CN208256615U - A kind of Proton-Transfer Reactions ion source and mass spectrograph - Google Patents

A kind of Proton-Transfer Reactions ion source and mass spectrograph Download PDF

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Publication number
CN208256615U
CN208256615U CN201820731210.1U CN201820731210U CN208256615U CN 208256615 U CN208256615 U CN 208256615U CN 201820731210 U CN201820731210 U CN 201820731210U CN 208256615 U CN208256615 U CN 208256615U
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ion
sample
tested
electrode
proton
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孙瑞瑞
黄培
孟庆慧
王欢欢
李淹博
张航
盛六四
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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Abstract

The utility model provides a kind of Proton-Transfer Reactions ion source and mass spectrograph, including initial ion source, the drift tube being connected with initial ion source and the rectilinear ion trap being connected with drift tube;Initial ion source is used to be passed through its internal initial reaction gas ionization into initial reaction ion;By being formed by the metal ring electrode of insulation central spacer, initial reaction ion occurs Proton-Transfer Reactions with sample to be tested molecular collision inside drift tube and generates sample to be tested ion drift tube;Rectilinear ion trap is the hollow cuboid being made of three pairs of plate electrodes, the electrode of rectilinear ion trap front end and the electrode of drift pipe end share, rectilinear ion trap, which is used to capture, enters its internal sample to be tested ion, and sample to be tested ion is evicted from after a certain period of time in storage sample to be tested ion, discontinuously exporting sample to be tested ion to mass spectrum, to substantially increase the sensitivity of mass spectrograph detection.

Description

A kind of Proton-Transfer Reactions ion source and mass spectrograph
Technical field
The utility model relates to mass spectrometry art field, more specifically to a kind of Proton-Transfer Reactions ion source and Mass spectrograph.
Background technique
Mass-spectrometric technique is a kind of effective pervasive experimental technique, has been widely used in chemistry, physics and biology etc. In research field.The common ionization source of mass spectrograph can be divided into four classes, i.e. electron impact ionization, chemi-ionization, desorption ionization and spray Mist ionization.
Proton-Transfer Reactions ion source belongs to one kind of chemi-ionization, and water vapour electric discharge is generally used to generate H3O+As Initial reaction ion collides during Driftdiffusion in drift tube with determinand M subsequently into drift tube, H3O+ It gives proton translocation to determinand M, makes its ionization.The reaction equation are as follows: H3O++M→H2O+MH+
Proton-Transfer Reactions ion source is combined with mass spectrum constitutes Proton transfer reaction mass spectrometry (Proton Transfer Reaction Mass Spectrometry, PTR-MS), it is a kind of volatile organic trace compounds online measuring technique.Proton The determinand ion of generation is transferred to Mass Spectrometer Method by transfer reaction ion source, and according to the intensity of determinand ion come quantitative true Determine the absolute concentration of determinand M.
But since the transmission of determinand ion is continuous, and the presence of mass spectrum duty ratio will lead to determinand ion Detection be it is discontinuous, therefore, in the determinand ion of transmission only have very little ratio ion can be detected so that matter The detection sensitivity of spectrometer is lower.
Utility model content
In view of this, the present invention provides a kind of Proton-Transfer Reactions ion source and mass spectrographs, to improve mass spectrograph Detection sensitivity.
To achieve the above object, the utility model provides the following technical solutions:
A kind of Proton-Transfer Reactions ion source, including initial ion source, the drift tube being connected with the initial ion source And the rectilinear ion trap being connected with the drift tube, the rectilinear ion trap are mounted in ion trap vacuum chamber;
The initial ion source is used to be passed through its internal initial reaction gas ionization into initial reaction ion;
The drift tube by the metal ring electrode of insulation central spacer by being formed, and the initial reaction ion is in the drift tube It is internal that Proton-Transfer Reactions generation sample to be tested ion occurs with sample to be tested molecular collision;
The rectilinear ion trap is the hollow cuboid being made of three pairs of plate electrodes, the electricity of the rectilinear ion trap front end Pole and it is described drift pipe end electrode share, the rectilinear ion trap be used for capture enter its inside described sample to be tested from Son, and after a certain period of time evict the sample to be tested ion from storing the sample to be tested ion.
Preferably, three pairs of plate electrodes include a pair of of the X electrode and X-axis and Z vertical with Y-axis and Z axis composition plane Axis constitutes vertical a pair of of the Y electrode of plane and a pair of of the Z electrode vertical with X-axis and Y-axis composition plane;
Apply reversed radio-frequency alternating current signal on the pair of X electrode and the pair of Y electrode, on the pair of Z electrode Apply d. c. voltage signal.
Preferably, the Z electrode of the rectilinear ion trap front end and the electrode of the drift pipe end share;
There is through-hole, the sample to be tested ion in the drift tube passes through the rectilinear ion trap front end Z on the Z electrode Through-hole on electrode enters the rectilinear ion trap, and the sample to be tested ion in the rectilinear ion trap passes through the rectangle Through-hole on the Z electrode of ion trap end is evicted from.
Preferably, the front end in the initial ion source has the first air inlet, and the end in the initial ion source has the One gas outlet;
First air inlet is used to be passed through initial reaction gas to the inside of the initial ion source;
First gas outlet is used to for the initial reaction gas not being ionized being discharged.
Preferably, the front end of the drift tube has the second air inlet, and the end of the drift tube has the second gas outlet;
Second air inlet is used to be passed through sample to be tested molecule to the inside of the drift tube;
Second gas outlet is used to for unreacted sample to be tested molecule being discharged;
The resistance of similar resistance is connected between the adjacent metal ring electrode;
When applying voltage on the electrode at the drift tube both ends, the drift tube is also used to carry out the ion of its inside Accelerate.
A kind of Proton transfer reaction mass spectrometry instrument, including as above described in any item Proton-Transfer Reactions ion sources and mass spectrum;
The mass spectrum is detected for the sample to be tested ion deported to the Proton-Transfer Reactions ion source, with Obtain the mass spectrogram of the sample to be tested ion.
Preferably, the mass spectrum is flight time mass spectrum, and the flight time mass spectrum is mounted in mass spectrum vacuum chamber, including Repulsion area, accelerating field, free flight area, reflecting mirror and ion detector;
The repulsion area is used for will be described in the deported sample to be tested ion push-in of the Proton-Transfer Reactions ion source Accelerating field;
The accelerating field is for accelerating the sample to be tested ion, so that the sample to be tested ion is described The flight of free flight area;
The reflecting mirror for will the sample to be tested ion reflections that fly in the free flight area to the ion Detector, so that the ion detector detects the sample to be tested ion.
Compared with prior art, technical solution provided by the utility model has the advantage that
Proton-Transfer Reactions ion source provided by the utility model and mass spectrograph, initial ion source is by initial reaction gas It is ionized into initial reaction ion, with sample to be tested molecular collision Proton-Transfer Reactions occurs for initial reaction ion inside drift tube Sample to be tested ion is generated, rectilinear ion trap capture enters its internal sample to be tested ion, and is storing the sample to be tested After a certain period of time, the sample to be tested ion is evicted from for ion, that is to say, that rectilinear ion trap can continue sample to be tested ion Storage releases detection after focusing again, therefore, can greatly improve the sensitivity of mass spectrograph detection.
Detailed description of the invention
In order to illustrate the embodiment of the utility model or the technical proposal in the existing technology more clearly, below will be to embodiment Or attached drawing needed to be used in the description of the prior art is briefly described, it should be apparent that, the accompanying drawings in the following description is only It is the embodiments of the present invention, for those of ordinary skill in the art, without creative efforts, also Other attached drawings can be obtained according to the attached drawing of offer.
Fig. 1 is a kind of structural schematic diagram of Proton-Transfer Reactions ion source provided by the embodiment of the utility model;
Fig. 2 is the structural schematic diagram of rectilinear ion trap provided by the embodiment of the utility model;
Fig. 3 is a kind of cross-sectional view of rectilinear ion trap provided by the embodiment of the utility model;
Fig. 4 is another cross-sectional view of rectilinear ion trap provided by the embodiment of the utility model;
Fig. 5 is the structural schematic diagram of Proton transfer reaction mass spectrometry instrument provided by the embodiment of the utility model.
Specific embodiment
As described in background, existing mass spectrum is discontinuous to the detection of determinand ion, and determinand ion Transmission be it is continuous, therefore, only have the ion of very little ratio that can be detected in the determinand ion of transmission, so that mass spectrum The detection sensitivity of instrument is lower.
Based on this, the utility model provides a kind of Proton-Transfer Reactions ion source, to overcome on of the existing technology Problem is stated, is connected including initial ion source, the drift tube being connected with the initial ion source and with the drift tube Rectilinear ion trap, the rectilinear ion trap are mounted in ion trap vacuum chamber;
The initial ion source is used to be passed through its internal initial reaction gas ionization into initial reaction ion;
The drift tube by the metal ring electrode of insulation central spacer by being formed, and the initial reaction ion is in the drift tube It is internal that Proton-Transfer Reactions generation sample to be tested ion occurs with sample to be tested molecular collision;
The rectilinear ion trap is the hollow cuboid being made of three pairs of plate electrodes, the electricity of the rectilinear ion trap front end Pole and it is described drift pipe end electrode share, the rectilinear ion trap be used for capture enter its inside described sample to be tested from Son, and storing the sample to be tested ion after a certain period of time, the sample to be tested ion is evicted from.
The utility model additionally provides a kind of Proton transfer reaction mass spectrometry instrument, including Proton-Transfer Reactions as described above from Component and flight time mass spectrum;
The flight time mass spectrum for the sample to be tested ion deported to the Proton-Transfer Reactions ion source into Row detection, to obtain the mass spectrogram of the sample to be tested ion.
Proton-Transfer Reactions ion source provided by the utility model and mass spectrograph, initial ion source are electric by initial reaction gas From at initial reaction ion, it is raw that with sample to be tested molecular collision Proton-Transfer Reactions occurs for initial reaction ion inside drift tube At sample to be tested ion, rectilinear ion trap capture enters its internal sample to be tested ion, and store the sample to be tested from Son after a certain period of time, the sample to be tested ion is evicted from, that is to say, that rectilinear ion trap can persistently deposit sample to be tested ion Storage releases detection after focusing again, therefore, can greatly improve the sensitivity of mass spectrograph detection.
It is the core concept of the utility model above, to enable the above objects, features, and advantages of the utility model more Add and become apparent, the following will be combined with the drawings in the embodiments of the present invention, to the technical scheme in the embodiment of the utility model It is clearly and completely described, it is clear that the described embodiments are only a part of the embodiments of the utility model, rather than complete The embodiment in portion.Based on the embodiments of the present invention, those of ordinary skill in the art are not before making creative work Every other embodiment obtained is put, is fallen within the protection scope of the utility model.
The utility model embodiment provides a kind of Proton-Transfer Reactions ion source, is mainly used in Proton-Transfer Reactions matter Spectrometer, as shown in Figure 1, the Proton-Transfer Reactions ion source includes initial ion source 1, the drift that is connected with initial ion source 1 Pipe 2 and the rectilinear ion trap 3 being connected with drift tube 2, the rectilinear ion trap are mounted in ion trap vacuum chamber 4.
Wherein, initial ion source 1 is used to be passed through its internal initial reaction gas ionization into initial reaction ion;
Drift tube 2 by the metal ring electrode 20 of insulation central spacer mainly by being formed, and initial reaction ion is inside drift tube 2 Proton-Transfer Reactions occurs with sample to be tested molecular collision and generates sample to be tested ion;
Rectilinear ion trap 3 is the hollow cuboid being made of three pairs of plate electrodes, the electrode of 3 front end of rectilinear ion trap and drift The electrode 23 for moving 2 end of pipe shares, and rectilinear ion trap 3, which is used to capture, enters its internal sample to be tested ion, and is depositing Storage sample to be tested ion after a certain period of time evicts sample to be tested ion from.
In the present embodiment by sharing the electrode of 2 end of drift tube and the electrode of 3 front end of rectilinear ion trap, eliminate Between ion transmission link, reduce the losses of ions in transmission process, improve mass spectrometric sensitivity, greatly simplifie Mass spectrometric structure.
In the present embodiment, as shown in Figure 1, the front end in initial ion source 1 has the first air inlet 10, initial ion source 1 End has the first gas outlet 11;First air inlet 10 is used to be passed through initial reaction gas to the inside of initial ion source 1;First goes out Port 11 is used to for the initial reaction gas not being ionized being discharged.
The front end of drift tube 2 has the second air inlet 21, and the end of drift tube 2 has the second gas outlet 22;Second air inlet Mouth 21 is used to be passed through sample to be tested molecule to the inside of drift tube 2;Second gas outlet 22 is used for unreacted sample to be tested molecule Discharge.Wherein, the resistance of similar resistance is connected between the adjacent metal ring electrode 20 of drift tube 2;When the electricity at 2 both ends of drift tube When extremely above applying DC voltage, drift tube 2 is also used to accelerate the ion of its inside.
In the present embodiment, as shown in Fig. 2, three pairs of plate electrodes in rectilinear ion trap 3 include constituting to put down with Y-axis and Z axis Vertical a pair of of the X electrode 30 in face constitutes vertical a pair of of the Y electrode 31 of plane with X-axis and Z axis and constitutes plane with X-axis and Y-axis Vertical a pair of of Z electrode 32, a pair of of X electrode 30, a pair of of Y electrode 31 and a pair of Z electrode 32 constitute hollow cuboid.
In the present embodiment, the Z electrode 32 of 3 front end of rectilinear ion trap and the electrode 23 of 2 end of drift tube are shared, also, such as Shown in Fig. 2 and Fig. 3, there is through-hole 320 on Z electrode 32, the sample to be tested ion in drift tube 2 passes through 3 front end Z of rectilinear ion trap Through-hole 320 on electrode 32 enters inside rectilinear ion trap 3, and the sample to be tested ion in rectilinear ion trap 3 passes through rectangular ion Through-hole 320 on 3 end Z electrode 32 of trap is evicted from.Wherein, the diameter of through-hole 320 can according to need design, and the utility model is simultaneously It is defined not to this.
It should be noted that as shown in Figure 2 and Figure 4, there is slit 301, the slit on the X electrode 30 in the present embodiment 301 can be used for evicting from for sample to be tested ion, need to only change the voltage signal on X electrode 30 and Y electrode 31, but It is that the utility model is defined not to this.
Optionally, the initial ion source 1 in the present embodiment is hollow cathode ion source, certainly, the utility model and not only It is limited to this, in other embodiments, can also be the ion source of other forms, for example, it is also possible to is electron impact ionization source, flat Face electrode DC discharge source, radioactive ionization gauge source, photoinduction ion source and microwave plasma source etc..
Optionally, the initial reaction gas in the present embodiment is water vapour, initial reaction ion is hydrogen ion H3O+, Certainly, the utility model is not limited to that, in other embodiments, initial reaction ion can also be NH4 +、NO+And O2 +Deng.
Since the proton affinity of most of volatile organic matter (VOCs) is greater than water, the main component in air N2、O2And CO2Deng proton affinity be less than water, therefore, H3O+Can with most of VOCs occur Proton-Transfer Reactions, without with Composition of air reacts, and therefore, generallys use hydrogen ion H3O+As initial reaction ion.
It is below hydrogen ion H by water vapour, initial reaction ion of initial reaction gas3O+For, to proton translocation The course of work in reactive ion source is illustrated.
As shown in Figure 1, being ionized to H30 hydroxonium ion after water vapour is from the first air inlet 10 into 1 inside of initial ion source Sub- H3O+, hydrogen ion H3O+Can aperture between initial ion source 1 and drift tube 2 enter inside drift tube 2, and not by Water vapour of ionization etc. can be discharged from the first gas outlet 11.
Hydrogen ion H3O+Into after 2 inside of drift tube, can with from the second air inlet 20 enter drift tube 2 inside to Sample molecule (such as VOCs) collision generation Proton-Transfer Reactions generation sample to be tested ion, and unreacted sample to be tested molecule Etc. can be discharged from the second gas outlet 21.
Since drift tube 2 by the metal ring electrode 20 of insulation central spacer by being formed, the electrode at 2 both ends of drift tube After upper application DC voltage, electric field can be formed inside drift tube 2, which can add the ion inside drift tube 2 Speed.That is, hydrogen ion H3O+Can collide under the acceleration of 2 electric field of drift tube with sample to be tested molecule life At sample to be tested ion.
Wherein, the H after acceleration3O+The kinetic energy of ion can pass through the ratio of change drift tube 2 internal electric field and gas number density (E/N) it adjusts, the unit of E/N is Td (1Td=10-17V*cm2).If E/N is too small, H3O+The kinetic energy of ion is less than normal, then not It can effectively prevent the formation of sample to be tested water body cluster ion, and sample to be tested water body cluster ion can be such that mass spectrogram complicates, it is unfavorable In the identification of sample to be tested ion;, whereas if E/N is excessive, H3O+The kinetic energy of ion is bigger than normal, and the result of collision can make to test sample The further fragmentation of product ion generates fragment ion, is also unfavorable for the identification of sample to be tested ion.Optionally, it is applied to drift tube 2 The DC voltage at both ends is within the scope of 3kv~5kv, and the value of E/N is within the scope of 100Td~140Td.
Since the electrode 23 of 2 end of drift tube can be shared with the Z electrode 32 of 3 front end of rectilinear ion trap, and on Z electrode 32 With through-hole 320, therefore, the sample to be tested ion generated in drift tube 2 can enter square by the through-hole 320 on Z electrode 32 Inside shape ion trap 3.
Apply reversed radio-frequency alternating current signal on a pair of of X electrode 30 and a pair of of Y electrode 31, can be formed in X/Y plane Radial quadrupole radio frequency electrical potential well.An axial potential trap can be formed by applying DC voltage on a pair of of Z electrode 32.Sample to be tested from After son enters rectilinear ion trap 3, is collided in rectilinear ion trap 3 with buffer gas molecules and lose axial kinetic energy, thus in axial direction It falls into direct current potential well;Meanwhile under the action of radial radio frequency electrical potential well, stability of the sample to be tested ion in X/Y plane Meet the requirement of Mathieu equation, so as to so that sample to be tested ion stores certain time in rectilinear ion trap 3.Later, Sample to be tested ion is under the promotion of axial potential by 3 end Z electrode 32 of ion beam extraction channel, that is, rectilinear ion trap Through-hole 320 leaves rectilinear ion trap 3.
That is, applying reversed radio-frequency alternating current signal on a pair of of X electrode 30 and a pair of of Y electrode 31, in a pair of of Z electricity It after applying DC voltage on pole 32, can capture into the sample to be tested ion inside rectilinear ion trap 3, and in storage to test sample Product ion after a certain period of time evicts sample to be tested ion from, so that the discontinuous arrival mass spectrum of sample to be tested ion is detected.
Wherein, the ion beam continuously transmitted is stored in rectilinear ion trap, the sample to be tested ion of storage with rectangle from It is focused on ion beam extraction channel after neutral gas molecule collision in sub- trap buffer gas, under the promotion of axial potential It is sent into Mass Spectrometer Method.It is pushed out detection again after persistently storing, focus due to the ion beam continuously transmitted, it can mention significantly The sensitivity of high instrument.
Rectilinear ion trap 3 in the present embodiment can work under the internal pressure of relatively high (0.01Pa~0.1Pa), Therefore, it can be used as buffer gas from the gas that drift tube 2 enters rectilinear ion trap 3, without additionally to rectangular ion It is passed through buffer gas in trap 3, so that the structure of rectilinear ion trap 3 is simpler, it is easier to process.The buffer gas can make The ion obtained into rectilinear ion trap 3 loses axial kinetic energy, to be captured by rectilinear ion trap 3.Wherein, in the present embodiment from Son enters rectilinear ion trap 3 from Z-direction, can substantially reduce the mass discrimination of ion.
It should be noted that the rectilinear ion trap 3 in the present embodiment is the basis from cylindrical ion trap and linear ion hydrazine On develop, it has the characteristics that cylindrical ion trap structure is simple, while it is a kind of linear ion hydrazine again, compared with tradition Three-dimensional ion trap, rectilinear ion trap 3 have capture ion efficiency is high, accommodate that amount of ions is more, space charge effect is weak and plus Tooling matches the advantages that relatively easy.
Proton-Transfer Reactions ion source provided by the embodiment of the utility model, initial ion source is by initial reaction gas ionization At initial reaction ion, initial reaction ion occurs Proton-Transfer Reactions with sample to be tested molecular collision inside drift tube and generates Sample to be tested ion, rectilinear ion trap capture enters its internal sample to be tested ion, and is storing the sample to be tested ion After a certain period of time, the sample to be tested ion is evicted from, that is to say, that rectilinear ion trap can persistently deposit sample to be tested ion Storage releases detection after focusing again, therefore, can greatly improve the sensitivity of mass spectrograph detection.
The utility model embodiment provides a kind of Proton transfer reaction mass spectrometry instrument, as shown in figure 5, including that proton translocation is anti- Ion source and mass spectrum 5 are answered, Proton-Transfer Reactions ion source is the Proton-Transfer Reactions ion source that any embodiment as above provides, should Mass spectrum 5 is for detecting the deported sample to be tested ion of Proton-Transfer Reactions ion source, to obtain sample to be tested ion Mass spectrogram.
Mass spectrum 5 in the present embodiment is flight time mass spectrum, and certainly, the utility model is not limited to that, in other realities It applies in example, the mass spectrum can be other kinds of mass spectrum.
As shown in figure 5, flight time mass spectrum 5 is mounted in mass spectrum vacuum chamber 6, including repulsion area 50, accelerating field 51, from By movement area 52, reflecting mirror 53 and ion detector 54;
Wherein, repulsion area 50 is used to the deported sample to be tested ion of Proton-Transfer Reactions ion source being pushed into accelerating field 51;Accelerating field 51 is for accelerating sample to be tested ion, so that sample to be tested ion flies in free flight area 52;Instead Penetrate mirror 53 for will the sample to be tested ion reflections that fly in free flight area 52 to ion detector 54 so that ion detector Sample to be tested ion is detected.
It is below hydrogen ion H by water vapour, initial reaction ion of initial reaction gas3O+For, to proton translocation The detection and analysis process for reacting mass spectrometric sample to be tested is illustrated.
With reference to Fig. 5, after water vapour is from the first air inlet 10 into 1 inside of initial ion source, it is ionized to hydrogen ion H3O+, hydrogen ion H3O+Aperture of the meeting between initial ion source 1 and drift tube 2 enters inside drift tube 2, and not electric From water vapour etc. can be discharged from the first gas outlet 11.
Hydrogen ion H3O+Into after 2 inside of drift tube, can with from the second air inlet 20 enter drift tube 2 inside to Sample molecule (such as VOCs) collision generation Proton-Transfer Reactions generation sample to be tested ion, and unreacted sample to be tested molecule Etc. can be discharged from the second gas outlet 21.
Since drift tube 2 by the metal ring electrode 20 of insulation central spacer by being formed, the electrode at 2 both ends of drift tube After upper application DC voltage, electric field can be formed inside drift tube 2, which can add the ion inside drift tube 2 Speed.That is, hydrogen ion H3O+Can collide under the acceleration of 2 electric field of drift tube with sample to be tested molecule life At sample to be tested ion.
Wherein, the H after acceleration3O+The kinetic energy of ion can pass through the ratio of change drift tube 2 internal electric field and gas number density (E/N) it adjusts, the unit of E/N is Td (1Td=10-17V*cm2).If E/N is too small, H3O+The kinetic energy of ion is less than normal, then not It can effectively prevent the formation of sample to be tested water body cluster ion, and sample to be tested water body cluster ion can be such that mass spectrogram complicates, it is unfavorable In the identification of sample to be tested ion;, whereas if E/N is excessive, H3O+The kinetic energy of ion is bigger than normal, and the result of collision can make to test sample The further fragmentation of product ion generates fragment ion, is also unfavorable for the identification of sample to be tested ion.Optionally, it is applied to drift tube 2 The DC voltage at both ends is within the scope of 3kv~5kv, and the value of E/N is within the scope of 100Td~140Td.
Since the electrode 23 of 2 end of drift tube can be shared with the Z electrode 32 of 3 front end of rectilinear ion trap, and on Z electrode 32 With through-hole 320, therefore, the sample to be tested ion generated in drift tube 2 can enter square by the through-hole 320 on Z electrode 32 Inside shape ion trap 3.
Apply reversed radio-frequency alternating current signal on a pair of of X electrode 30 and a pair of of Y electrode 31, can be formed in X/Y plane Radial quadrupole radio frequency electrical potential well.An axial potential trap can be formed by applying DC voltage on a pair of of Z electrode 32.Sample to be tested from After son enters rectilinear ion trap 3, is collided in rectilinear ion trap 3 with buffer gas molecules and lose axial kinetic energy, thus in axial direction It falls into direct current potential well;Meanwhile under the action of radial radio frequency electrical potential well, stability of the sample to be tested ion in X/Y plane Meet the requirement of Mathieu equation, so as to so that sample to be tested ion stores certain time in rectilinear ion trap 3.Later, Sample to be tested ion is under the promotion of axial potential by 3 end Z electrode 32 of ion beam extraction channel, that is, rectilinear ion trap Through-hole 320 leaves rectilinear ion trap 3.
That is, applying reversed radio-frequency alternating current signal on a pair of of X electrode 30 and a pair of of Y electrode 31, in a pair of of Z electricity It after applying DC voltage on pole 32, can capture into the sample to be tested ion inside rectilinear ion trap 3, and in storage to test sample Product ion after a certain period of time evicts sample to be tested ion from the through-hole 320 on 3 end Z electrode 32 of rectilinear ion trap from.
Deported sample to be tested ion enters repulsion area 50 after storage focuses, to be measured under the promotion of pulse repulsion voltage Sample ions enter accelerating field 51, and accelerating field 51 accelerates sample to be tested ion, so that sample to be tested ion obtains Certain kinetic energy, and free flight area 52 fly, reflecting mirror 53 to the sample to be tested ion to fly in free flight area 52 into After row reflection compensation, so that sample to be tested ion arrives separately at ion detector 54, so that ion detector 54 is to sample to be tested Ion is detected.
Proton transfer reaction mass spectrometry instrument provided by the embodiment of the utility model, initial ion source is by initial reaction gas ionization At initial reaction ion, initial reaction ion occurs Proton-Transfer Reactions with sample to be tested molecular collision inside drift tube and generates Sample to be tested ion, rectilinear ion trap capture enters its internal sample to be tested ion, and is storing the sample to be tested ion After a certain period of time, the sample to be tested ion is evicted from, that is to say, that rectilinear ion trap can persistently deposit sample to be tested ion Storage releases detection after focusing again, therefore, can greatly improve the sensitivity of mass spectrograph detection.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other The difference of embodiment, the same or similar parts in each embodiment may refer to each other.To the upper of the disclosed embodiments It states bright, can be realized professional and technical personnel in the field or using the utility model.Various modifications to these embodiments pair It will be apparent for those skilled in the art, the general principles defined herein can not depart from this reality In the case where with novel spirit or scope, realize in other embodiments.Therefore, the utility model is not intended to be limited to this These embodiments shown in text, and it is to fit to the widest scope consistent with the principles and novel features disclosed herein.

Claims (7)

1. a kind of Proton-Transfer Reactions ion source, which is characterized in that be connected including initial ion source, with the initial ion source Drift tube and the rectilinear ion trap that is connected with the drift tube, the rectilinear ion trap be mounted on ion trap vacuum chamber It is interior;
The initial ion source is used to be passed through its internal initial reaction gas ionization into initial reaction ion;
The drift tube by the metal ring electrode of insulation central spacer by being formed, and the initial reaction ion is inside the drift tube Proton-Transfer Reactions occurs with sample to be tested molecular collision and generates sample to be tested ion;
The rectilinear ion trap is the hollow cuboid being made of three pairs of plate electrodes, the electrode of the rectilinear ion trap front end with The electrode of the drift pipe end shares, and the rectilinear ion trap, which is used to capture, enters its internal sample to be tested ion, And the sample to be tested ion is evicted from after a certain period of time storing the sample to be tested ion.
2. Proton-Transfer Reactions ion source according to claim 1, which is characterized in that three pairs of plate electrodes include with Y-axis and Z axis constitute vertical a pair of of the X electrode of plane, a pair of of the Y electrode vertical with X-axis and Z axis composition plane and with X-axis and Y Axis constitutes vertical a pair of of the Z electrode of plane;
Apply reversed radio-frequency alternating current signal on the pair of X electrode and the pair of Y electrode, applies on the pair of Z electrode D. c. voltage signal.
3. Proton-Transfer Reactions ion source according to claim 2, which is characterized in that the Z of the rectilinear ion trap front end Electrode and the electrode of the drift pipe end share;
There is through-hole, the sample to be tested ion in the drift tube passes through the rectilinear ion trap front end Z electrode on the Z electrode On through-hole enter the rectilinear ion trap, the sample to be tested ion in the rectilinear ion trap passes through the rectangular ion Through-hole on the Z electrode of trap end is evicted from.
4. Proton-Transfer Reactions ion source according to claim 1, which is characterized in that the front end in the initial ion source has There is the first air inlet, the end in the initial ion source has the first gas outlet;
First air inlet is used to be passed through initial reaction gas to the inside of the initial ion source;
First gas outlet is used to for the initial reaction gas not being ionized being discharged.
5. Proton-Transfer Reactions ion source according to claim 1, which is characterized in that the front end of the drift tube has the The end of two air inlets, the drift tube has the second gas outlet;
Second air inlet is used to be passed through sample to be tested molecule to the inside of the drift tube;
Second gas outlet is used to for unreacted sample to be tested molecule being discharged;
The resistance of similar resistance is connected between the adjacent metal ring electrode;
When applying voltage on the electrode at the drift tube both ends, the drift tube is also used to add the ion of its inside Speed.
6. a kind of Proton transfer reaction mass spectrometry instrument, which is characterized in that including the described in any item proton translocations of Claims 1 to 5 Reactive ion source and mass spectrum;
The mass spectrum is detected for the sample to be tested ion deported to the Proton-Transfer Reactions ion source, to obtain The mass spectrogram of the sample to be tested ion.
7. mass spectrograph according to claim 6, which is characterized in that the mass spectrum is flight time mass spectrum, when the flight Between mass spectrum be mounted in mass spectrum vacuum chamber, including repulsion area, accelerating field, free flight area, reflecting mirror and ion detector;
The repulsion area is used to the deported sample to be tested ion of the Proton-Transfer Reactions ion source being pushed into the acceleration Electric field;
The accelerating field is for accelerating the sample to be tested ion, so that the sample to be tested ion is in the freedom Movement area flight;
The reflecting mirror for will the sample to be tested ion reflections that fly in the free flight area to the ion detection Device, so that the ion detector detects the sample to be tested ion.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108538700A (en) * 2018-05-15 2018-09-14 中国科学技术大学 A kind of Proton-Transfer Reactions ion source, mass spectrograph and its detection method
CN110277301A (en) * 2019-06-28 2019-09-24 清华大学深圳研究生院 A kind of air pressure inside ion trap unevenly distributed and its working method
CN112599397A (en) * 2020-12-14 2021-04-02 兰州空间技术物理研究所 Storage type ion source
CN114334598A (en) * 2021-12-25 2022-04-12 广州禾信仪器股份有限公司 Mass spectrometer, sample ionization platform and ion source thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108538700A (en) * 2018-05-15 2018-09-14 中国科学技术大学 A kind of Proton-Transfer Reactions ion source, mass spectrograph and its detection method
CN108538700B (en) * 2018-05-15 2024-02-23 中国科学技术大学 Proton transfer reaction ion source, mass spectrometer and detection method thereof
CN110277301A (en) * 2019-06-28 2019-09-24 清华大学深圳研究生院 A kind of air pressure inside ion trap unevenly distributed and its working method
CN112599397A (en) * 2020-12-14 2021-04-02 兰州空间技术物理研究所 Storage type ion source
CN114334598A (en) * 2021-12-25 2022-04-12 广州禾信仪器股份有限公司 Mass spectrometer, sample ionization platform and ion source thereof

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