CN103033556B - The device of the direct electron spray ionisation of sample and mass spectrometric analysis method on micro-fluidic chip - Google Patents
The device of the direct electron spray ionisation of sample and mass spectrometric analysis method on micro-fluidic chip Download PDFInfo
- Publication number
- CN103033556B CN103033556B CN201210580139.9A CN201210580139A CN103033556B CN 103033556 B CN103033556 B CN 103033556B CN 201210580139 A CN201210580139 A CN 201210580139A CN 103033556 B CN103033556 B CN 103033556B
- Authority
- CN
- China
- Prior art keywords
- micro
- fluidic chip
- sample
- electrode
- chip
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention belongs to micro fluidic chip technical field, be specially a kind of device and mass spectrometric analysis method of the direct electron spray ionisation of sample on micro-fluidic chip.Apparatus of the present invention at least comprise: the three-dimensional manipulating platform placing micro-fluidic chip; Electrode and the pulsed high voltage generator of spray voltage are provided, described in provide the electrode of spray voltage and the liquid in micro-fluidic chip not to occur directly to contact; And be arranged on the other mass spectrum of ionization device.The present invention, without the need to making or connect original design of nozzle needle or change chip microchannel on micro-fluidic chip, can utilize the charge and discharge process of pulse voltage, to the solution example direct ionization in chip microchannel, carry out mass spectrophotometry.In addition, this device mesohigh motor without directly contacting, can not affect the original function of micro-fluidic chip with solution because chemical reaction occurs electrode.This device is simple to operate, convenient, is applicable to the direct ionization of sample on micro-fluidic chip, mass spectrophotometry.
Description
Technical field
The invention belongs to micro fluidic chip technical field, be specifically related to a kind of device and the mass spectrometric analysis method that can be used for the direct electron spray ionisation of sample on micro-fluidic chip.
Background technology
Microfluidic chip analysis take chip as operating platform, simultaneously based on analytical chemistry, with micro electronmechanical process technology for relying on, with microchannel network for architectural feature, target is the function whole laboratory, comprising sampling, dilution, reagent adding, reaction, separation, detection etc. is integrated on microchip, and can repeatedly use.Microfluidic chip analysis technology have liquid flow controlled, consume sample and the feature such as reagent is few, analysis speed is fast, it is analyzed while can carrying out up to a hundred samples within even shorter time a few minutes, and can the pre-service of canbe used on line sample and the overall process of analysis.Because it is in the great potential in the field such as biology, chemistry, medical science, develop into the new focus of the subject crossing researchs such as biology, chemistry, medical science, fluid, electronics, material, a machinery.Also be based on These characteristics, Flow Control analysis chip is called as " chip lab " (lab-on-a-chip) in the U.S., is called as " micro-confluence analysis chip " (micrototalanalyticalsystems) in Europe.
Nowadays, microfluidic chip technology is used for the emphasis that the research of life science develops into analysis field development already, and mass spectrum also extensively receives the welcome of scientist as a kind of sensitive detection means.Micro-fluidic chip and mass spectrographic coupling technique combine micro-fluidic chip and mass spectrographic advantage, become the focus of everybody research.In micro-fluidic and mass spectrographic interface, a lot of experts and scholars have been had to attempt.Beginning people are used in the aperture of chip and insert kapillary derivation analysis liquid, then through threeway, add that voltage and conventional electrospray nozzle needle carry out spraying thus carry out Mass Spectrometer Method, this mode of operation is simple, if but using that to receive the nozzle needle spraying of upgrading flow velocity routine unstable, the signal obtained is just very poor; The Lin Ping Cheng seminar of the Dalian Chemistry and Physics Institute improves this spray pattern, employs sheath flow liquid body, make spraying signal stabilization, but sheath flow liquid dilutes sample to a certain extent, sacrifices mass spectrographic sensitivity; The Luo Guoan seminar of Tsing-Hua University, processes porous membrane structure to realize current lead-through on micro-fluidic chip, and as chip and mass spectrographic interface, but job sequence is complicated, also not easily spread; In recent years, there is scholar to explore successively and mass spectrographic shower nozzle was integrated on chip, each own respective mode, but all needed extra operation relative complex, not easily grasped.
In commercialization, micro-fluidic chip has various business-like chip listing successively, comprise lectin chip, antibody chip etc., in chip mass spectrometry, Agilent company is proposed its chip mass spectrometer system at first, be electron spray Spray needle device be integrated in above chip itself, although Sensitivity Stability is all fine, price also costly.In order to address such a problem, the present invention is a kind of easy without the need to revising chip path, can complete sample ionization in passage, and for the technique device of mass spectrophotometry, simple to operate, with low cost, do not need extra processing chip system just well can complete Mass Spectrometer Method.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of devices and methods therefor of the direct electron spray ionisation of sample on micro-fluidic chip, is problem existing in mass spectrometry in order to solve existing micro fluidic device.
For achieving the above object and other relevant objects, the invention provides a kind of device of the direct electron spray ionisation of sample on micro-fluidic chip, this device at least comprises:
For placing the three-dimensional manipulating platform of micro-fluidic chip;
The electrode of spray voltage is provided; This electrode is fixed on micro-fluidic chip inside, or is placed in outside chip, independent setting;
The pulsed high voltage generator of spray voltage is provided, in order to make to produce induced charge in the solution in the microchannel of micro-fluidic chip in charge and discharge process, thus forms spraying;
And be arranged at the other mass spectrum of ionization device, for mass spectrophotometry.
In this device, described electrode and the liquid in micro-fluidic chip passage do not occur directly to contact.
In this device, described pulsed high voltage generator is direct current pulse power source, and output mode can be single pulse or continuous impulse.
In this device, without the need to installing nozzle needle or the design of amendment chip channel on chip additional.
The present invention also comprises the mass spectrometric analysis method of the direct electron spray ionisation of sample on micro-fluidic chip, and concrete steps are:
(1) electrode being connected with high-voltage pulse power source is placed in the back side (chip front side is towards mass spectrum injection port) of micro-fluidic chip microchannel outlet, in electrode and passage, solution spacing is 0.5 ~ 2mm;
(2) regulate three-dimensional manipulating platform, micro-fluidic chip outlet is adjusted to apart from mass spectrum injection port 5 ~ 10mm;
(3) fluid sample is passed in micro-fluidic chip;
(4) provide high-voltage pulse signal to described electrode, in electrode and passage, between solution, form electric capacity; In charge and discharge process, the solution surface of channel exit produces a large amount of electric charge, and electron spray phenomenon occurs, thus the sample in ionization microchannel, carry out mass spectrophotometry.
The present invention without the need to revising the via design in chip, can complete sample in passage ionization and for mass spectrophotometry.Simple to operate, with low cost, the coupling of microfluidic chip technology and analytical technique of mass spectrum just well can be realized without the need to extra processing chip.
Accompanying drawing explanation
Fig. 1 is apparatus of the present invention structural diagrams.Wherein, (a) is the device schematic diagram of the direct electron spray ionisation of sample on micro-fluidic chip of the present invention; B () is placed in outside chip for electrode, the independent schematic diagram arranged; (c) for electrode be fixed on micro-fluidic chip inner time device schematic diagram.
Fig. 2 is the device schematic diagram of the direct electron spray ionisation of another sample on micro-fluidic chip of the present invention.
Fig. 3 is the present invention when not adopting the design of sample cell in exit, microchannel, the device schematic diagram of the direct electron spray ionisation of sample on micro-fluidic chip.
Fig. 4 be the present invention when microchannel is designed to groove, interrupt from groove the device schematic diagram of the direct electron spray ionisation of sample for micro-fluidic chip extracting sample ionization.
Number in the figure: 1 is high-voltage pulse power source, 2 is electrode, and 3 is micro-fluidic chip, and 4 is microchannel, and 5 is mass spectrum, and 6 is platform, and 7 is insulation course.
Embodiment
Below by way of instantiation, embodiments of the present invention are described, those skilled in the art the content disclosed by this instructions can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this instructions also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Consult shown in Fig. 1 to Fig. 4.It should be noted that, the diagram provided in the present embodiment only illustrates basic conception of the present invention in a schematic way, then only the assembly relevant with the present invention is shown in graphic but not component count, shape and size when implementing according to reality is drawn, it is actual when the implementing kenel of each assembly, quantity and ratio can according to needing random change, and its assembly layout kenel also may be more complicated.
Can without the need to changing micro-fluidic chip design in order to realize one, the method and apparatus of microflow control technique and mass-spectrometric technique coupling can be realized preferably, the invention provides a kind of pulse power that utilizes, the mass spectrum electron-spray ionization device directly contacted without the need to electrode and fluid sample in passage and mass spectrometric analysis method thereof.This device is simple to operate, with low cost, can complete the coupling of various types of micro-fluidic chip and analytical technique of mass spectrum preferably.
The present invention relates to a kind of easy without the need to revising chip path, sample ionization in passage can be completed, and for the technique device of mass spectrophotometry, simple to operate, with low cost, do not need extra processing chip system just well can complete Mass Spectrometer Method.Device involved in the present invention mainly comprises: the three-dimensional manipulating platform placing micro-fluidic chip; Electrode and the pulsed high voltage generator of spray voltage are provided; The described electrode of spray voltage and the liquid in micro-fluidic chip of providing does not occur directly to contact; And be arranged on the other mass spectrum of ionization device.
Described micro-fluidic chip can be fixed on three-dimensional regulation platform, regulates the position between its exit, microchannel and mass spectrum, makes channel outlet be in suitable position, can the sample of ionization be made to enter mass spectrophotometry preferably after spraying is formed.This device uses the high-voltage power supply that can produce pulse direct current, and output frequency is 1Hz ~ 10kHz, and output voltage is at 3 ~ 15kV, and concrete output frequency and output voltage specifically need regulate according to analyzed sample type and flow velocity etc.Described micro-fluidic chip need select the good material of insulativity, when solution flows near exit in passage, forms electric capacity between solution and electrode.
A mass spectrometric analysis method for the direct electron spray ionisation of sample on micro-fluidic chip, concrete steps are:
1) electrode being connected with high-voltage pulse power source is placed in the back side (chip front side is towards mass spectrum injection port) of chip microchannel outlet, in electrode and passage, solution spacing is 0.5 ~ 2mm;
2) regulate three-dimensional manipulating platform, chip outlet is adjusted to apart from mass spectrum injection port 5 ~ 10mm;
3) described fluid sample is passed in micro-fluidic chip;
4) provide high-voltage pulse signal to described electrode, in electrode and passage, between solution, form electric capacity.In charge and discharge process, the solution surface of channel exit produces a large amount of electric charge, and electron spray phenomenon occurs, thus the sample in ionization microchannel, carry out mass spectrophotometry.
embodiment 1
As shown in Figure 1, micro-fluidic chip 3, is fixed on its three-dimensional regulation platform 6.Regulate three-dimensional regulation platform, make the outlet of its microchannel 4 be positioned at 5 ~ 10mm place before the injection port of mass spectrum 5, so that can ionization preferably when ionizing.Testing liquid is passed into sample microchannel 4, by the exit of Liquid transfer to microchannel.Make pulse power supply 1, export the high-voltage signal of pulse direct current on pole plate 2, output frequency is 1Hz ~ 10kHz, and output voltage is at 3 ~ 15kV, and concrete output frequency and output voltage specifically need regulate according to analyzed sample type and flow velocity etc.
When power supply 1 is in the rising edge of pulse output, solution can form electrostatic double layer and (assemble negative charge near electrode place because of charging, positive charge is assembled) away from electrode place, a large amount of positive charge can assembled near the exit, microchannel of mass spectrum injection port (the injection port earthing of casing), and Taylor centrum is formed under the effect of surface tension and coulomb repulsion, there is electron spray, thus make the sample molecule positively charged in solution.When power supply 1 is in the negative edge of pulse output, the positive charge that electrode 2 gathers can flow through the resistance (adopting 500M Ω in this device) of ground connection, completes electric discharge.In discharge process, the solution in passage can gather negative charge at channel exit.On battery lead plate, discharge time is shorter, and the negative charge that exit, microchannel is assembled will be more.Now, just easily make sample molecule electronegative.
As mentioned above, this device can make testing sample alternately produce positive ion and negative ion in a pulsed fashion.If the mass spectrum 5 of institute's coupling is placed in positive ion detecting pattern, then the positive ion signal of sample in passage can be detected; If mass spectrometer is placed in anionic textiles pattern, then can detect the negative ion signals of sample.If the mass spectrometer of institute's coupling has (or can switch fast) simultaneously carry out positive and negative ion mode detection, then in can producing sample in the lump, positive and negative ion detects.
embodiment 2
The present embodiment and embodiment 1 device similar, difference is only that the design in the exit, microchannel of the micro-fluidic chip of institute's coupling is different from shown in example 1.As shown in Figure 2, all there is opening in the micro-pond of the sample in exit, microchannel at the upper and lower faces of chip.Now need at electrode 2 Surface coating insulation course 7(thickness 0.5mm ~ 2mm).The electrode 2 being coated with insulation course 7 is placed in one end of microchannel outlet, the other end points to mass spectrum injection port.As described in embodiment 1, sample flows into behind the micro-pond of sample through sample microchannel 4, under the effect of the pulse high-voltage of power supply 2 output, produces sample ions, detects for mass spectrum 5.
embodiment 3
The present embodiment and embodiment 1 device similar, difference is only that the design in the exit, microchannel of the micro-fluidic chip of institute's coupling is different from shown in example 1.The design not adopting the micro-pond of sample in the exit of sample microchannel 4, sample directly flows out in microchannel.Now, as shown in Figure 3, electrode 2 need be placed on the chip sides near exit, sample microchannel 4.As described in embodiment 1, sample, after sample microchannel 4 flow to channel exit, under the effect of the pulse high-voltage of power supply 2 output, produces sample ions, detects for mass spectrum 5.
embodiment 4
The present embodiment and embodiment 1 device similar, difference is only that the design of the microchannel of the micro-fluidic chip of institute's coupling is different from shown in example 1.As shown in Figure 3, on this kind of chip, sample microchannel 4 is open type groove.The present invention also can carry out desorb and ionization in the stage casing of this kind of passage to liquid in passage.Now, electrode 2 need the corresponding chip back position of the section of being placed on and sampling.As described in embodiment one, sample flows through sampling section during through sample microchannel 4, under the pulse high-voltage effect that power supply 2 exports, produce sample ions, detect for mass spectrum 5.
As described in above-described embodiment 1 ~ example 4, the present invention near micro-fluidic chip exit, can utilize the charge and discharge process to electrode of high voltage pulse, makes solution example can make sample generation electron spray without the need to directly contacting with electrode, thus ionized sample, carry out Mass Spectrometer Method.In the method, charged electrode does not directly contact with solution to be measured, can not affect the original function of micro-fluidic chip because chemical reaction occurs electrode.In addition, this device can adapt to the via design of the micro-fluidic chip of various ways, without the need to carrying out extra amendment to the sample channel of micro-fluidic chip, can realize the coupling of microfluidic chip technology and analytical technique of mass spectrum preferably
In sum, the present invention effectively overcomes various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (5)
1. the device of the direct electron spray ionisation of sample on micro-fluidic chip, it is characterized in that, this device at least comprises:
For placing the three-dimensional manipulating platform of micro-fluidic chip;
The electrode of spray voltage is provided; This electrode is fixed on micro-fluidic chip inside, or is placed in outside chip, independent setting;
The pulsed high voltage generator of spray voltage is provided, in order to make to produce induced charge in the solution in the microchannel of micro-fluidic chip in charge and discharge process, thus forms spraying;
And be arranged at the other mass spectrum of ionization device, for mass spectrophotometry;
Wherein, described for providing the electrode of spray voltage and the liquid in micro-fluidic chip not to occur directly to contact.
2. the device of the direct electron spray ionisation of sample on micro-fluidic chip according to claim 1, it is characterized in that: described power supply is DC pulse high-voltage power supply, output mode is single pulse or continuous impulse.
3. the device of the direct electron spray ionisation of sample on micro-fluidic chip according to claim 2, is characterized in that: the output frequency of described DC pulse high-voltage power supply is 1Hz ~ 10kHz, and output voltage is 3 ~ 15kV.
4. the device of the direct electron spray ionisation of sample on micro-fluidic chip according to claim 1, is characterized in that: described power supply is AC power.
5. a mass spectrometric analysis method for the direct electron spray ionisation of device sample on micro-fluidic chip adopting one of claim 1-3 described, is characterized in that concrete steps are:
(1) electrode being connected with high-voltage pulse power source is placed in the back side of micro-fluidic chip microchannel outlet, micro-fluidic chip is just facing to mass spectrum injection port, and in electrode and passage, solution spacing is 0.5 ~ 2mm;
(2) regulate three-dimensional manipulating platform, micro-fluidic chip outlet is adjusted to apart from mass spectrum injection port 5 ~ 10mm;
(3) fluid sample is passed in micro-fluidic chip;
(4) provide high-voltage pulse signal to described electrode, in electrode and passage, between solution, form electric capacity; In charge and discharge process, the solution surface of channel exit produces a large amount of electric charge, and electron spray phenomenon occurs, thus the sample in ionization microchannel, carry out mass spectrophotometry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210580139.9A CN103033556B (en) | 2012-12-28 | 2012-12-28 | The device of the direct electron spray ionisation of sample and mass spectrometric analysis method on micro-fluidic chip |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210580139.9A CN103033556B (en) | 2012-12-28 | 2012-12-28 | The device of the direct electron spray ionisation of sample and mass spectrometric analysis method on micro-fluidic chip |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103033556A CN103033556A (en) | 2013-04-10 |
| CN103033556B true CN103033556B (en) | 2016-04-13 |
Family
ID=48020671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210580139.9A Expired - Fee Related CN103033556B (en) | 2012-12-28 | 2012-12-28 | The device of the direct electron spray ionisation of sample and mass spectrometric analysis method on micro-fluidic chip |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103033556B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109331893B (en) * | 2018-11-22 | 2021-07-23 | 复旦大学 | Micro-fluidic free flow paper chromatography array spray mass spectrometry combined device |
| CN110060916A (en) * | 2019-04-09 | 2019-07-26 | 武汉大学 | A kind of mass spectrometer for the online photochemical reaction research of high-throughput drop |
| CN110491768A (en) * | 2019-09-17 | 2019-11-22 | 中国科学院成都生物研究所 | A kind of microballon electron spray array high throughput analysis device and method |
| CN111308000A (en) * | 2020-03-24 | 2020-06-19 | 宁波大学 | Mass spectrometry system based on electrospray |
| CN113327836B (en) * | 2021-05-28 | 2022-11-18 | 深圳先进技术研究院 | Sample loading device for mass spectrometer |
| CN114496717A (en) * | 2022-01-18 | 2022-05-13 | 中国科学院成都生物研究所 | Electrospray excitation device and ionization method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1437760A (en) * | 1999-12-30 | 2003-08-20 | 阿德维昂生物科学公司 | Multiple electrospray device, system and methods |
| CN1498129A (en) * | 2001-01-26 | 2004-05-19 | 阿德维昂生物科学公司 | Robotic autosampler for automated electrospray from microfluidic chip |
| CN102466655A (en) * | 2010-11-16 | 2012-05-23 | 上海华质生物技术有限公司 | Detection device and method of combined use of micro-fluidic chip and mass spectrometry |
| CN102568998A (en) * | 2011-12-22 | 2012-07-11 | 清华大学 | Non-contact alternating current electrospray ionization device and method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7007710B2 (en) * | 2003-04-21 | 2006-03-07 | Predicant Biosciences, Inc. | Microfluidic devices and methods |
| US20050072915A1 (en) * | 2003-10-07 | 2005-04-07 | Biospect Inc. | Methods and apparatus for self-optimization of electrospray ionization devices |
| US20060060769A1 (en) * | 2004-09-21 | 2006-03-23 | Predicant Biosciences, Inc. | Electrospray apparatus with an integrated electrode |
| CN101599409B (en) * | 2009-07-23 | 2014-07-30 | 上海华质生物技术有限公司 | Electric spray ion source |
-
2012
- 2012-12-28 CN CN201210580139.9A patent/CN103033556B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1437760A (en) * | 1999-12-30 | 2003-08-20 | 阿德维昂生物科学公司 | Multiple electrospray device, system and methods |
| CN1498129A (en) * | 2001-01-26 | 2004-05-19 | 阿德维昂生物科学公司 | Robotic autosampler for automated electrospray from microfluidic chip |
| CN102466655A (en) * | 2010-11-16 | 2012-05-23 | 上海华质生物技术有限公司 | Detection device and method of combined use of micro-fluidic chip and mass spectrometry |
| CN102568998A (en) * | 2011-12-22 | 2012-07-11 | 清华大学 | Non-contact alternating current electrospray ionization device and method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103033556A (en) | 2013-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103033556B (en) | The device of the direct electron spray ionisation of sample and mass spectrometric analysis method on micro-fluidic chip | |
| US11476106B2 (en) | Methods and systems for increasing sensitivity of direct sampling interfaces for mass spectrometric analysis | |
| CA2955865C (en) | Ion funnel for efficient transmission of low mass-to-charge ratio ions with reduced gas flow at the exit | |
| CA2401772C (en) | Tandem high field asymmetric waveform ion mobility spectrometry (faims)/ion mobility spectrometry | |
| CN108417473B (en) | Concentric APCI surface ionization ion source and ion guide and methods of use thereof | |
| CN102466655B (en) | A kind of micro-fluidic chip and mass spectrometry pick-up unit and method | |
| CN103048378B (en) | MS acquisition and ionization device and method thereof for the ionization of sample extracting directly | |
| WO2005050159A2 (en) | Ion mobility spectrometry method and apparatus | |
| CN104576287B (en) | Ion source system and mass spectrometer for atmospheric pressure interface | |
| EP2793248A2 (en) | Multimode ionization device | |
| CN101881752A (en) | Micro two-dimensional ionic migration spectrometer | |
| CN109603932B (en) | Double-focusing micro-fluid chip | |
| CN104124131A (en) | Mass spectrum ion source and mass spectrometer | |
| EP2898308A1 (en) | Sample probe inlet flow system | |
| CN208336147U (en) | The plasma ionization device of Atmospheric particulates | |
| CN109887829A (en) | A kind of ionization source device detected simultaneously based on VUV lamp negative ions | |
| CA2525095A1 (en) | Ion mobility separation devices | |
| JP2014512000A (en) | Method for ionizing a liquid sample by dielectric insulating electrospray ionization and then analyzing the mass spectrum of the generated sample ion | |
| CN104237371A (en) | Simple device for realizing real-time direct injection analysis of mass spectrometer and application of simple device | |
| CN106463330B (en) | Multidimensional ion isolation | |
| Tsao et al. | A piezo-ring-on-chip microfluidic device for simple and low-cost mass spectrometry interfacing | |
| CN218157732U (en) | Gas chromatography-mass spectrometer with real-time online gas detection function | |
| CN106601583A (en) | Space focusing conical high field asymmetric waveform transference tube | |
| WO2015085651A1 (en) | Quadrupole rod mass analysis device for bidirectional introduction and transmission of ions | |
| CN209544279U (en) | A kind of chemical reaction intermediate Mass Spectrometer Method device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160413 Termination date: 20181228 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |