CN103000484A - Mass spectrum analyzer and analyzing method thereof - Google Patents

Mass spectrum analyzer and analyzing method thereof Download PDF

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CN103000484A
CN103000484A CN 201210536824 CN201210536824A CN103000484A CN 103000484 A CN103000484 A CN 103000484A CN 201210536824 CN201210536824 CN 201210536824 CN 201210536824 A CN201210536824 A CN 201210536824A CN 103000484 A CN103000484 A CN 103000484A
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ion
magnetic field
annular
electrode
mass spectrometer
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丁贤忠
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SHANGHAI SISHAN MASS SPECTRUM INSTRUMENT CO Ltd
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SHANGHAI SISHAN MASS SPECTRUM INSTRUMENT CO Ltd
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Abstract

The invention relates to the technical field of mass analysis of analytical instruments, in particular to a mass spectrum analyzer and an analyzing method thereof. The mass spectrum analyzer comprises a magnetic field generating device, a vacuum system, an ion source, an ion accelerator and a series of electrodes. The magnetic field generating device is used for forming a high-strength magnetic field in annular space, an annular axle line exists in the annular space, and magnetic lines of the high-strength magnetic field and the axle line are orthogonal; the vacuum system is used for forming ultrahigh vacuum in the annular space; the ion source is used for generating analyzed ions; the ion accelerator accelerates the analyzed ions which enter an ion annular motion track basically along the axle line and sustain circumnutation for a while; at least parts of the electrodes arranged around the annular axle line are used for detecting image charges induced on the ions in a circumnutation process. According to the mass spectrum analyzer and the analyzing method thereof, the image current signal frequency is improved effectively, the limit electrodes can prevent ions from being diffused and escaping, the magnetic field distribution is even, the mass spectrum quality is improved effectively, and the market prospect is good.

Description

A kind of mass spectrometer and analytical method thereof
[technical field]
The present invention relates to the quality analysis technical field in the analytical instrument, specifically a kind of mass spectrometer and analytical method thereof.
[background technology]
Mass spectrometer claims again mass spectrograph, be for separating of with the instrument that detects different chemical or biotic component, it according to charged particle elect magnetic field motion state and result different, carry out the quasi-instrument that the separation and detection material forms by the mass discrepancy of material atom, molecule or molecular fragment.Magnetic mass spectrometer is a kind of of mass spectrometer, and it has experienced very long developing history.Fourier transform magnetic synchrometer from traditional magnetic-deflection mass spectrometer, magnetic omegatron mass spectrometer, to modern age, i.e. FTICR is to utilize the motion of charged ion in magnetic field to analyze their kind.Mass resolution refers to that mass spectrometer tells the ability of variety classes molecule.Generally speaking, mass resolution is more high better.The mass spectrometric mass resolution of the FTICR of latest report has reached up to ten million, is that the mass spectrometer of any other form is incomparable.
In the FTICR mass spectrometer, the general uniform magnetic field that adopts superconducting coil to produce a few to tens of teslas, the center bore of coil is generally 50 ~ 100mm, analyzed ion is introduced into ICR Cell by the multistage bar of guiding along the magnetic field center axle, the trap chamber of namely circling round, and by axial direct current potential well it is caught.And radially, ion is subjected to the constraint in magnetic field, thereby is bound in the convolution trap chamber.Captive ion accumulated in the center of convolution trap chamber before this, and the electrode in convolution trap chamber adds and excites high frequency voltage subsequently, makes various ions successively by resonant excitation, and the tracks radius increases to a relatively large radius.When ion was done large radius circumnutation, the detecting electrode in convolution trap chamber induced image current, and its frequency is corresponding to the circumnutation frequency of ion, and it and ion mass-to-charge ratio are inversely proportional to.Detect, amplify the image current of the various ions of record, and convert frequency spectrum to Fourier transform, be the mass spectrum that the reflection ion distributes by mass-to-charge ratio.
According to theory of classical physics, the circumnutation frequencies omega c=qB/m of ion, and the mass spectral:mass spectrographic mass resolution of Fourier transform can be obtained by following formula:
Figure BDA0000257431371
, wherein, f=ω/2 π, T mMeasuring Time for image current.
In order to obtain capable of high resolution, will improve ion cyclotron frequency or increase Measuring Time.Usually mass spectrometer work has high requirements to efficient and flux, and per second wishes to adopt several mass spectrograms, at this moment, only has by increasing magnetic field intensity B and then realizing improving cyclotron frequency f and realize high resolution.So use superconducting magnet to become indispensable technology, and in the ion excitation process, produce the magnetron motion pattern, in the scope of whole trap chamber, magnetic field intensity must be very even, electric field strength also must satisfy the specific distribution condition accurately, so the FTICR mass spectrometer also is the most expensive mass spectrometer of cost.And, also very high with superconducting coil maintenance and the use cost of liquid He cooling, be unfavorable for large-scale popularization.
China is rare earth big country, the existing very great development of in recent years rare-earth permanent magnet development, and intensity reaches the neodymium alloy magnet of 1 tesla can be produced in batches, and low price.Characterization of a small FTICR mass spectrometer based on a permanent magnet one literary composition (Anal. Chem. people such as L C Zeller, 1993,65 (15), pp 2116 – 2118) propose to produce magnetic field with permanent magnet in and offer cyclotron resonance formula mass spectrometer, but it is easy absolutely not that the cross section more than diameter 50mm produces uniform high-intensity magnetic field, not only total magnetic flux surpasses the amount that general magnet can provide, nor be evenly distributed in whole cross section easily, so permanent magnetism cyclotron resonance formula mass spectrometer fails to be rapidly developed.
[summary of the invention]
Purpose of the present invention is exactly in order to solve deficiency of the prior art, a kind of novel structure, safe and reliable is provided, solution can improve a kind of mass spectrometer and the analytical method thereof of fourier transform mass spectrometer image current signal frequency at the design problem than the magnetic omegatron mass spectrometer under the low magnetic flux amount.
For achieving the above object, a kind of mass spectrometer is provided, comprise the voltage on one group of rotational symmetric permanent magnet and ion accelerator and the electrode, it is characterized in that the left and right sides of centring magnet post 1 is respectively equipped with the magnet 2 of half hollow, two and half hollow magnets, 2 length are higher than the length of centring magnet post 1, central authorities at an upper portion thereof and at a lower portion thereof are respectively equipped with the first cavity and the second cavity structure, bottom in the first cavity structure is ion storage device 5, be respectively equipped with ion accelerator 3 and vacuum chamber 4 on the top of ion storage device 5, centre at vacuum chamber 4, be provided with the up and down equidistant electrode that uniformly-spaced is arranged in parallel 81 and electrode 82 or several electrodes, be provided with electrod-array 6 and array 7 in the left and right sides of electrode 81 and electrode 82, described half hollow magnet 2 is combined in the mode of series connection by the end cap magnet, make annular space generation magnetic field between two end caps, described centring magnet post is the permanent magnet post, it the magnetic line of force in space by the magnetic line of force of above-mentioned annular space institute around, consist of high-strength magnetic field, the axis quadrature of the magnetic line of force in high-strength magnetic field and annular space, described vacuum chamber 4 consists of ultra high vacuum at above-mentioned annular space, the ion of described ion accelerator 3 is along the ion circulatory motion track circumnutation of annular axis, analyzed ion in the ion accelerator is accelerated, voltage on a series of electrodes around the described annular axis, the magnetic direction that is formed in annular space is controlled the electric field strong and weak of ion.
The high-strength magnetic field intensity that forms at an annular space is not less than 5000 Gausses, or is not less than at least 1000 Gausses.
Ion accelerator accelerates to certain momentum by the per unit electric charge before making ion enter circular orbit, when the required centripetal force of circular motion is provided by magnetic field force fully, has:
Figure BDA0000257431372
, i.e. ω c=Bq/m, the mass-to-charge ratio m/q of it and ion is inversely proportional, because magnetic field force does not do work to ion, the speed absolute value that ion enters before and after the circular orbit is constant, according to , then mv=BqR namely corresponding to certain orbit radius R and certain magnetic field intensity B, needs to have certain momentum BqR before the ion incidence, and orbit radius is certain, and the charge number of ion is larger, and required momentum is larger.
Ion storage device is a three-dimensional ion trap or linear ion trap.
Ion storage device is provided with the ion that is captured in wherein and applies pulse and draw electric field force.
Ion storage device applies duration that pulse draws electric field and is accelerated the time of drawing less than the analyzed ion of minimum mass from described ion storage device being captured in wherein ion.
The electric field form of about beam ion that the voltage on a series of electrodes forms is the annular quadrupole field along annular axis.
The electric field of about beam ion that voltage on a series of electrodes forms comprises the three-dimensional quadrupole field with the rotating shaft coaxle of annular axis.
A series of electrodes are divided into a plurality of sectors and different voltage in addition in annular circumferential, make ion experience the voltage fluctuation of each sector when annular axis rotatablely moves, thereby are formed on the electric field that focuses on to annular axis on the magnetic direction.
The present invention also comprises a kind of analytical method of mass spectrometer, and it comprises following methods:
Employing comprises the magnetic field producing method of permanent magnet, makes in an annulus, to produce substantially uniform high-strength magnetic field, and an annular axis quadrature in the magnetic line of force in magnetic field and the annulus;
Annulus is evacuated to ultra high vacuum;
Produce analyzed ion, they are accelerated and are injected in this annular space, and near the tracks annular axis, the circumnutation of certain time;
Around the ion circulatory motion track in space, toroidal magnetic field, a series of electrodes are set, in ion continues the circumnutation process, detect on the electrode by the image charge signal of ion induction, and be converted to mass spectrum.
The present invention compares with prior art, and it has improved the image current signal frequency effectively, has solved in the prior art at the design problem than the magnetic omegatron mass spectrometer under the low magnetic flux amount.The restriction electrode of its setting can prevent ion diffusion escape, makes magnetic field distribution even, the mass spectral:mass spectrographic quality of Effective Raise, and safe and reliable, market prospects are good.
[description of drawings]
Fig. 1 is the device exemplary plot of utilizing permanent magnet to produce annular high-strength field region in the embodiment of the invention and setting up annular ion trajectory in this zone;
Fig. 2 accelerates to enter circular orbit and image current detection schematic diagram by the analyzed ion that is stored in ion trap in the embodiment of the invention;
Fig. 3 be in the embodiment of the invention toroidal vacuum chamber at the sectional view on R-Z plane;
Fig. 4 be in the embodiment of the invention toroidal vacuum chamber at the sectional view on R-Z plane;
Fig. 5 (a) provides the axial restraint ion to disperse and pick up a kind of electrode structure schematic diagram of image charge in the embodiment of the invention;
Fig. 5 (b) provides the axial restraint ion to disperse and pick up the another kind of electrode structure schematic diagram of image charge in the embodiment of the invention;
Fig. 5 (c) provides the axial restraint ion to disperse and pick up another electrode structure schematic diagram of image charge in the embodiment of the invention;
Fig. 6 is created in the z direction to the enforcement illustration of the electrode design of ion aggregate capabilities in the embodiment of the invention;
As shown in the figure, comprise among the figure: centring magnet post 1, end cap magnet 2, ion accelerator 3, vacuum chamber 4, ion storage device 5, electrod-array 6, electrod-array 7, annular center axle 9,21. signal amplifiers, ion cloud 22, ion trap 23, ion 24, restraining force 31, circular orbit 41, electrode container 42, electrode container 43, electrode container 44, electrode container 45, electrode 52, electrode 53, electrode 54, electrode 55, electrode 61, electrode 62, electrode 63, electrode 64, electrode 81, electrode 82, electrod-array 601, electrod-array 602;
Specifying Fig. 1 is Figure of abstract of the present invention.
[embodiment]
The invention will be further described below in conjunction with accompanying drawing, and the structure of this apparatus and method and principle are very clearly concerning this professional people.Should be appreciated that specific embodiment described herein only is used for explaining the present invention, be not intended to limit the present invention.
The inventor studies discovery, if with cyclotron resonance method excited ion orbit radius, just must provide the uniform high strength Distribution of Magnetic Field on the whole cross section of operating room.And obtain the stage at the ion later image current that is excited, and ion only moves at the track of relatively large radius, and the magnetic field of the central area that motion frequency and radius are less has nothing to do.The present invention proposes a kind of magnetic mass spectral:mass spectrographic analytical method of circling round, the magnetic field producing method that comprises permanent magnet comprising employing, make in the basic uniformly magnetic field that produces in the annulus more than 1000 Gausses, and an annular axis quadrature in the magnetic line of force in magnetic field and the annulus; Annulus is evacuated to ultra high vacuum; Produce analyzed ion, they are accelerated and are injected in this annular space, and in the tracks along annular axis direction, the circumnutation of certain time; Around the ion circulatory motion track in space, toroidal magnetic field, a series of electrodes are set, in ion continues the circumnutation process, detect on the electrode by the image charge signal of ion induction, and be converted to mass signal.Its intermediate ion makes ion have the certain momentum of per unit electric charge from ion source to the accelerator that enters circular orbit.
On the other hand, the present invention proposes a kind of magnetic omegatron mass spectrometer device, comprising: adopt the magnetic field generation device that comprises permanent magnet, in order to form high-strength magnetic field at an annular space; Vacuum system is in order to form ultra high vacuum at above-mentioned annular space; Ion source and ion accelerator produce analyzed ion, and make them enter the ion circulatory motion track of annular space, the circumnutation that continues for some time after acceleration; A plurality of electrodes are set around the ion circulatory motion track in space, toroidal magnetic field, are used for continuing the circumnutation process at ion, detect on the electrode by the image charge signal of ion induction, and be converted to mass spectrogram.
Be clear and definite so-called high-strength magnetic field, the so-called high-strength magnetic field that magnetic field generation device produces refers generally to the above basic uniformly magnetic field of 5000 Gausses, such as under the suitable condition of pole shoe material, might reach several teslas.In any case at least also have more than 1000 Gausses.Can in annular space, define the axis of an annular, the magnetic line of force and this annular axis quadrature in the high-strength magnetic field that magnetic field generation device produces.
The present invention has also further proposed ion accelerator before speeding-up ion injects a certain circular orbit of above-mentioned annular space, and the mode that available pulse is accelerated accelerates to certain momentum with ion by unit charge.
A plurality of electrodes around the above-mentioned tracks can be a series of annular axis electrode on every side, image charges that one of them part is induced in above-mentioned circumnutation process thereon for detection of ion of placing.And the voltage on these a series of electrodes in annular space, is formed on the electric field of about beam ion on the magnetic direction simultaneously.
As shown in Figure 1, mass spectrometer comprises one group of rotational symmetric permanent magnet, it can be divided into centring magnet post 1 and two pairs of end cap magnets 2, combines according to the mode of magnetic field series connection, makes and produce a high-intensity basic uniform magnetic field B in the annular space between two end cap pole shoes.Permanent magnet post centered by the main magnet in this example, it spatially by above-mentioned annular space institute around.Because the magnetic line of force of permanent magnet is imported into the limited annular space of width, this magnetic field effect of converging can easily obtain the above high-intensity magnetic field of 5000 Gausses.A toroidal vacuum chamber 4 is arranged in this magnetic field, and be equipped with a series of electrodes 81 of distributing along circular orbit, 82 and be distributed with electrode or electrod- array 6,7 at two side rings.Circular orbit can be exactly the annular center axle 9 of annular space, but also can be positioned at apart from the scope of annular center axle one segment distance according to the difference of ion initial momentum.The ion of tangentially incident is subject to the effect of magnetic field force beyond from the toroidal magnetic field.Because the central shaft of the direction of magnetic field B and annular space, i.e. ion trajectory direction quadrature, the magnetic field force direction is the radial direction of circular orbit, points to the rotary middle spindle z of annular space, ion moves in a circle in the toroidal magnetic field.When the required centripetal force of circular motion is provided by magnetic field force fully, have:
Figure BDA0000257431374
(1), i.e. ω c=Bq/m (2)
The mass-to-charge ratio m/q of it and ion is inversely proportional.Because magnetic field force does not do work to ion, the speed absolute value that ion enters before and after the circular orbit is constant, and according to (1) formula, mv=BqR namely corresponding to certain orbit radius R and certain magnetic field intensity B, needs to have certain momentum BqR before the ion incidence.So orbit radius is certain, the charge number of ion is larger, and required momentum is larger.
In order to satisfy this requirement, the present invention proposes following ion implantation apparatus.
As shown in Figure 2, ion is produced by any ion source, and is stored in the ion trap 23, and this ion trap can be a three-dimensional quadrupole ion, also can be a linear ion trap.Take linear ion trap as example, ion can from its axial introducing, after the collision cooling, form the linear ion cloud 22 that is distributed in middle shaft attachment.Now wherein a pair of, namely add a dipole short pulse between the electrode of x direction, the duration tp of this pulse is less than the derivative time of ion, and so all ions have obtained the momentum Ftp of an x direction under impulse action.F=Eq wherein, E is dipole electric field intensity, q is ionic charge, so the momentum of ion outgoing is Eqtp, it is directly proportional with the charge number of ion, but irrelevant with mass-to-charge ratio.
Ion 24 with certain momentum from ion trap 23 after the outgoing, enter the circular orbit of toroidal vacuum chamber 4 inside, moved in a circle by magnetic fields, in order to prevent that ion from spreading escape along the z direction of principal axis to both sides, in vacuum chamber 4, be provided with the restriction electrode, form certain electric field, the restriction ion is dispersed escape what the axial velocity component of z caused.Formation restriction ion has multiple in z directional divergence electric field form, now illustrate with following 3 kinds.
Scheme one, as shown in Figure 3, in vacuum chamber 4, electrode is divided into the electrod-array 6 that distributes along urceolus, electrode or electrod-array 7 with the inner core distribution, and electrode or the electrod-array of two side ring distributions, wherein electrod-array 6 may be split into electrode 61, electrode 62, electrode 63 ... for positive ion mode, current potential on the electrode 81,82 is than the current potential polarization of electrod-array 6, electrod-array 7, forming one assembles in axle z direction, at the annular quadrupole field of radially dispersing, this quadrupole field may comprise other high-order multipole fields certainly.This formation electrode 81 and 82 can split into a plurality of ring electrodes, to form the form of optimum field.Ion is marked by the direction of electric field force when this circular orbit operation by arrow, as long as track is radially near the center of this annular quadrupole field, the annular center axle 9 of aforesaid annular space namely, the radial component of electric field is just close to zero, magnetic field force plays a leading role, and the circular motion frequency of ion is not subjected to the impact of electric field.And axially, in case the center of ion deflection annular quadrupole field will be subject to a restraining force 31 of pointing to the center, make ion get back to the center of track.
Scheme two, similar with Fig. 3, use electrod-array to surround a circular passage that surrounds ion trajectory, as shown in Figure 4, in vacuum chamber 4, be distributed in the electrod-array on the urceolus, comprise electrode 61,62,63 ... with the electrode 7 that is distributed on the inner core, curved distribution on the R-Z cross section.More preferably, electrode 6,7 inner surface, namely the one side towards ion is to make the hyperboloid with common axis of rotation, electrode 81,82 then still is comprised of two groups of electrod-arrays, each ring electrode in the array is added with different voltage, makes in ion circular orbit space to form with circular orbit around the three-dimensional quadrupole field of the rotation of rotating shaft z axle.If when the radius of electrod-array was wider certainly, both having made did not have electrod- array 6,7, can form yet and rotate preferably quadrupole field.Among Fig. 4, the active force of this quadrupole field to ion marked by arrow 31.In that axially it makes ion convergent arrive median plane, be z=0, radially then the repulsion ion away from axis, but since this electric field action power much smaller than the radial effect power in magnetic field, ion still obtains enough centripetal force and moves in a circle, and just frequency ratio (2) formula of circular motion is smaller.
On the physics, can be expressed as:
ω = ω c 2 + ( ω c 2 ) 2 - ω t 2
ω wherein tFor ion at the motion frequency that is axially retrained back and forth, it is relevant with quadripolar electric field intensity, but irrelevant with orbit radius, so even ion is different because of initial condition, depart from slightly the central orbit radius, its speed can not change thereupon yet, helps to improve resolution.
Scheme three, Fig. 5 a shows a part of circular arc in circular orbit space, along the circular orbit 41 of ion, electrode forms the passage 42,43,44,45 of segmentation ... periodically be equipped with on these passages+,-,+, the voltage of-polarity, just add such as electrode container 42,43 add negative ..., ion is when passing this series of passages at a high speed, in the passage of these segmentations, and the electric field between passage and the passage can make ion convergent to the annular center circular orbit, prevents that ion from dispersing at magnetic direction.Certainly these passages might not be made by a closed duct, can be as Fig. 5 b ,+,-, + ,-periodic voltage only be added in the electrode 52,53,54 of two end faces, on 55, still respectively be same current potential and be positioned at inner periphery electrode 46,47, even save these electrodes at all, shown in Fig. 5 c.
The image current that rotatablely moves and induce in order to detect ion, above-mentioned various types of track restrictions electrodes all will be separated into some sections along circumference, namely as shown in Figure 1 electrod-array 6, are separated into the electrode 61,62,63 that shows among Fig. 2,64 etc.Limit the formation scheme of electric field for above-mentioned different z direction, cutting apart along the electrode of circumference also has different modes, in scheme three, the electrode 42,43,44,45 of Fig. 5 a ... separating of nature, these a series of electrodes 42,43,44,45 have just become the image current pickoff electrode naturally like this.Although will add certain current potential on it, as long as coupling circuit reasonable in design just can not affect picking up of image charge, this point is existing precedent in the design of existing FTICR trap, will not state more.
Fig. 6 provides again a scheme of comparatively optimizing of this class electrode design.It adopts the scheme of Fig. 5 c substantially, a pair of annular electrode array 601,602 coaxial parallel placements, 16 effects that sector mirror image current pickoff electrode 61 is undertaken the track restrictions electrode simultaneously on it.Just increased track correction electrode 62,63,64,65 in the ion porch.Odd number is one group in 16 every the sector mirror image current pickoff electrodes, and even numbers is another group, and the connection with reference to figure 2 connects separately, and signal is delivered to differential amplifier.Different from Fig. 2 is that the odd number group also will be linked on the different direct voltages with high resistance or inductance with the even numbers group, makes the certain voltage of maintenance between odd number group and the even numbers group, is used for producing axially converging the field, undertakes track in axial restriction.Certainly signal also will with electric capacity every directly, only allow the image current of alternation pass through before delivering to differential amplifier.
Press the structural design of Fig. 6, ion rotatablely moves a week, and image current is 8 pulsation periods behind differential amplification.When doing the FTMS analysis, signal frequency improves 8 times, is equivalent to magnetic field and improves 8 times.
It is worth mentioning that when ion enters the zone, toroidal magnetic field outside magnetic field, need to be through the fringing field in one section magnetic field.The effect of track correction electrode 62,64 is to apply deflecting electric field in the moment of ion incidence, makes ion can enter smoothly circular orbit.After the ion injection, revise the deflecting electric field of electrode generation and can cancel, also can change into and produce necessary correction electric field, the centripetal force that magnetic field provides is revised.
For scheme one, two, both can cut apart Fig. 3,4 electrode 6, form a plurality of image current pickoff electrodes, also can cut apart electrode 7 and form a plurality of image current pickoff electrodes, the a plurality of image current pickoff electrodes that can also use electrode 81,82 segmentation to form, certainly the electrod-array segmentation can also be linked together by electric capacity again, contribute total image current.Gather simultaneously the method for image current about electrode upper offset DC potential, existing a lot of precedents will not be stated more in the design of existing FTICR trap.
That adopts in the above-mentioned example is arranged on a toroidal vacuum chamber in the zone, toroidal magnetic field, and this point is also nonessential.Also can put into together ultra-high vacuum system to magnetic field generation devices such as permanent magnets.
In sum, the concrete arrangement of system and the scheme that designs the restriction electrode of magnetic direction around the circular orbit and pick up the electrode of image current have various ways, understanding under the prerequisite of basic ideas of the present invention, the professional person can design more combining form in the industry, but still covered by the present invention.

Claims (10)

1. mass spectrometer, comprise the voltage on one group of rotational symmetric permanent magnet and ion accelerator and the electrode, it is characterized in that the left and right sides of centring magnet post (1) is respectively equipped with the magnet (2) of half hollow, two and half hollow magnet (2) length are higher than the length of centring magnet post (1), central authorities at an upper portion thereof and at a lower portion thereof are respectively equipped with the first cavity and the second cavity structure, bottom in the first cavity structure is ion storage device (5), be respectively equipped with ion accelerator (3) and vacuum chamber (4) on the top of ion storage device (5), centre in vacuum chamber (4), be provided with the up and down equidistant electrode that uniformly-spaced is arranged in parallel (81) and electrode (82) or several electrodes, be provided with electrod-array (6) and array (7) in the left and right sides of electrode (81) and electrode (82), described half hollow magnet (2) is combined in the mode of series connection by the end cap magnet, make annular space generation magnetic field between two end caps, described centring magnet post is the permanent magnet post, it the magnetic line of force in space by the magnetic line of force of above-mentioned annular space institute around, consist of high-strength magnetic field, the axis quadrature of the magnetic line of force in high-strength magnetic field and annular space, described vacuum chamber (4) consists of ultra high vacuum at above-mentioned annular space, the ion of described ion accelerator (3) is along the ion circulatory motion track circumnutation of annular axis, analyzed ion in the ion accelerator is accelerated, voltage on a series of electrodes around the described annular axis, the magnetic direction that is formed in annular space is controlled the electric field strong and weak of ion.
2. a kind of mass spectrometer as claimed in claim 1 is characterized in that being not less than 5000 Gausses in the high-strength magnetic field intensity that an annular space forms, or is not less than at least 1000 Gausses.
3. a kind of mass spectrometer as claimed in claim 1 is characterized in that accelerating to certain momentum by the per unit electric charge before ion accelerator makes ion enter circular orbit, when the required centripetal force of circular motion is provided by magnetic field force fully, has: , i.e. ω c=Bq/m, the mass-to-charge ratio m/q of it and ion is inversely proportional, because magnetic field force does not do work to ion, the speed absolute value that ion enters before and after the circular orbit is constant, according to
Figure FDA0000257431362
, then mv=BqR namely corresponding to certain orbit radius R and certain magnetic field intensity B, needs to have certain momentum BqR before the ion incidence, and orbit radius is certain, and the charge number of ion is larger, and required momentum is larger.
4. a kind of mass spectrometer as claimed in claim 1 is characterized in that ion storage device is a three-dimensional ion trap or linear ion trap.
5. a kind of mass spectrometer as claimed in claim 1 is characterized in that ion storage device is provided with the ion that is captured in wherein and applies pulse and draw electric field force.
6. such as claim 1 or 5 described a kind of mass spectrometers, it is characterized in that ion storage device applies duration that pulse draws electric field and is accelerated the time of drawing less than the analyzed ion of minimum mass from described ion storage device being captured in wherein ion.
7. a kind of mass spectrometer as claimed in claim 1 is characterized in that the electric field form of about beam ion that the voltage on a series of electrodes forms is the annular quadrupole field along annular axis.
8. a kind of mass spectrometer as claimed in claim 1, the electric field that it is characterized in that about beam ion that the voltage on a series of electrodes forms comprise the three-dimensional quadrupole field with the rotating shaft coaxle of annular axis.
9. a kind of mass spectrometer as claimed in claim 1, it is characterized in that a series of electrodes are divided into a plurality of sectors and different voltage in addition in annular circumferential, make ion when annular axis rotatablely moves, experience the voltage fluctuation of each sector, thereby be formed on the electric field that focuses on to annular axis on the magnetic direction.
10. the analytical method of a mass spectrometer is characterized in that comprising following methods:
Employing comprises the magnetic field producing method of permanent magnet, makes in an annulus, to produce substantially uniform high-strength magnetic field, and an annular axis quadrature in the magnetic line of force in magnetic field and the annulus;
Annulus is evacuated to ultra high vacuum;
Produce analyzed ion, they are accelerated and are injected in this annular space, and near the tracks annular axis, the circumnutation of certain time;
Around the ion circulatory motion track in space, toroidal magnetic field, a series of electrodes are set, in ion continues the circumnutation process, detect on the electrode by the image charge signal of ion induction, and be converted to mass spectrum.
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