cascade mass spectrometry, high sensitivity and more convenient.Simultaneously, because can the application structure more simple square ion trap with the printed-wiring board (PWB) making, its instrument cost can be more cheap, and operation and maintenance also can be more simple.

Claims (19)

1 one kinds are carried out the method for cascade mass spectrometry with a plurality of ion traps, comprise the following step:
In first ion trap, produce radio frequency capture electric field, in order to catch the ion of multiple mass-to-charge ratio based on quadrupole field;
In first ion trap, produce, make the ion of a certain mass-to-charge ratio be subjected to resonance excitation and reach bigger motional amplitude in this direction along the dipole excitation alternating electric field of the certain frequency of the rectilinear direction that connects an ion trap center, first ion trap center to the second;
In dipole excitation alternating electric field particular phases, in first ion trap, produce to discharge impulse electric field, the above-mentioned ion that reaches a certain mass-to-charge ratio of bigger motional amplitude is escaped and enter in second ion trap, and the ion of other mass-to-charge ratioes is still stayed in first ion trap;
In second ion trap, produce the radio frequency capture electric field, above-mentioned ion or its product ion that enters second ion trap is hunted down second ion trap.
The method of 2 cascade mass spectrometries according to claim 1 is characterized in that further comprising, and in second ion trap, the superimposed pulse retarding field reduces the above-mentioned ion kinetic energy that enters second ion trap, is caught by the electric field of second ion trap.
The method of 3 cascade mass spectrometries according to claim 1, it is characterized in that further comprising, in second ion trap, inject collision gas, make the above-mentioned ion that enters second ion trap reduce kinetic energy, caught by the electric field of second ion trap because of collision.
The method of 4 cascade mass spectrometries according to claim 1, it is characterized in that further comprising, in second ion trap, inject collision gas, make the above-mentioned ion that enters second ion trap because of collision cracking take place, at least a product ion is caught by the electric field of second ion trap after the cracking.
The method of 5 cascade mass spectrometries according to claim 1 is characterized in that described first ion trap and second ion trap are the linear ion trap, and the substantially parallel placement of the axis of two traps has groove can make ion transfer arrive the other side between two traps.
6 methods of cascade mass spectrometry according to claim 1 or 5, the dipole excitation alternating electric field that it is characterized in that described certain frequency is the recurrent pulses alternating electric field.
7 methods according to the described cascade mass spectrometry of one of claim 1 to 6 is characterized in that the electric field intensity of described wherein dipole excitation is enough to make the ion of above-mentioned selected mass-to-charge ratio to be subjected to resonance excitation surpasses ion trap field radius to motional amplitude half.
8 methods according to the described cascade mass spectrometry of one of claim 2 to 7, at least one is the linear ion trap with rectangular cross section to it is characterized in that described linear ion trap.
9 methods according to the described cascade mass spectrometry of one of claim 2 to 7 is characterized in that described first and second linear ion trap all have rectangular cross section, and by between the one side partition wall that comprises the groove in electrode and the electrode separate.
10 according to Claim 8 or the method for one of 9 described cascade mass spectrometries, it is characterized in that the described borderline electrode of linear ion trap with rectangular cross section is made of insulator or semi-conductive on-chip P.e.c..
11 methods according to the described cascade mass spectrometry of one of claim 1 to 10 is characterized in that described discharge impulse electric field is by the release electric field that produces away from the pulse voltage at least one electrode of second ion trap one side that is positioned at that is added in first ion trap
12 methods according to the described cascade mass spectrometry of one of claim 1 to 10 is characterized in that described discharge impulse electric field is by being added in the electric field of drawing that pulse voltage at least one electrode between first ion trap and second ion trap produces.
13 methods according to the described cascade mass spectrometry of one of claim 1 to 10 is characterized in that described discharge impulse electric field comprises the quadrupole field that the pulse voltage at least one electrode that is added in first ion trap produces.
The method of 14 cascade mass spectrometries according to claim 6 is characterized in that further comprising:
Scanning the frequency of above-mentioned radio frequency capture electric field or intensity makes in second ion trap ion be subjected to resonance excitation according to mass-to-charge ratio and shines ion detector outside the trap.
The method of 15 cascade mass spectrometries according to claim 6 is characterized in that describedly further comprising:
Produce the dipole excitation alternating electric field in second ion trap, the frequency that scans above-mentioned dipole excitation alternating electric field makes in second ion trap ion be subjected to resonance excitation successively according to mass-to-charge ratio and shines ion detector outside the trap.
The method of 16 cascade mass spectrometries according to claim 6 is characterized in that describedly further comprising:
Outside second ion trap, Time-of flight analyzer is set;
In second ion trap, produce pulse and draw electric field, make the ion in second ion trap introduce Time-of flight analyzer, according to flight time acquisition mass spectrophotometry.
The method of 17 1 kinds of selectivity transmission ions between two linear ion traps side by side comprises the following step:
In first ion trap, produce radio frequency capture electric field, in order to catch the ion of multiple mass-to-charge ratio based on quadrupole field;
In first ion trap, produce, make the ion of a certain mass-to-charge ratio be subjected to resonance excitation and reach bigger motional amplitude along the dipole excitation alternating electric field of the certain frequency of the rectilinear direction that connects an ion trap center, first ion trap center to the second;
In dipole excitation alternating electric field particular phases, in first ion trap, produce to discharge impulse electric field, the above-mentioned ion that reaches a certain mass-to-charge ratio of bigger motional amplitude is discharged in second ion trap, and the ion of other mass-to-charge ratioes is still stayed in first ion trap;
In second ion trap, produce the radio frequency capture electric field, above-mentioned ion or its product ion that enters second ion trap is hunted down second ion trap.
The device of 18 1 kinds of ion storage and analysis comprises:
At least two placed side by side and in the linear ion trap memory block of lateral communication;
Make in the ion storage district voltage source device that produces the radio frequency capture electric field that is used to catch ion;
Be used to be superimposed upon voltage source and the coupling device of first ion storage district to the dipole alternating electric field of the selective resonance excitation of mass-to-charge ratio;
Be used for being expelled to direction the pulse voltage generating means of the high-speed pulse electric field in second ion storage district perpendicular to ion storage district axis at the ion that first ion storage district generation will be excited.
19 1 kinds of ion storage according to claim 18 and the device that separates further comprise the pulse voltage generating means in order to produce the high-speed pulse electric field that makes ion retardation second memory block.
CNA2008100331992A 2008-01-29 2008-01-29 Method for cascade mass spectrometry by using multiple ion traps Pending CN101320016A (en)

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