CN103745905B - A kind of particulate ion trap mass spectrometer with low-temperature charge detector - Google Patents
A kind of particulate ion trap mass spectrometer with low-temperature charge detector Download PDFInfo
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- CN103745905B CN103745905B CN201410005139.5A CN201410005139A CN103745905B CN 103745905 B CN103745905 B CN 103745905B CN 201410005139 A CN201410005139 A CN 201410005139A CN 103745905 B CN103745905 B CN 103745905B
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- liquid nitrogen
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Abstract
The invention discloses a kind of particulate ion trap mass spectrometer with low-temperature charge detector.Comprise ion strap mass analyzer, induced with laser sound wave desorption ionization source and electric charge detector; Upper end electrode and lower end electrode be axially equipped with through hole a; The center position of ring electrode is provided with through hole b; Electric charge detector is located at the bottom of ion strap mass analyzer, and is provided with insulating ceramics ring between ion strap mass analyzer and electric charge detector; Electric charge detector surface is provided with electro-magnetic shielding cover, and the corresponding position, position of electro-magnetic shielding cover and through hole a is provided with through hole c; Induced with laser sound wave desorption ionization source comprises sample target and laser; It also comprises cooled with liquid nitrogen device, and cooled with liquid nitrogen device comprises airtight cavity, and airtight cavity is connected with liquid nitrogen effuser with liquid nitrogen inflow pipe; Airtight cavity is located at the bottom of electric charge detector, and is contact cooperation.The present invention, owing to have employed liquid nitrogen stream velocity control device, can regulate the temperature of electric charge detector, thus realizes the flexible control of electric charge detector noise level.
Description
Technical field
The present invention relates to a kind of mass spectrometer, be specifically related to a kind of particulate ion trap mass spectrometer with low-temperature charge detector.
Background technology
Particulate matter such as large aerosol, biologic grain (virus, cell) etc. are extensively present in occurring in nature.Because these particles have important impact for atmospheric environment and health, therefore measuring it and characterize is an important topic in analytical test.As everyone knows, the quality of molecule is the intrinsic character of molecule, and equally, the quality of particle is also an important parameter of characterizing particles material.Ion trap particle mass spectrum is a kind of new method measuring granular mass that latest developments are got up.In experimentation, the particulate matter being separated sucking-off by induced with laser sound wave desorb source enters ion strap mass analyzer, its mass-to-charge ratio and carried charge are recorded by ion strap mass analyzer and electric charge detector respectively, thus achieve quick, the Accurate Determining of granular mass.With particulate ion trap mass spectrum for instrument, people successfully determine the quality of polystyrene spheres and various kinds of cell.But particulate ion trap mass spectrum also has many deficiencies, and wherein one of problem demanding prompt solution is the background noise how reducing electric charge detector, improve the mass spectrographic resolution of particle.At present, the average noise of electric charge detector is about 600e, according to the some linear that carried charge and the particle size of particle exist, the particle only having more than 1 μm carried charge higher could be detected effectively, and this just significantly limit particulate ion trap mass spectrometer to analysis more short grained below micron order.
Therefore, need to provide a kind of particulate ion trap mass spectrometer that can reduce background noise, to improve mass spectrometric detection perform.
Summary of the invention
The object of this invention is to provide a kind of particulate ion trap mass spectrometer with low-temperature charge detector, the present invention is by realizing the reduction of its background noise to the sub-cooled of electric charge detector, thus for expanding particulate ion trap mass spectrographic mass range, realize single virus, the quality determination of bacterium lays the foundation.
A kind of particulate ion trap mass spectrometer with low-temperature charge detector provided by the present invention, comprises ion strap mass analyzer, induced with laser sound wave desorption ionization source and electric charge detector; Described ion strap mass analyzer comprises upper end electrode, ring electrode and lower end electrode; Described upper end electrode and described lower end electrode are located at the two ends of described ring electrode respectively, and described ring electrode and be equipped with insulating ceramics ring between described upper end electrode and described lower end electrode; Described upper end electrode and described lower end electrode be axially equipped with through hole a; The center position of described ring electrode is provided with through hole b;
Described electric charge detector is located at the bottom of described ion strap mass analyzer, and is provided with insulating ceramics ring between described ion strap mass analyzer and described electric charge detector; Described electric charge detector surface is provided with an electro-magnetic shielding cover, and the corresponding position, position of described electro-magnetic shielding cover and described through hole a is provided with through hole c; Described induced with laser sound wave desorption ionization source comprises sample target and laser, and nearly described through hole b place is located at by described sample target;
Described particulate ion trap mass spectrometer also comprises cooled with liquid nitrogen device, and described cooled with liquid nitrogen device comprises an airtight cavity, and described airtight cavity is connected with liquid nitrogen effuser with liquid nitrogen inflow pipe; Described airtight cavity is located at the bottom of described electric charge detector, and is contact cooperation.
In described particulate ion trap mass spectrometer, the shape and size of described airtight cavity are consistent with the shape and size of described electric charge detector respectively, to ensure that described cooled with liquid nitrogen device and described electric charge detector can close contacts.
In described particulate ion trap mass spectrometer, described liquid nitrogen inflow pipe is connected with the bottom of described airtight cavity;
Described liquid nitrogen effuser is connected with the bottom of described airtight cavity, and extends to the top place of described airtight cavity.
In described particulate ion trap mass spectrometer, the top of described airtight cavity is provided with a groove, described liquid nitrogen effuser extends in described groove, whole closed cavity can be full of after liquid nitrogen can be made after arranging like this to flow into, can the form of liquid nitrogen flow out from described liquid nitrogen effuser when liquid nitrogen flow velocity is large time, the nitrogen form that can gasify when liquid nitrogen flow velocity is little time flows out from described liquid nitrogen effuser, thus realizes the control to chilling temperature.
In described particulate ion trap mass spectrometer, the height of described airtight cavity can be 10 ~ 20mm;
The height of described groove can be 3 ~ 5mm, and the distance between the liquid nitrogen arrival end of described liquid nitrogen effuser and described groove top can be 1 ~ 2mm.
In described particulate ion trap mass spectrometer, described particulate ion trap mass spectrometer also comprises liquid nitrogen stream velocity control device; Described liquid nitrogen stream velocity control device comprises liquid nitrogen container, flowmeter and microfluidic valve; Described liquid nitrogen inflow pipe is connected with described liquid nitrogen container, and described liquid nitrogen container is also connected with a nitrogen pipeline, described nitrogen pipeline is provided with successively described flowmeter and described microfluidic valve, and one end of nearly described liquid nitrogen container is located at by described flowmeter; The nitrogen passed into by described nitrogen pipeline can make the pressure in described liquid nitrogen container increase, thus the liquid nitrogen in described liquid nitrogen container can be pressed in described airtight cavity, and the size by passing into nitrogen flow rate controls the speed that liquid nitrogen flows into described airtight cavity, to realize controlling the temperature of described electric charge detector, during as needed temperature constant, then nitrogen flow rate can be controlled be a steady state value; During as heated up, then nitrogen flow rate can be improved; During as lowered the temperature, then can stop logical nitrogen or reduce nitrogen flow rate.
In described particulate ion trap mass spectrometer, bottom described electric charge detector, be provided with a temperature sensor, with the temperature of electric charge detector described in Real-Time Monitoring.
The present invention is owing to taking above technical scheme, and it has the following advantages:
1, the present invention lowers the temperature to electric charge detector owing to adopting liquid nitrogen, the minimum temperature of detector that makes reaches-190 DEG C, significantly reduce the thermal noise of electric charge detector, for the quality determination that mass spectrographic for ion trap particle range of application is extended to bacterium and virus is laid a good foundation.
2, the present invention is owing to have employed liquid nitrogen stream velocity control device, can regulate the temperature of electric charge detector, thus realizes the flexible control of electric charge detector noise level.
3, the present invention is owing to adopting ion strap mass analyzer and electric charge detector, can obtain mass-to-charge ratio and the charge number of bead ion simultaneously, therefore, achieve the Fast Measurement to granular mass and mass distribution.
4, the present invention is owing to adopting ion strap mass analyzer, it is low to the requirement of vacuum degree, can at more rough operate under vacuum conditions, required vacuum condition only needs mechanical pump just can provide, for the mass spectrometric further simplification of particle provides favourable condition.
Accompanying drawing explanation
Fig. 1 is the mass spectrometric structural representation of particulate ion trap that the present invention has low-temperature charge detector.
Fig. 2 is the mass spectrometric cutaway view of particulate ion trap that the present invention has low-temperature charge detector.
Fig. 3 is the schematic diagram of induced with laser sound wave desorption ionization source in particle mass spectrometer of the present invention.
Fig. 4 is the structural representation of liquid nitrogen stream velocity control device in particle mass spectrometer of the present invention.
Fig. 5 is the noise of particle mass spectrometer of the present invention electric charge detector under condition of different temperatures.
In figure, each mark is as follows:
1 upper end electrode, 2 ring electrodes, 3 lower end electrode, 4 electric charge detectors, 5 ceramic rings, 6 signal output parts, 7 input end of analog signal, 8 cooled with liquid nitrogen devices, 9 airtight cavities, 10 liquid nitrogen inflow pipes, 11 liquid nitrogen effusers, 12 grooves, 13 induced with laser sound wave desorption ionization source, 14 sample targets, 15 laser, 16 flowmeters, 17 nitrogen pipeline, 18 liquid nitrogen containers, 19 microfluidic valves.
Embodiment
Following the present invention will be further described by reference to the accompanying drawings, but the present invention is not limited to following examples.
As depicted in figs. 1 and 2, the particulate ion trap mass spectrometer with low-temperature charge detector provided by the invention comprises induced with laser sound wave desorption ionization source 13, ion strap mass analyzer, electric charge detector 4, cooled with liquid nitrogen device 8 and liquid nitrogen stream velocity control device.This ion strap mass analyzer comprises a upper end electrode 1, ring electrode 2 and lower end electrode 3, and upper end electrode 1, ring electrode 2 and lower end electrode 3 are hyperboloid shape, and its outside is rectangle.The radius of ring electrode 2 is 10mm, and upper end electrode 1 and the distance between lower end electrode 3 and trap center are 7.07mm, upper end electrode 1 and be equipped with insulating ceramics ring (not shown) between lower end electrode 3 and ring electrode 2, avoids it to contact with each other and is short-circuited.Upper end electrode 1 and lower end electrode 3 to be axially equipped with through hole a(not shown in the figures), the center position of ring electrode 2 is provided with through hole b.Electric charge detector 4 is located at the bottom of ion strap mass analyzer, and both distances are 10mm, and separate with insulating ceramics ring 5 between the two.For avoiding electromagnetic interference, the additional electro-magnetic shielding cover (not shown) in electric charge detector 4 surface, and on this electro-magnetic shielding cover, be provided with through hole c(with the corresponding position, position of through hole a not shown in the figures).Electric charge detector 4 comprises signal output part 6 and input end of analog signal 7.Signal output part 6 is connected with external signal harvester, for gathering the signal of electric charge detector.The analog signal inputting a standard at input end of analog signal 7 can realize the correction to electric charge detector response.
As shown in Figure 3, in the present invention, induced with laser sound wave desorption ionization source 13 comprises sample target 14 and laser (not shown), and nearly through hole b place is located at by sample target 14, and laser 15 pairs of samples that laser is launched carry out desorption ionization.
As depicted in figs. 1 and 2, cooled with liquid nitrogen device 8 comprises an airtight cavity 9, and this airtight cavity 9 is connected with liquid nitrogen effuser 11 with liquid nitrogen inflow pipe 10.Airtight cavity 9 is located at the bottom of electric charge detector 4, and is contact cooperation.Liquid nitrogen inflow pipe 10 is connected with the bottom of airtight cavity 9; The top of airtight cavity 9 is provided with a groove 12, liquid nitrogen effuser 11 is connected with the bottom of airtight cavity 9, and extend in groove 12, such can make liquid nitrogen flow into after can be full of whole airtight cavity 9, flow out from liquid nitrogen effuser 11 with liquid nitrogen form when liquid nitrogen flow velocity is large, flow out from liquid nitrogen effuser 11 with the nitrogen form of gasification time liquid nitrogen flow velocity is little, thus realize the control to chilling temperature.
Liquid nitrogen flow velocity in the present invention is controlled by liquid nitrogen stream velocity control device as shown in Figure 4.This liquid nitrogen stream velocity control device comprises liquid nitrogen container 18, flowmeter 16 and microfluidic valve 19; Wherein liquid nitrogen inflow pipe 7 is connected with liquid nitrogen container 18, and liquid nitrogen container 18 is also connected with a nitrogen pipeline 17, and nitrogen pipeline 17 sets gradually flowmeter 16 and microfluidic valve 19, and one end of nearly liquid nitrogen container 18 is located at by flowmeter 16.
Use the process of above-mentioned liquid nitrogen stream velocity control device control liquid nitrogen flow velocity as follows: high pure nitrogen enters from nitrogen pipeline 17 entrance, and its flow velocity can be measured in real time by flowmeter 16 and be regulated and controled by microfluidic valve 19.The nitrogen flowed into makes the pressure in liquid nitrogen container 18 increase, thus is pressed into by liquid nitrogen in the airtight cavity 9 of cooled with liquid nitrogen device.During temperature stabilization, the flow velocity of nitrogen can be controlled in 0.4 ~ 0.6mL/min, and when needing to lower the temperature, flow velocity can increase nitrogen flow rate to 0.8 ~ 1.0mL/min, needs then to stop nitrogen flowing into or turn down nitrogen flow rate at below 0.3mL/min when heating up.
In order to the temperature of electric charge detector 4 can be monitored in real time, can a temperature sensor (not shown) be set bottom electric charge detector 4.
In particulate ion trap mass spectrometer of the present invention, the height of airtight cavity 9 can be 10 ~ 20mm, and the height of groove 12 can be 3 ~ 5mm, and the distance between the liquid nitrogen arrival end of liquid nitrogen effuser 11 and groove 12 top can be 1 ~ 2mm.
When using the present invention to have the particulate ion trap mass spectrometer of low-temperature charge detector, induced with laser sound wave desorption ionization source 13 is utilized to make particle desorb and enter into ion strap mass analyzer, by changing the imprison condition of ion trap, namely scanning imprison voltage or frequency make ion become unstable and outside trap of dishing out detect by electric charge detector.Utilize cooled with liquid nitrogen device and liquid nitrogen stream velocity control device the temperature of electric charge detector can be controlled in specific scope.
When the temperature decreases, the noise of electric charge detector obviously reduces, and as shown in Figure 5, when normal temperature (20 DEG C), the average noise of detector is 0.01V, as Fig. 5 a) shown in; When temperature is reduced to-64 DEG C, the average noise of detector reduces half, is 0.005V, as Fig. 5 b) shown in.
In above-mentioned testing process, ion trap internal gas pressure can be controlled in the fixed value between 1.50 ~ 3.00Pa, and RF voltage added by ring electrode can be a fixed value between 800 ~ 1000V, and RF frequency scanning interval can be 450 ~ 100Hz.
The various embodiments described above are only for illustration of the present invention; the applying mode of voltage, the structure of each parts, size, setting position and shape all can change to some extent; on the basis of technical solution of the present invention; all improvement of carrying out individual part according to the principle of the invention and equivalents, all should not get rid of outside protection scope of the present invention.
Claims (6)
1. there is a particulate ion trap mass spectrometer for low-temperature charge detector, comprise ion strap mass analyzer, induced with laser sound wave desorption ionization source and electric charge detector; Described ion strap mass analyzer comprises upper end electrode, ring electrode and lower end electrode; Described upper end electrode and described lower end electrode are located at the two ends of described ring electrode respectively, and described ring electrode and be equipped with insulating ceramics ring between described upper end electrode and described lower end electrode; Described upper end electrode and described lower end electrode be axially equipped with through hole a; The center position of described ring electrode is provided with through hole b;
Described electric charge detector is located at the bottom of described ion strap mass analyzer, and is provided with insulating ceramics ring between described ion strap mass analyzer and described electric charge detector; Described electric charge detector surface is provided with an electro-magnetic shielding cover, and the corresponding position, position of described electro-magnetic shielding cover and described through hole a is provided with through hole c; Described induced with laser sound wave desorption ionization source comprises sample target and laser, and nearly described through hole b place is located at by described sample target; It is characterized in that:
Described particulate ion trap mass spectrometer also comprises cooled with liquid nitrogen device, and described cooled with liquid nitrogen device comprises an airtight cavity, and described airtight cavity is connected with liquid nitrogen effuser with liquid nitrogen inflow pipe; Described airtight cavity is located at the bottom of described electric charge detector, and is contact cooperation;
The top of described airtight cavity is provided with a groove, and described liquid nitrogen effuser extends in described groove.
2. particulate ion trap mass spectrometer according to claim 1, is characterized in that: the shape and size of described airtight cavity are consistent with the shape and size of described electric charge detector respectively.
3. particulate ion trap mass spectrometer according to claim 1, is characterized in that: described liquid nitrogen inflow pipe is connected with the bottom of described airtight cavity;
Described liquid nitrogen effuser is connected with the bottom of described airtight cavity, and extends to the top place of described airtight cavity.
4. particulate ion trap mass spectrometer according to claim 1, is characterized in that: the height of described airtight cavity is 10 ~ 20mm;
The height of described groove is 3 ~ 5mm, and the distance between the liquid nitrogen arrival end of described liquid nitrogen effuser and described groove top is 1 ~ 2mm.
5. particulate ion trap mass spectrometer according to claim 1, is characterized in that: described particulate ion trap mass spectrometer also comprises liquid nitrogen stream velocity control device;
Described liquid nitrogen stream velocity control device comprises liquid nitrogen container, flowmeter and microfluidic valve; Described liquid nitrogen inflow pipe is connected with described liquid nitrogen container, and described liquid nitrogen container is also connected with a nitrogen pipeline, described nitrogen pipeline is provided with successively described flowmeter and described microfluidic valve, and one end of nearly described liquid nitrogen container is located at by described flowmeter.
6. particulate ion trap mass spectrometer according to claim 1, is characterized in that: be provided with a temperature sensor bottom described electric charge detector.
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| CN201410005139.5A CN103745905B (en) | 2014-01-06 | 2014-01-06 | A kind of particulate ion trap mass spectrometer with low-temperature charge detector |
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| CN103745905B true CN103745905B (en) | 2016-03-16 |
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| GB201802917D0 (en) * | 2018-02-22 | 2018-04-11 | Micromass Ltd | Charge detection mass spectrometry |
| US11842891B2 (en) | 2020-04-09 | 2023-12-12 | Waters Technologies Corporation | Ion detector |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4473748A (en) * | 1981-03-18 | 1984-09-25 | Tokyo Shibaura Denki Kabushiki Kaisha | Neutral particle analyzer |
| US5640010A (en) * | 1994-08-03 | 1997-06-17 | Twerenbold; Damian | Mass spectrometer for macromolecules with cryogenic particle detectors |
| US5994694A (en) * | 1996-12-06 | 1999-11-30 | The Regents Of The University Of California | Ultra-high-mass mass spectrometry with charge discrimination using cryogenic detectors |
| CN102034668A (en) * | 2010-10-09 | 2011-04-27 | 中国科学院化学研究所 | Cylindrical ion trap mass spectrometer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7960689B2 (en) * | 2009-06-06 | 2011-06-14 | Andreas Landrock | Method and system for internal chemical ionization with water in ion trap mass spectrometry |
| GB201208812D0 (en) * | 2012-05-18 | 2012-07-04 | Micromass Ltd | Cryogenic collision cell |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4473748A (en) * | 1981-03-18 | 1984-09-25 | Tokyo Shibaura Denki Kabushiki Kaisha | Neutral particle analyzer |
| US5640010A (en) * | 1994-08-03 | 1997-06-17 | Twerenbold; Damian | Mass spectrometer for macromolecules with cryogenic particle detectors |
| US5994694A (en) * | 1996-12-06 | 1999-11-30 | The Regents Of The University Of California | Ultra-high-mass mass spectrometry with charge discrimination using cryogenic detectors |
| CN102034668A (en) * | 2010-10-09 | 2011-04-27 | 中国科学院化学研究所 | Cylindrical ion trap mass spectrometer |
Non-Patent Citations (1)
| Title |
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| "离子阱颗粒物质谱";熊彩桥等;《现代科学仪器》;20111031(第5期);第51-54页 * |
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