CN206595226U - A kind of mass spectrograph of electrospray ion source device and detectable reactive intermediate - Google Patents
A kind of mass spectrograph of electrospray ion source device and detectable reactive intermediate Download PDFInfo
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- CN206595226U CN206595226U CN201720272415.3U CN201720272415U CN206595226U CN 206595226 U CN206595226 U CN 206595226U CN 201720272415 U CN201720272415 U CN 201720272415U CN 206595226 U CN206595226 U CN 206595226U
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Abstract
The utility model discloses a kind of electrospray ion source device and the mass spectrograph of detectable reactive intermediate.Wherein, the electrospray ion source device includes the sampling device for sample introduction, for the electrospray device for spraying the Part I sample in sampling device in the form of electron spray, and curved surface chemical reactor, the curved surface of the curved surface chemical reactor is arranged on the jet path of electron spray.Curved surface chemical reactor is arranged on the jet path of the electron spray of electrospray ion source device by the utility model so that chemical reaction occurs inside ion gun, monitoring chemical reaction process and can detect the short reactive intermediate of existence time in real time；And interference of the electron spray high voltage to chemical reaction is avoided, make the detection of electrospray ionization mass spectrum more accurate, can more reflect the real conditions of system to be detected.
Description
Technical field
The utility model is related to field of mass spectrometry, and in particular to a kind of electrospray ion source device and detectable reactive intermediate
Mass spectrograph.
Background technology
Organic chemistry is the structure, property, the subject prepared for studying organic compound, is epochmaking one point in chemistry
Branch.The research of organic chemical reactionses mechanism can help us to be better understood from chemical reaction, Rule Summary, and be possible to chemistry
Whether reaction is carried out and product structure property etc. is predicted, therefore is one important content of organic chemistry subject, is being had
Occupied an important position in chemical machine development.
Organic chemical reactionses study mechanism mainly includes calculating chemical method and chemical experiment method.Calculate chemical method base
In quantum chemistry principle, using computer simulation molecular structure, the reaction mechanism mechanism of reaction, the important information such as energy, simulation chemical reaction
Overall process, to deepen the understanding to reaction.
Test method mainly uses the instrument monitoring such as nuclear-magnetism, mass spectrum, infrared course of reaction or detection, analysis experiment knot
Really.And then the important informations such as reaction rate, product, accessory substance, intermediate are obtained, the scientists pry reaction mechanism mechanism of reaction is helped, is known
Know reaction principle.
Experimental method is to study the basis of chemical reaction mechanism, but is due to laboratory apparatus sensitivity, resolution ratio, time chi
The limitation of degree etc., it is difficult to monitoring reaction course, in addition high activity reaction intermediates helpful to understanding reaction mechanism in real time
Plant and also be difficult to monitoring.Therefore exploitation can monitoring reaction course in real time, the instrument of catching reaction active intermediate kind seems particularly
It is important, there is strategic directing meaning to the research of organic reaction mechanism.
Mass spectrum (being called mass spectrography) is a kind of and spectrum spectrum method arranged side by side, refers to be widely used in respectively on ordinary meaning
By preparing, separating, detect gaseous ion come a kind of know-how of authenticating compound in individual ambit.Mass spectrography is once
Abundant structural information can be provided in analysis.In numerous analysis test methods, mass spectrometric methods be considered as it is a kind of simultaneously
The universality method for possessing high specific and high sensitivity and being widely applied.Mass spectrometer is general by Sample introduction system
The part such as system, ion gun, mass analyzer, detector, data handling system is constituted.
Mass spectral analysis is a kind of analysis method of measurement ion mass-to-charge ratio (mass-charge ratio), and its general principle is to make examination
Each component is ionized in an ion source in sample, generates the charged ion of different mass-to-charge ratioes, the effect of accelerated electric field, formed from
Beamlet, into mass analyzer.In the mass analyser, electric field or magnetic field is recycled to make the ion of different mass-to-charge ratioes spatially
Or separated on the time, or through the mode of filtering, they are respectively focused on detector and mass spectrogram is obtained, and then analyze true
Fixed its quality, structural information.
Electrospray ionization mass spectrum uses electrospray ion source device.Electron spray ionisation is a kind of soft ionization method, compared to tradition
Mass spectrum ionizes mode, and it can more fully retain analyte molecules structure, therefore have very big in the analysis of large biological molecule
Advantage.Further, since its soft ionization feature, point minor structures such as unstable molecule, high activity species can be retained to a certain extent,
A kind of strong instrument is provided for the research of organic chemical reactionses mechanism.But the reactive intermediate much chemically reacted is deposited
It is extremely short in the time, in Millisecond even Microsecond grade.And electrospray ionization mass spectrum sample introduction pipeline is longer, sample injection time typically second rank with
On, it is difficult to detect the short reactive intermediate of existence time.
There is high voltage in other electron spray process, have electrochemical reaction, and electrochemical reaction is possible to system
Interfere, many reaction intermediate active species are possible to further react in pipeline, therefore testing result is difficult anti-
Real system is answered, this brings bigger difficulty to study on mechanism.
Therefore, the active intermediate kind and it is possible to prevente effectively from electrochemical reaction that can detect that existence time is short are developed
The electrospray ionization mass spectrum detection method of interference is to carry out chemical reaction mechanism research urgent problem using electrospray ionization mass spectrum.
Utility model content
The application provides the mass spectrograph of a kind of electrospray ion source device and detectable reactive intermediate, is deposited in order to detect
In the chemical reactivity intermediate that the time is short.
According to of the present utility model in a first aspect, the utility model provides a kind of electrospray ion source device, including for
The sampling device of sample introduction, for the electrospray device for spraying the Part I sample in sampling device in the form of electron spray,
And curved surface chemical reactor, the curved surface of the curved surface chemical reactor is on the jet path of electron spray.
Described electrospray ion source device, wherein, the curved surface that the curved surface chemical reactor is contacted with electron spray is used for
Part II sample is loaded, the Part II sample can chemically react with the Part I sample.
Described electrospray ion source device, wherein, the electron spray incides angle on the curved surface for 100 ° extremely
150°。
Described electrospray ion source device, wherein, the electrospray ion source device also includes reactor base, described
Curved surface chemical reactor is arranged in the reactor base, and the reactor base can adjust curved surface chemical reactor predetermined
Displacement on direction, the predetermined direction includes the one or more in X-direction, Y direction, Z-direction.
Described electrospray ion source device, wherein, the sampling device includes sampling pump, injection port and sample feeding pipe, institute
Stating electrospray device includes capillary pipe spray pin and direct current voltage generator, and the injection port is sprayed by sample feeding pipe and capillary
Mist pin is connected；The sampling pump is used to convey the Part I sample in sample feeding pipe, it is sprayed from capillary pipe spray pin, directly
Flow device for generating voltage and high voltage electric field is applied to capillary pipe spray pin, make Part I sample after capillary pipe spray pin, mist
The tiny droplet with electric charge of chemical conversion and ejection, form electron spray.
Described electrospray ion source device, wherein, the Part I sample is to include the molten of Part I reactant
Liquid, Part II sample includes Part II reactant that can be with Part I reactant reaction.
Described electrospray ion source device, wherein, the curved surface that the curved surface chemical reactor is contacted with electron spray is interior
Concave curved surface.
Described electrospray ion source device, wherein, the curved surface that the curved surface chemical reactor is contacted with electron spray is corresponding
Central angle be 30 ° to 90 °.
Described electrospray ion source device, wherein, the reactor base includes：It is fixed on electrospray ion source device
Pedestal on cavity inner wall, is vertically arranged on the pedestal and is vertically directed part, is arranged in the way of it can move described
It is vertically directed the support member on part, and reactor support bar；Being horizontally disposed with the support member has guide groove, the reactor
Support bar is arranged in guide groove in the way of it can move.
According to second aspect of the present utility model, the utility model provides a kind of matter of detectable reactive intermediate
Spectrometer, including：Mass analyzer, ion detector and electrospray ion source device as described above；
The mass analyzer is by the mixture of Part I sample and Part II example reaction by mass-to-charge ratio point
Open, the ion detector is detected to the ion after mass analyzer is separated.
The beneficial effects of the utility model：Curved surface chemical reactor is arranged on to the electron spray of electrospray ion source device
On jet path, due to chemical reaction occur inside ion gun, can in real time monitoring chemical reaction process and detect existence time
Short reactive intermediate；And interference of the high voltage to chemical reaction is avoided, make the detection of electrospray ionization mass spectrum more smart
Really, the real conditions of system to be detected can more be reflected.
Brief description of the drawings
The operating diagram for the embodiment of electrospray ion source device one that Fig. 1 provides for the utility model；
In the embodiment of electrospray ion source device one that Fig. 2 provides for the utility model, the stereogram of reactor base；
In the embodiment of electrospray ion source device one that Fig. 3 provides for the utility model, the composition figure of reactor base；
Embodiment
The application is described in further detail below by embodiment combination accompanying drawing.
The term definition used in the utility model：
Electron spray-solvent flows through capillary with ionic or polar sample molecule, and it is high to add one in the exit of capillary
Piezoelectric field, in the presence of Coulomb force, sample can spray in the exit of capillary, be atomized into tiny with electric charge
Droplet, this phenomenon is referred to as electron spray.
Electrospray ion source device-realize the ion gun that material molecule is ionized using electron spray principle, is electrospray ionization mass spectrum
Significant components.
Electrospray ionization mass spectrum-mass spectrum equipped with electrospray ion source device is referred to as electrospray ionization mass spectrum.
Reaction mechanism-reaction mechanism be used in chemistry describing a certain chemical change via whole elementary reactions.Though
The material transformation that so whole chemical change occurs may it is obvious that but in order to verify the reaction mechanism of this process, usually need
Other means are wanted to verify.
Organic chemical reactionses intermediate-and in the organic chemical reactionses of part, reactant is not to directly generate product, and
It is to generate product by several intermediate structures, these intermediate structures are exactly organic reaction intermediate, their generally activity are very high
It is very unstable, it is also difficult to which that detection is determined, but is the important evidence for understanding organic reaction mechanism.
Curved surface chemical reactor is introduced electrospray ion source device by the utility model, while progress is chemically reacted,
The drop of reaction system mixture immediately enters mass spectrometer and is detected.Reaction is shortened to occur to the detected time, from
And the short reactive intermediate of existence time yardstick can be detected.
In the utility model embodiment one, referring to Fig. 1, the utility model provides a kind of electrospray ion source device, bag
Include housing (not shown), sampling device (not shown), electrospray device 10 and curved surface chemical reactor 30.It is curving
The curved surface for learning reactor 30 is located on the jet path of (being arranged on) electron spray 20.
Sampling device is used for sample introduction, specifically includes sampling pump, injection port and sample feeding pipe.
Electrospray device 10 is used to spray the Part I sample in sampling device in the form of electron spray；It includes hair
Tubule spray needle and direct current voltage generator, injection port are connected by sample feeding pipe with capillary pipe spray pin；Sampling pump is used for pump
The Part I sample in sample feeding pipe is sent, it is sprayed from capillary pipe spray pin；Direct current voltage generator is sprayed to capillary
Mist pin applies high voltage electric field, makes Part I sample 110 after capillary pipe spray pin, is atomized into the tiny mist with electric charge
Drip and spray, form electron spray 20.
The curved surface 310 that curved surface chemical reactor 30 is contacted with electron spray 20 is used to load Part II sample 320, second
Sample 320 is divided to be chemically reacted with Part I sample 110.
Enclosure interior is provided with cavity, and the spout and curved surface chemical reactor 30 of capillary pipe spray pin are arranged at cavity
It is interior.
Curved surface chemical reactor 30 is arranged on inside electrospray ion source device by the utility model, Part I sample with
Chemically reacted after the mixing of Part II sample, occur to the detected time to greatly shorten from reaction, mass spectrum can be detected
To the short reactivity species of existence time yardstick, and generation and the synchronous progress of detection are reacted, can monitored in real time chemical anti-
The progress answered；In addition, reaction occurs near curved surface chemical reactor 30, away from spray capillary high voltage electric field region, keep away
The generation of electrochemical reaction is exempted from.Therefore, this method can monitoring chemical reaction in real time, during catching reaction in various activity
Mesosome, so as to provide a kind of strong analysis tool for organic chemistry study mechanism.
Further, the face 310 that curved surface chemical reactor 30 is contacted with electron spray 20 is inner sunken face.Using inner sunken face
There is following advantage：Relative to horizontal surface (plane) or convex surface, load sample (the Part II sample on inner sunken face surface
320) it is more difficult to be washed, the monitoring of long period can be provided；Further, since ion signal intensity and spraying connect with curved surface
Tactile angle is relevant, and curved surface has bigger adjustable extent, it is easier to carry out the parameter optimization in terms of angle.It is preferred that, institute
The circular arc that inner sunken face can be indent is stated, the angle that electron spray is incided on the curved surface is relevant with reaction system, optimal
Incident angle is preferably between 100 ° to 150 °, in other words, with injection road on the curved surface 310 of the curved surface chemical reactor 30
Angle formed by the tangent line and jet path of the point that footpath is overlapped is 100 ° to 150 °.
For reduction detection limit, strengthen mass signal, every geometric parameter of curved surface chemical reactor 30 is optimized.
Specifically, the corresponding central angle of curved surface 310 is preferably 30 ° to 90 °；The placement of Part II sample 320 has been ensured, can have been made again
The mixture of reaction enters mass analyzer entrance.
Placement Part II sample 320 is optimal at the port of export (right hand edge in Fig. 1) 0-6mm positions on curved surface 310.
This fragment position can react Part I sample and Part II sample 320, be stayed in after reducing reaction to greatest extent again
Time in ion source chamber body, improve mass signal intensity.
The vertical range of the port of export of capillary pipe spray pin to curved surface 310 is preferably 2-10mm, i.e. capillary pipe spray pin
The vertical range of the port of export to Part II sample 320 is preferably 2-10mm, the mass signal intensity and mass spectrum of this distance segment
Figure is optimal.
Referring to Fig. 2, electrospray ion source device also includes reactor base, reactor base is fixed in cavity.It is bent
Face chemical reactor 30 is arranged in reactor base, and reactor base can adjust curved surface chemical reactor 30 in a predetermined direction
Displacement, predetermined direction include X-direction, Y direction, Z-direction in one or more, it is, of course, also possible to including curved surface
The rotationally clockwise direction of chemical reactor 30, counter clockwise direction etc..Curved surface chemical reactor is adjusted by reactor base
30 position, provides convenience to detection.
Specifically, reactor base includes：The pedestal 410 on electrospray ion source device cavity inner wall is fixed on, vertically
It is arranged on pedestal 410 and is vertically directed part 420, the support member being vertically directed on part 420 is arranged in the way of it can move
430, and reactor support bar 440；Being horizontally disposed with support member 430 has guide groove 431, one end of reactor support bar 440
It is arranged in the way of it can move in guide groove 431.Thus, the present embodiment is by being vertically directed part 420 and support member 430
Coordinate, the movement (Z axis) of the in the vertical direction of curved surface chemical reactor 30 is realized, by reactor support bar 440 in guide groove
Moving horizontally in 431 realizes the position adjustment (X-axis) of curved surface chemical reactor 30 in the horizontal direction, curved surface chemical reactor
30 move the position adjustment of achievable Y direction along the axial direction of reactor support bar 440, are easy to optimization curved surface chemical reaction
The position of device 30.
Referring to Fig. 3, pedestal 410 can be fixed on the side-wall shaft in ion source chamber body.Be vertically directed part 420 be provided with it is recessed
Groove guide rail 421, one end of support member 430 is adapted to grooved rail 421, so as to be slided vertically in grooved rail 421.Guide groove
431 are arranged on the other end of support member 430, and the present embodiment is rectangular channel.Reactor support bar 440 includes rod member 441, fixed successively
Block 442 and sliding block 443 on rod member 441.Sliding block 443 is adapted to guide groove 431, is slided in guide groove 431.Block
442 prevent reactor support bar 440 from being dropped through guide groove 431.
Curved surface chemical reactor 30 is provided with the mounting hole being adapted to rod member 441.It is preferred that, curved surface chemical reactor 30 is
Column, its side sets the curved surface of an indent.The optional stainless steel of material of curved surface chemical reactor 30, lucite gathers
Tetrafluoroethene etc..It is preferred that, during mass spectrum positive ion mode (electron spray 20 is cation), the material of curved surface 310 is lucite
Curved surface chemical reactor 30 is preferable；During negative ion mode (electron spray 20 is anion), the material of curved surface 310 is polytetrafluoroethylene (PTFE)
Curved surface chemical reactor 30 is preferable.
Because curved surface chemical reactor 30 is fixed in reactor base, angle can be automatically adjusted, is convenient for changing.Curved surface
Chemical reactor 30 is adjusted after good position in reactor base, can be fixed by the one or more in bolt, stud, engaging
Mode is fixed.
Certainly, above-mentioned vertical, level, X-axis, Y-axis, Z axis etc. are putting position according to Fig. 2 coordinates in other words
It is fixed that system comes, and is for the ease of the concrete structure of description reactor base.Actually reactor base might not in cavity
In the putting position shown in Fig. 2.
Further, Part I sample is to include the solution of Part I reactant, and Part II sample is comprising can be with
The Part II reactant of Part I reactant reaction.Part II sample can be solid or liquid etc., and it is coated in song
On face 310.Part I reactant can only include a kind of reactant, can also include a variety of reactants；Include a variety of reactants
When, do not react between a variety of reactants.Certainly, Part II reactant can only include a kind of reactant, can also include
A variety of reactants；During comprising a variety of reactants, do not reacted between a variety of reactants.That is, the utility model is by will be to be checked
The reactant for surveying chemical reaction is divided into two parts, and this two parts reactant reacts after being contacted on curved surface chemical reactor, immediately
Detected into mass spectrograph, realize the real-time detection of chemical reaction.
It is anti-with two kinds when being applied to organic chemical reactionses monitoring in real time and the detection unstable chemical reaction intermediate of high activity
Exemplified by the reaction for answering thing, i.e., Part I reactant contains a kind of reactant, and Part II reactant includes a kind of reactant.By its
A kind of middle reactant is coated on the curved surface of curved surface chemical reactor 30；Another reactant is dissolved in solvent, from injection port injection,
Then it is sprayed onto with Sprayable on the curved surface of curved surface chemical reactor 30, the reactant on curved surface is dissociateed and comes and further sends out
Raw reaction, final reaction mixture is by Mass Spectrometer Method.If the reactions of three kinds of reactants will can then not react wherein
Two kinds of reactant mixing are put into solvent or are placed on curved surface, method of testing is ibid as an entirety.
The electrospray ion source device that the utility model is provided, can also be to material surface sample, and biological tissue samples are straight
Connect analysis.In mass spectral analysis, it is sometimes desirable to which some surfaces are analyzed with (such as explosive substance detection, Pesticides Testing
Deng), and conventional method must be handled surface in advance, and surface mass is transferred in solvent and detected.Traditional detection
The low inconvenience of means efficiency, and solvent has diluting effect, causes ion signal intensity decreases.
And the electrospray ion source device for using the utility model to provide easily can be detected directly to surface, no
Sample pretreatment is needed, is provided convenience for detection.Experimentation is to take a fritter surface (such as 0.5*0.5cm) to be analyzed
On the curved surface for being fixed on curved surface chemical reactor 30, then detected with suitable solvent.
Similarly, biological tissue's fritter can also be directly anchored into reactor surface to be detected, without pre-processing, greatly
It is convenient that ground provides for biological fabric analysis.
It follows that utilizing EFI by the way that chemical reaction equipment introducing electrospray ion source device technical scheme is realized
The real-time monitoring chemical reaction process of mist mass spectrum and the short reactive intermediate of detection existence time；By the way that curved surface is chemically reacted
Device be introduced into electrospray ion source device technical scheme realize removal analytical technique of mass spectrum in electrochemical reaction treat detection architecture
Interference, make the detection of electrospray ionization mass spectrum more accurate, can more reflect the real conditions of system to be detected.
In the utility model second embodiment, a kind of mass spectrograph of detectable reactive intermediate is also provided, it includes：Quality
Analyzer, ion detector and electrospray ion source device as above.Part I sample reacts with Part II sample chemical
Reactive intermediate etc. be directly entered mass analyzer entrance 510；Mass analyzer is by Part I sample and Part II sample
The mixture of product reaction is separated by mass-to-charge ratio, and ion detector is detected to the ion after mass analyzer is separated.
Further, the distance of the port of export of curved surface 310 and mass analyzer entrance 510 is 2-5mm, and curved surface 310 goes out
Mouth end specific mass analyzer entrance 510 is higher by 0-3mm, is arranged such, mass signal intensity and test limit are optimal.
It can be seen that, the utility model is the built-in curved surface chemical reactor of mass spectrometric electrospray ion source device, utilizes this
Curved surface chemical reactor can realize organic chemical reactionses monitoring in real time and the detection unstable chemical reaction intermediate of high activity；And
And can be without sample pretreatment directly to material surface sample, biological tissue samples are analyzed.Curved surface chemical reactor leads to
Cross the base being attached thereto, it is possible to achieve the three-dimensional regulation and angulation change of curved surface chemical reactor；Curved surface chemical reactor
Shape and material can be convenient for changing to tackle various differential responses systems.
Above content is to combine the further description that specific embodiment is made to the application, it is impossible to assert this Shen
Specific implementation please is confined to these explanations.For the application person of an ordinary skill in the technical field, do not taking off
On the premise of from the design of the application utility model, some simple deduction or replace can also be made.
Claims (10)
1. a kind of electrospray ion source device, it is characterised in that including the sampling device for sample introduction, for by sampling device
The electrospray device that is sprayed in the form of electron spray of Part I sample, and curved surface chemical reactor, the curved surface chemistry
The curved surface of reactor is located on the jet path of electron spray.
2. electrospray ion source device according to claim 1, it is characterised in that the curved surface chemical reactor and EFI
The curved surface of mist contact is used to load Part II sample, and with the Part I sample chemistry can occur for the Part II sample
Reaction.
3. electrospray ion source device according to claim 1 or 2, it is characterised in that the electron spray incides described
Angle on curved surface is 100 ° to 150 °.
4. electrospray ion source device according to claim 1 or 2, it is characterised in that the electrospray ion source device
Also include reactor base, the curved surface chemical reactor is arranged in the reactor base, and the reactor base is adjustable
The displacement of pitch surface chemical reactor in a predetermined direction, the predetermined direction is included in X-direction, Y direction, Z-direction
One or more.
5. electrospray ion source device according to claim 1 or 2, it is characterised in that the sampling device includes sample introduction
Pump, injection port and sample feeding pipe, the electrospray device include capillary pipe spray pin and direct current voltage generator, the injection port
Connected by sample feeding pipe with capillary pipe spray pin；The sampling pump is used to convey Part I sample in sample feeding pipe, make its from
Sprayed in capillary pipe spray pin, direct current voltage generator applies high voltage electric field to capillary pipe spray pin, makes Part I sample
After capillary pipe spray pin, the tiny droplet with electric charge and ejection are atomized into, electron spray is formed.
6. electrospray ion source device according to claim 2, it is characterised in that the Part I sample is comprising the
The solution of a part of reactant, Part II sample includes Part II reactant that can be with Part I reactant reaction.
7. electrospray ion source device according to claim 1 or 2, it is characterised in that the curved surface chemical reactor with
The curved surface of electron spray contact is inner sunken face.
8. electrospray ion source device according to claim 1 or 2, it is characterised in that the curved surface chemical reactor with
The corresponding central angle of curved surface of electron spray contact is 30 ° to 90 °.
9. electrospray ion source device according to claim 4, it is characterised in that the reactor base includes：It is fixed
Pedestal on electrospray ion source device cavity inner wall, is vertically arranged on the pedestal and is vertically directed part, that can move
Dynamic mode is arranged on the support member being vertically directed on part, and reactor support bar；It is horizontally disposed with the support member
There is guide groove, the reactor support bar is arranged in guide groove in the way of it can move.
10. a kind of mass spectrograph of detectable reactive intermediate, it is characterised in that including：Mass analyzer, ion detector and such as
Electrospray ion source device described in claim 1-9 any one；The mass analyzer is by Part I sample and second
The mixture of sample segment reaction is separated by mass-to-charge ratio, and the ion detector enters to the ion after mass analyzer is separated
Row detection.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201720272415.3U CN206595226U (en) | 2017-03-20 | 2017-03-20 | A kind of mass spectrograph of electrospray ion source device and detectable reactive intermediate |
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| CN201720272415.3U CN206595226U (en) | 2017-03-20 | 2017-03-20 | A kind of mass spectrograph of electrospray ion source device and detectable reactive intermediate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106920735A (en) * | 2017-03-20 | 2017-07-04 | 北京大学深圳研究生院 | Can detect method, electrospray ion source device and the mass spectrograph of reactive intermediate |
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2017
- 2017-03-20 CN CN201720272415.3U patent/CN206595226U/en not_active Withdrawn - After Issue
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106920735A (en) * | 2017-03-20 | 2017-07-04 | 北京大学深圳研究生院 | Can detect method, electrospray ion source device and the mass spectrograph of reactive intermediate |
| CN106920735B (en) * | 2017-03-20 | 2018-10-16 | 北京大学深圳研究生院 | Method, electrospray ion source device and the mass spectrograph of detectable reactive intermediate |
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