CN102592937B - Quality analysis method based on restricted theory of relativity and mass spectroscope - Google Patents
Quality analysis method based on restricted theory of relativity and mass spectroscope Download PDFInfo
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- CN102592937B CN102592937B CN201210063341.4A CN201210063341A CN102592937B CN 102592937 B CN102592937 B CN 102592937B CN 201210063341 A CN201210063341 A CN 201210063341A CN 102592937 B CN102592937 B CN 102592937B
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Abstract
The invention belongs to the technical field of quality analysis and particularly discloses a quality analysis method based on the restricted theory of relativity and a mass spectroscope. The method comprises the following steps of: introducing irons of an object to be measured into an iron source area; accelerating the irons to 3*105m/s or more by using an accelerating electric field; introducing the irons into a field-free flying area to freely fly; introducing the irons into an iron detector; and determining the static mass of the irons according to the flying time of the irons in the field-free flying area. The mass spectroscope based on the method comprises the iron source area, the accelerating electric field, a field-free drift tube and the iron detector, wherein the accelerating electric field consists of three or more pulsed high voltages; and the pulsed high voltages are provided by corresponding electrodes. Data measured by the method and the mass spectroscope is the real mass-to-charge ratio of the irons, so the mass is accurate and is not required to be corrected; the mass spectroscope is high in sensitivity and resolution; the quality detection up limit is only limited by the detector; and the mass spectroscope is high in analysis speed, does not require scanning and can realize full-spectrum analysis within tens of seconds.
Description
Technical field
The invention belongs to quality analysis technical field, be specifically related to a kind of mass analysis method and mass spectrometer based on special relativity.
Technical background
Mass spectral analysis is a kind of analytical method of measuring ion charge-mass ratio, and its basic principle is, determinand is ionized in ion source, generates charged ion.The ion being produced by ion source is introduced into mass analyzer, and recycling is distributed in the mass of ion that electric field in mass analyzer or magnetic field and the interaction result of ion are determined different charge-mass ratios.Known mass spectrographic mass analyzer has multiple, as magnetic analyzer, Time-of flight analyzer, quadrupole mass filter, ion trap and ion cyclotron resonance analyzer etc.Compare with other mass analyzers, time of flight mass analyzer has the advantages such as simple in structure, highly sensitive and mass range is wide.A lot of mass-to-charge ratioes are greater than to 10000 ion carries out mass spectral analysis and realizes with time of flight mass analyzer.
Utilize mass spectrometer to measure ion matter lotus numeric ratio and often have certain deviation with the actual matter lotus numerical value of ion, extent can represent by so-called mass measurement precision partially.Obviously, mass measurement precision is higher, shows that the actual mass-to-charge ratio value of apparatus measures result and ion is more approaching.Therefore, mass measurement precision is one of important parameter of weighing a mass spectrometer quality.At present the mass measurement precision of general reasonable time of flight mass analyzer also can only be accurate to tens or several ppm.It is generally acknowledged, the quality of mass measurement precision depends on precision and the electronic equipment of the machining of instrument, due to instrument working power, input and treatment system itself imperfect.
Existing analytical technique of mass spectrum, they are based upon on electromagnetism and theory of mechanics basis, and the quality analysis technology being based upon on Relativistic Theory basis does not also occur.
Summary of the invention
The object of the invention is to propose that a kind of certainty of measurement is high, the simple mass analysis method of device structure and device.
The mass analysis method that the present invention proposes, be a kind of by special relativity theory the method for quality analysis.Utilize the motion of matter important results relevant to material mass in Relativistic Theory, or the quality of object and the relation of movement velocity, mass analysis method set up.Below we discuss the principle that the theory of relativity is analyzed for mass of object.
1, the rest mass of object, moving-mass and movement velocity.
According to Relativistic Theory, an object with speed v motion, its quality m
vits quality m in static will be different from
0.Its moving-mass m
vwith rest mass m
0meet following relation:
（1）
In above formula, c represents the light velocity, according to formula (1), obtains:
（2）
Quality analysis generally, refers to the quality m that analyzes object in static situation
0, according to (2) formula, expect m
0, need to measure movement velocity v and the quality m under this movement velocity state of object
v;
According to current measuring technique, measure the movement velocity of an object and easily accomplish, but it is much more difficult directly to measure the quality of object in a motion.But we can obtain the quality of object in motion with round-about way, its method is:
By a quality, be m
0ion in electrical potential difference, be to accelerate in V electric field, if the initial velocity of ion is approximately zero, the kinetic energy of this ion after accelerated is:
（3）
In formula e be ion with electric charge.
Change (3) formula, obtain:
（4）
Obviously, although people are difficult to measure the quality of motion intermediate ion, if know the accelerating voltage V of ion, and measure the movement velocity v after this ion is accelerated, can calculate according to (4) formula its moving-mass m
v.
(2) and (4) are merged, obtain:
（5）
According to formula (5), just can be by the accelerating voltage value V of ion, and obtain this from proton rest mass by the movement velocity v that measures it, we just can utilize special relativity to set up a kind of new mass analysis method like this.
2, the foundation of the mass analysis method based on special relativity.
As shown in Figure 1, accelerating field 11 of model, ion, through the effect of accelerating field 11, flies into field-free flight district 12, then by ion acceptor 13, is received.Suppose that a quality is m
0, in the electrically charged charged particle for the e electric field that is E in electric field strength, suppose that the distance that this particle moves in electric field is d, the energy K=eEd=that this particle obtains after this electric field that moves out of
, speed v=
if speed when we can measure charged ion and fly out electric field, can accurately extrapolate the quality of ion and the ratio of electric charge.
The speed of the particle of a high-speed motion of Accurate Determining is very difficult often, so we can infer their quality by measuring the Particles Moving needed time of certain distance by another fairly simple method.
Suppose after a kind of sample is ionized generation ion in ion source and arrived certain speed v by electric field acceleration, then enter field-free region and make linear uniform motion.Finally fly to ion signal detector (being ion acceptor) received.Suppose that above-mentioned particle has flown a segment distance L(in mass spectrometer in field-free flight district,
lthe length that represents field-free drift tube), its time t used is:
t=
(6)
Or
(7)
, according to formula (1), can obtain:
=
（8）
Therefore, utilize formula (8), as long as measure certain ion flight certain distance time t used, can accurately obtain the quality of this ion.
In the present invention, determinand ion enters into ion source region, by accelerating field, determinand ion is accelerated to 3 * 10
5m/s and more than, then enter field-free flight district and do free flight, after enter ion detector and be measured to.
3, based on said method, can set up the mass spectrometer that utilizes special relativity, as shown in Figure 2, it comprises its former basic structure: an ion source region, an accelerating region (being accelerating field), a field-free drift tube (field-free flight district), an ion detector.This accelerating field can be comprised of more than three or three high voltage pulses, and these high voltage pulses are provided by counter electrode.In current mass spectrometer, the present invention proposes the structure of this accelerating field first.And yet there are no accelerating field ion is accelerated to 3 * 10
5m/s and above method thereof.
The ion beam that the ion source of analyte is produced is incorporated in ion source region, adds a high voltage pulse between the accelerating electrode in ion source region, and ion is released to ion source region, enters accelerating field; Ion enters field-free drift tube in accelerating field after accelerating, and with constant speed, flies to ion acceptor; The charge-mass ratio of analyte
m 0/
eand the time
tmeet following relation:
=
, in this formula
erepresent that analyte institute is electrically charged,
erepresent accelerating field intensity,
drepresent the distance that analyte moves in accelerating field,
lthe length that represents field-free drift tube,
crepresent the light velocity.
With the mass spectrometer that special relativity is set up, there are several advantages, the first, the data of surveying are the real mass-to-charge ratio of ion, quality is accurate, without correction; The second, for measuring macromolecular substances, during the large biological molecule that particularly will seek quickness at large flux, analysis speed is analyzed, advantage is obvious, the impact without consideration speed on mass change; The 3rd, sensitivity is good, resolution is high, and the quality testing upper limit is limited by ion detector only, and analysis speed is fast, without scanning, can in the time, realize full analysis of spectrum in tens microseconds.
Accompanying drawing explanation
Fig. 1 is the mass spectrum operation principle schematic diagram that utilizes special relativity to set up.
Fig. 2 is the mass spectrometer schematic diagram that a kind of utilization utilizes special relativity to set up.
Number in the figure: 11 is accelerating field, 12Wei field-free flight district, 13 is ion acceptor.21 is ion source, and 22 is ion beam, and 23 is ion source region, 24,25,26Wei accelerator district, and 27,28,29,30,31,37 is electrode, 32,33,34,35 is high voltage pulse, 36Wei field-free flight district, 38 is ion detector.
Embodiment
Fig. 2 is utilize special relativity Foundation mass spectrometric a kind of, and the ion beam 22 that ion source 21 produces is introduced in the ion source region 23 of mass of ion detector, now between ion accelerating electrode 27 and 28, adds a high voltage pulse HV
132, ion is pushed out ion source region 23, enters in accelerator district 24, now on ion accelerating electrode 28 and 29, adds a high voltage pulse HV again
233, ion is pushed out accelerator district 24, enters in accelerator district 25, now on ion accelerating electrode 29 and 30, adds a high voltage pulse HV again
334, ion is pushed out accelerator district 25, enters accelerator district 26, now on ion accelerating electrode 30 and 31, adds a high voltage pulse HV again
435, ion is pushed out accelerator district 26, crosses electrode 31, enters field-free flight district 36 and does free flight, and ion recrosses electrode 37, arrives ion detector 38.Time according to ion in the motion of field-free flight district
tcan determine the mass-to-charge ratio of ion.
Suppose that a part amount is 1000.0000 minute subsample, is produced the ion of positive monovalence by ion source.This ion is accelerated to 3 * 10
5after m/s, entering a distance is that the field-free flight district of 5 meters does free flight, after enter ion detector and be measured to.
With general mass spectrometer, as conventional flight time mass spectrum, do not adopt the theoretical formula (1) of the special relativity that the present invention provides to carry out mass calibration, the molecular weight recording is the moving-mass m of ion in fact
vrather than should be from proton rest mass m
0,
, moving-mass m
vwith rest mass m
0between can produce 0.0005 deviation, the ion mass-to-charge ratio of measuring is inaccurate, if expect actual static molecular weight, must calibrate with standard sample.Employing is based upon the mass spectrometer on special relativity basis, and the molecular weight that can directly record this ion is 1000.0000, consistent with rest mass, and mass-to-charge ratio is accurately without calibration, field-free flight district L=5m, and the time of ion motion is 1.6*10
-5s, analysis speed is exceedingly fast.
Therefore, the mass spectrometer of setting up by special relativity, the data of surveying are the real mass-to-charge ratio of ion, quality is accurate, without correction; And sensitivity is good, resolution is high, the quality testing upper limit is limited by ion detector only, and analysis speed is fast, without scanning, can in the time, realize full analysis of spectrum in tens microseconds.
Claims (2)
1. the mass analysis method based on special relativity, is characterized in that by accelerating field, determinand ion being accelerated to 3 * 10 after determinand ion enters into ion source region
5m/s or more than, then enter field-free flight district and do free flight, then enter ion detector, be measured to, according to ion, in the time of field-free flight district flight, determining should be from proton rest mass, its formula is:
=
，
In formula,
erepresent that analyte institute is electrically charged,
erepresent accelerating field intensity,
drepresent the distance that analyte moves in accelerating field,
lthe length that represents field-free drift tube,
crepresent the light velocity.
2. the mass spectrometer based on mass analysis method claimed in claim 1, is characterized in that comprising: an ion source region, an accelerating field, a field-free drift tube, an ion detector; Described accelerating field is comprised of more than three or three high voltage pulses, and these high voltage pulses are provided by counter electrode;
The ion beam that the ion source of analyte is produced is incorporated in ion source region, between the accelerating electrode in ion source region, add a high voltage pulse, ion is released to ion source region, enter accelerating field, after ion is accelerated in accelerating field, enter field-free drift tube, with constant speed, fly to ion detector, the mass-to-charge ratio of analyte
m 0/
eand the time
tmeet following relation:
=
, wherein,
erepresent that analyte institute is electrically charged,
erepresent accelerating field intensity,
drepresent the distance that analyte moves in accelerating field,
lthe length that represents field-free drift tube,
crepresent the light velocity.
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| CN107240543B (en) * | 2017-07-26 | 2023-06-27 | 合肥美亚光电技术股份有限公司 | Time-of-flight mass spectrometer with double-field acceleration region |
| CN110911264A (en) * | 2019-12-20 | 2020-03-24 | 中国计量科学研究院 | Ion signal detection device and method for time-of-flight mass spectrometer |
| CN111029242A (en) * | 2019-12-20 | 2020-04-17 | 中国计量科学研究院 | Ion signal detection device and method for quadrupole rod mass analyzer |
| CN110931341A (en) * | 2019-12-30 | 2020-03-27 | 中国计量科学研究院 | Ion signal detection device and method for ion trap mass spectrometer |
| CN112986303A (en) * | 2021-02-07 | 2021-06-18 | 中国建筑材料科学研究总院有限公司 | Method for detecting secondary electron emission yield on surface of ion-induced material |
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| CN101601119A (en) * | 2006-12-11 | 2009-12-09 | 株式会社岛津制作所 | Time-of-flight mass spectrometer and in time-of-flight mass spectrometer, analyze the method for ion |
| CN201628700U (en) * | 2010-03-18 | 2010-11-10 | 广州禾信分析仪器有限公司 | Time-of-flight mass spectrometer with wide dynamic range |
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| CN101601119A (en) * | 2006-12-11 | 2009-12-09 | 株式会社岛津制作所 | Time-of-flight mass spectrometer and in time-of-flight mass spectrometer, analyze the method for ion |
| CN201628700U (en) * | 2010-03-18 | 2010-11-10 | 广州禾信分析仪器有限公司 | Time-of-flight mass spectrometer with wide dynamic range |
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