CN110060916A - A kind of mass spectrometer for the online photochemical reaction research of high-throughput drop - Google Patents
A kind of mass spectrometer for the online photochemical reaction research of high-throughput drop Download PDFInfo
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- CN110060916A CN110060916A CN201910280595.3A CN201910280595A CN110060916A CN 110060916 A CN110060916 A CN 110060916A CN 201910280595 A CN201910280595 A CN 201910280595A CN 110060916 A CN110060916 A CN 110060916A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/0027—Methods for using particle spectrometers
- H01J49/0031—Step by step routines describing the use of the apparatus
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
- H01J49/0431—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples
- H01J49/0445—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples with means for introducing as a spray, a jet or an aerosol
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
- H01J49/165—Electrospray ionisation
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Abstract
The invention discloses a kind of mass spectrometers for the online photochemical reaction research of high-throughput drop, including light-source system, mass spectrometry system and induction drop type ion source system, mass spectrometry system is for carrying out on-line mass spectroscopy analysis and research, mass spectrograph injection port end ground connection, incuding drop type ion source system includes electrode plate, chip substrate, chip supporting plate and high-voltage dc pulse power, chip substrate is fixed on chip supporting plate, reaction drop is used to prepare on chip substrate, electrode plate is set to chip supporting plate bottom, high-voltage dc pulse power is used to generate drop on induction chip substrate between electrode plate and mass spectrograph injection port and polarized high voltage pulse electric field occurs, light-source system is used to react drop on chip substrate and provide controllable illumination.The present invention have high flux screening photochemical reaction condition and on-line analysis photochemical reaction process difunctional effect, therefore pharmaceutical synthesis, photocatalysis and in terms of have potential utility value.
Description
Technical field
The invention belongs to photochemical reaction fields, are related to a kind of photochemical reaction equipment, and in particular to a kind of high throughput liquid
Drip the mass spectrometer of online photochemical reaction research.
Background technique
Photochemical reaction refers to the chemical reaction that substance occurs under illumination condition.For example, the Plant Light cooperation in nature
With the photochemical pollution etc. that the formation of ozone and vehicle exhaust are formed in air in atmosphere.It is anti-that photochemistry occurs
The principle answered is considerably complicated, and the wave-length coverage (100 to 1000nm) that photochemical reaction is related to light not only, which occurs, with it light, but also
It is related with the radical life length generated in photochemical reaction and its active power.Photochemical complexity causes various types of
Chemical reaction, it is more important in terms of photocatalysis especially in synthesis chemistry, it is primarily due to photocatalysis and is solved using photon energy
Demand to reaction temperature and other new impurity are not introduced, light-catalyzed reaction already becomes one important point of synthesis chemistry
Branch.
Highly sensitive, high specific and the analytical technique of mass spectrum of high accuracy be one of the important means of in analysis detection,
Simultaneously there are powerful qualitative and quantitation capabilities to promote rapid development of the mass-spectrometric technique in various fields, one of them is pair
Synthesize the mechanism study of chemistry.But traditional off-line analysis not only complex steps, sample consumption is big, more importantly can not
Observe short-life reaction intermediate, it is very unfavorable to the research of reaction mechanism.The development of on-line mass spectroscopy analytical technology is solution
Certainly this problem provides a kind of thinking, 2016, has a kind of online photochemical reaction mass spectrometric analysis method of document report, adopts
On-line mass spectroscopy discovery and the mechanism study of light-catalyzed reaction are realized with Nanoliter electrospray mass spectrometry method
(Angew.Chem.Int.Ed.2016,55,9345-9349).But the photochemistry that this method only allows to carry out single sample is anti-
It should analyze in real time, and electrode needs to be inserted into the solution of capillary, and this method is caused to be restricted, high throughput can not be carried out
Multiple-reaction monitoring and analysis.Therefore, the present invention proposes a kind of contactless online photochemistry mass spectral analysis of high-throughput drop
Device can be used for various photochemically reactive real-time online Mass Spectras.
In consideration of it, the mass spectrometer for designing and building the online photochemical reaction research of high-throughput drop becomes the present invention
The patent technical issues that need to address.
Summary of the invention
In order to realize high-throughput online photochemical reaction Mass Spectra, the present invention proposes a kind of contactless drop type
Online photochemistry mass spectrometer.Have the function of that high-throughput and on-line analysis photochemical reaction is difunctional, therefore can
With a large amount of analysis feasibility photosynthesis chemical reactions, synthetic drug, photocatalysis and in terms of there is potential utilization
Value.Solve off-line analysis complex steps traditional in the prior art, the big technical problem of sample consumption.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that:
A kind of mass spectrometer for the online photochemical reaction research of high-throughput drop, it is characterised in that: including light
Source system, mass spectrometry system and contactless induction drop type ion source system, the mass spectrometry system use EFI
Mist mass spectrograph, for carrying out on-line mass spectroscopy analysis and research, mass spectrograph injection port end ground connection, the induction drop type ion source system
Including electrode plate, chip substrate, chip supporting plate and high-voltage dc pulse power, the chip substrate is fixed on chip supporting plate,
Reaction drop is used to prepare on chip substrate, the electrode plate is set to chip supporting plate bottom, and the high-voltage dc pulse power is used
Polarized high voltage pulse electric field occurs in generating drop on induction chip substrate between electrode plate and mass spectrograph injection port, it is described
Light-source system is used to react drop on chip substrate and provide controllable illumination.
Further, the chip substrate is made of insulating substrate.
Further, the chip supporting plate is mounted in three-dimensional mobile platform, adjusts chip support by three-dimensional mobile platform
The position of plate, so as to adjust the reaction drop participation reaction corresponding with mass spectrograph injection port of different location on chip substrate.
Further, the induction drop type ion source system and light-source system are mounted on mass spectral analysis by suspension arrangement
On the mass spectrograph injection port of system.
Further, the suspension arrangement includes suspension clamp arm and support plate, and the suspension clamp arm upper end is for being clamped in
On mass spectrograph injection port, suspension clamp arm lower end is fixedly linked with support plate, and the three-dimensional mobile platform installation is on the supporting plate.
Further, the light-source system includes laser and laser adjusting rod, and the laser is mounted on laser adjusting
On bar, the laser adjusting rod installation on the supporting plate, is controlled by the position of the adjustable laser of laser adjusting rod
To the light position of chip substrate.
Further, the electrode plate is installed on the supporting plate by electrode regulating bar, can be adjusted by electrode regulating bar
The height and position for the pole plate that economizes on electricity.
Further, the light that the laser generates is visible wavelength.
Further, the high-voltage dc pulse power is made of power supply, signal generator and high-voltage amplifier, is generated most
Height is no more than the pulse direct current high pressure of 10kV.
It is a kind of to carry out photochemically reactive mass spectral analysis side in real-time online research drop using above-mentioned mass spectrometer
Method, which comprises the following steps:
Step 1, mass spectrometer are put up, and the drop containing photochemical reaction object solution is prepared on chip substrate,
Adjustment laser matching can trigger photochemically reactive visible light source；
Chip substrate containing solution droplets is placed on chip supporting plate by step 2, adjusts chip by three-dimensional mobile platform
The position of supporting plate makes a drop on chip substrate be directed at mass spectrograph injection port, regulates the position of electrode plate and laser；
Step 3, opening laser are irradiated on chip substrate to reaction test liquid, while or lag starting DC pulse
Power-supply system, so that liquid generates polarization on chip substrate, generation electron spray, which enters in mass spectrograph, to be analyzed by mass spectrometry；
Step 4, adjustment chip substrate position, laser parameter or high-voltage dc pulse power parameter, carry out next group of examination
It tests.
The medicine have the advantages that
In the present invention, in the case where incuding drop type ion source system, drop non-contact electrode is reacted, reduces electrode bring shadow
It rings, and the mode for loading reaction drop is simple, high-throughput the features such as reacting drop more.Three-dimensional mobile platform, control system make
Reaction screening is versatile and flexible, reduces the workload of researcher, while can be carried out screening of the light to reaction system of different-waveband,
Enrich light-catalyzed reaction.The present invention has not only expanded mass spectrum on-line analysis in the research of photosynthesis chemical aspect, but also high pass
Amount screening has positive impetus to photochemical development is studied.The present invention has high flux screening photochemical reaction condition
With the difunctional effect of on-line analysis photochemical reaction process, therefore it is anti-to can be used for largely analyzing feasibility photosynthesis chemistry
Answer, pharmaceutical synthesis, photocatalysis and in terms of have potential utility value.
Detailed description of the invention
Fig. 1 is mass spectrometer structural schematic diagram in the embodiment of the present invention.
Fig. 2 is mass spectrometer schematic illustration in the embodiment of the present invention.
1- mass spectrograph, 2- mass spectrograph injection port, 3- laser, 4- chip substrate, 5- chip supporting plate, 6- electrode plate, 7- electricity
Pole adjusting rod, 8- three-dimensional mobile platform, 9- support plate, 10- suspension clamp arm, 11- mounting plate, 12- high-voltage dc pulse power,
13- laser adjusting rod, 14- drop.
Specific embodiment
The embodiment of the present invention establishes photochemically reactive mass spectrometric analysis method in a kind of real-time online research drop, thus logical
The drop rapid reaction simulation photochemical syntheses process for crossing micro volume, provides the key molecule information in reaction process, improves
The photochemically reactive flux of on-line mass spectroscopy technique study.The realization means of this method are that preparation is containing photochemical on chip substrate 4
The drop 14 of reactant solution is learned, matching can trigger photochemically reactive visible light source, cause in light source irradiation drop 14
While photochemical reaction, apply between the mass spectrograph injection port 2 above pulse direct current high pressure and drop 14 below drop 14
High voltage electric field is formed, drop 14 polarizes under high electric field induction.Charge density on 14 surface of drop runs up to certain threshold
When value, it may occur that electron spray ionizes the determinand in reaction system, to be detected by mass spectrum real-time online.From application electric field
It is about Millisecond to the time for forming electron spray, therefore this method can be used to observe in reaction process in short-life reaction
Mesosome.Entirely spraying generating process can regard solution capacitor charge and discharge behavior in electrostatic field as.
The present invention is using the direct photochemically reactive device of electron spray in situ study of drop 14 by different module compositions.Such as
Shown in Fig. 1, a kind of mass spectrometer for the online photochemical reaction research of high-throughput drop, including light-source system, mass spectrum
Analysis system and contactless induction drop type ion source system, the mass spectrometry system use electrospray mass spectrometer 1, use
In carrying out on-line mass spectroscopy analysis and research, 2 end of mass spectrograph injection port ground connection, the induction drop type ion source system includes electrode plate
6, chip substrate 4, chip supporting plate 5 and high-voltage dc pulse power 12, the chip substrate 4 are fixed on chip supporting plate 5, chip
Reaction drop 14 is used to prepare on substrate 4, the electrode plate 6 is set to 5 bottom of chip supporting plate, the high-voltage dc pulse power 12
Polarized pulsed high-voltage occurs for generating drop 14 on induction chip substrate 4 between electrode plate 6 and mass spectrograph injection port 2
, the light-source system is used to provide controllable illumination for reaction drop 14 on chip substrate 4.
The chip supporting plate 5 is mounted in three-dimensional mobile platform 8, and the position of chip supporting plate 5 is adjusted by three-dimensional mobile platform 8
It sets, so as to adjust the participation reaction corresponding with mass spectrograph injection port 2 of reaction drop 14 of different location on chip substrate 4.The sense
Drop type ion source system and light-source system is answered to be mounted on the mass spectrograph injection port 2 of mass spectrometry system by suspension arrangement.
The suspension arrangement includes suspension clamp arm 10 and support plate 9, and 10 upper end of suspension clamp arm is for being clamped in mass spectrograph injection port 2
On, suspension 10 lower end of clamp arm is fixedly linked with support plate 9, and the support plate 9 is fixed with mounting plate 11, and the mounting plate 11 is
Plate equipped with array fixation hole, is easily installed various equipment, and the three-dimensional mobile platform 8 is bolted on mounting plate 11
On.It there also is provided three-dimensional mobile controller on mounting plate 11, the chip substrate 4 being placed on chip supporting plate 5 can be three
It ties up under the drive of mobile platform 8 in three direction translationals of x, y, z.
The specific structure of 10 upper end of clamp arm is hung depending on the shape of mass spectrograph injection port 2, can be clip clamping
It can be hanger to hang, naturally it is also possible to it is other detachable fixed forms, for example bolt is fixed, buckle is fixed etc., tool
Body embodiment does not constitute influence to technical solution of the present invention implementation, therefore details are not described herein.
The light-source system includes laser 3 and laser adjusting rod 13, and the laser 3 is mounted on laser adjusting rod 13
On, the laser adjusting rod 13 is mounted in support plate 9, by the position of the adjustable laser 3 of laser adjusting rod 13 to
Control the light position to chip substrate 4.In the present embodiment, light source by use visible wavelength, power milliwatt to watt it
Between and adjustable miniature LED laser light source, such as wavelength 405nm, 450nm, 532nm etc., can be with when being radiated on drop 14
Very quick activation photochemical reaction system, certainly in the prior art laser 3 can for self-contained laser head position and
Pose adjustment device is existing well-known technique, therefore repeats no more.
The high-voltage dc pulse power 12 is made of power supply, signal generator and high-voltage amplifier, is generated not more than
Cross the pulse direct current high pressure of 10kV.In the present embodiment, high-voltage dc pulse power 12 uses signal generator and high-voltage amplifier
Generate pulse direct current high pressure, voltage 10kV.The chip substrate 4 of insulation is usually the heat insulating lamella of glass or other materials,
For length and width between 100mm-100mm, thickness can pass through the chip base of the fixed supports insulative of chip supporting plate 5 between 1mm-5mm
Plate 4.The reaction solution that respective volume is added dropwise in pipettor can be used, also can use glass bar and pick other simple sides such as reaction solution
Formula pipettes a small amount of solution.Chip substrate 4 can by simply modify or wax spray printing the methods of can prepare it is various not
Chip with pattern reacts array, to realize high-throughput photochemical reaction Mass Spectra.Chip supporting plate 5 passes through company in experiment
It connects arm to be fixed in three-dimensional mobile platform 8, electrode plate 6 is apart from about several millimeters of chip supporting plate 5 of distance.It can be in research process
Using the higher solvent of boiling point, to reduce the volatilization of solvent in photochemical reaction and analytic process.The chip liquid drop battle array prepared
Column can be stored in the closed vessel for filling solvent, keep certain solvent vapour pressure, and the solvent volatilization for solving drop 14 is asked
Topic.
In the embodiment of the present invention, high-voltage dc pulse power 12 is by high-voltage amplifier, multimode function generator, oscillography
Device, controller and electrode plate 6 form, and voltage can be between positive and negative 10kV, and pulse frequency can be implemented between 0-1000Hz
Example high-voltage dc pulse power 12 will can be directly connected to civilian using directly purchase commercialization high voltage power supply amplifier (ground connection)
Alternating current is to obtain the high-voltage electricity of the positive and negative 10Kv of adjustable high pressure；It is combined the function generator of commercialization, any wave mode again, leads to
Overregulating wave mode and rate-adaptive pacemaker has the pulse voltage of wave mode, and realization carries out this process that charges to drop 14.Electrode plate 6
Material is conductive metal or nonmetallic, and area is without limitation, and usually in 5cm × 5cm or so, electrode plate 6 is fixed on electrode regulating bar 7
On, it can move freely.
Three-dimensional mobile platform 8 will be using directly purchase commercialization optical 3-dimensional mobile platform in embodiment, can be with fixed core
Piece supporting plate 5, can the 5 progress three-dimensional space movement of computer control chip supporting plate.
As a kind of more excellent embodiment, the laser 3 of different-waveband can be adjusted by the switching of software control laser 3
Height of the laser 3 apart from chip substrate 4 is saved, the spot size being radiated on reaction drop 14 and watt level etc..Light source
Vertical irradiation is on drop 14, with electrode in a vertical direction.The laser 3 of different-waveband has: 365nm, 405nm,
450nm, 480nm, 532nm etc..
Modules of the present invention are suspended on mass spectrograph injection port 2 by suspension arrangement.The suspension arrangement includes suspension
Clamp arm 10 and support plate 9,10 upper end of suspension clamp arm for being clamped in mass spectrograph injection port 2, suspension 10 lower end of clamp arm with
Support plate 9 is fixedly linked, and a mounting plate 11 is fixedly installed in support plate 9, and the mounting plate 11 is equipped with the fixation of array
Hole, the three-dimensional mobile platform 8, laser adjusting rod 13 and electrode regulating bar 7 are fixed on mounting plate 11, and chip supporting plate 5 passes through
Cantilever is mounted in three-dimensional mobile platform 8, and for electrode plate 6 below chip supporting plate 5, laser 3 is described above chip supporting plate 5
Electrode regulating bar 7 is either electric pushrod can be mechanical arm, can be controlled by control system for adjusting height
System, but when it is electric pushrod, adjust can be using choosing different fixation holes on mounting plate 11 for position in 11 plane of mounting plate
Mode adjust, the laser adjusting rod 13 similarly can adjust laser 3 using electric pushrod or mechanical arm mode
Position, position adjustment mode as electrode plate 6, certainly in the prior art the most self-contained laser head positions of laser 3 and
Pose adjustment device is existing well-known technique, therefore repeats no more.
It is to be noted that the three-dimensional mobile platform 8 used in the embodiment of the present invention is using three-dimensional conventional in the prior art
Mobile platform, specific structure do not impact the embodiment of the present invention, specifically can such as use three groups of leading screw and nut mechanisms
The three-dimensional mobile platform of composition, three groups of leading screw and nut mechanisms are once connected i.e. respectively along tri- direction settings of x, y and z
Three-dimensional mobile platform is constituted, specific structure repeats no more.
Visible light source integrates common wave band for using the laser of directly customization commercialization different-waveband in embodiment
Single laser can carry out spot size, the adjustment of different-waveband, power using computerized control system.
Mass spectrometer will use the linear ion hydrazine matter of the Thermo Fisher company of this laboratory equipment in embodiment
Spectrometer (LTQ XLTM) and orbit trap high-resolution mass spectrometer (Orbitrap EliteTM) it is used as quality analysis and detection system.It is real
Also by the software systems of integral traffic control modules, such as three-dimensional mobile platform 8, light-source system, high voltage direct current arteries and veins during testing
Power supply 12, mass spectrograph 1 etc. are rushed, each step rational and orderly is carried out.It can be with as a kind of more excellent embodiment, in research process
Using programming languages such as C/C++ or Labview, writes corresponding program and carrys out coordinated control modules, realize automation control,
It is to be noted that the above-mentioned automation control of the present invention realizes that various pieces of the present invention can be manual using prior art function
Control is complete, and automatic control only improves working efficiency, is not the essential part that technical solution of the present invention is implemented.
Specific embodiment described herein, only illustrates that spirit of the invention.Technology belonging to the present invention
The technical staff in field can carry out various modifications or supplement to described specific embodiment or using similar
Mode substitutes, and however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (10)
1. a kind of mass spectrometer for the online photochemical reaction research of high-throughput drop, it is characterised in that: including light source
System, mass spectrometry system and contactless induction drop type ion source system, the mass spectrometry system use electron spray
Mass spectrograph, for carrying out on-line mass spectroscopy analysis and research, mass spectrograph injection port end ground connection, the induction drop type ion source system packet
Electrode plate, chip substrate, chip supporting plate and high-voltage dc pulse power are included, the chip substrate is fixed on chip supporting plate, core
Reaction drop is used to prepare on plate base, the electrode plate is set to chip supporting plate bottom, and the high-voltage dc pulse power is used for
Drop on induction chip substrate is generated between electrode plate and mass spectrograph injection port, and polarized high voltage pulse electric field, the light occurs
Source system is used to react drop on chip substrate and provide controllable illumination.
2. mass spectrometer as described in claim 1, it is characterised in that: the chip substrate is made of insulating substrate.
3. mass spectrometer as claimed in claim 2, it is characterised in that: the chip supporting plate is mounted on three-dimensional mobile platform
On, by three-dimensional mobile platform adjust chip supporting plate position, so as to adjust different location on chip substrate reaction drop with
Mass spectrograph injection port is corresponding to participate in reaction.
4. mass spectrometer as claimed in claim 3, it is characterised in that: the induction drop type ion source system and light source
System is mounted on the mass spectrograph injection port of mass spectrometry system by suspension arrangement.
5. mass spectrometer as claimed in claim 4, it is characterised in that: the suspension arrangement includes suspension clamp arm and support
Plate, for being clamped in mass spectrograph injection port, suspension clamp arm lower end is fixedly linked with support plate, described for the suspension clamp arm upper end
Three-dimensional mobile platform is installed on the supporting plate.
6. mass spectrometer as claimed in claim 5, it is characterised in that: the light-source system includes laser and laser tune
Pole, the laser are mounted on laser adjusting rod, and the laser adjusting rod installation on the supporting plate, passes through laser adjusting rod
The position of adjustable laser is to which control is to the light position of chip substrate.
7. mass spectrometer as claimed in claim 6, it is characterised in that: the electrode plate is mounted on by electrode regulating bar
In support plate, pass through the height and position of the adjustable electrode plate of electrode regulating bar.
8. the mass spectrometer as described in claim 1-7 any one, it is characterised in that: the light that the laser generates is
Visible wavelength.
9. the mass spectrometer as described in claim 1-7 any one, it is characterised in that: the high-voltage dc pulse power
It is made of power supply, signal generator and high-voltage amplifier, generates the pulse direct current high pressure of not more than 10kV.
10. a kind of using photochemically reactive in mass spectrometer progress real-time online research drop according to any one of claims 8
Mass spectrometric analysis method, which comprises the following steps:
Step 1, mass spectrometer are put up, and the drop containing photochemical reaction object solution, adjustment are prepared on chip substrate
Laser matching can trigger photochemically reactive visible light source；
Chip substrate containing solution droplets is placed on chip supporting plate by step 2, adjusts chip supporting plate by three-dimensional mobile platform
Position, so that a drop on chip substrate is directed at mass spectrograph injection port, regulate the position of electrode plate and laser；
Step 3, opening laser are irradiated on chip substrate to reaction test liquid, while or lag starting direct current pulse power source
System, so that liquid generates polarization on chip substrate, generation electron spray, which enters in mass spectrograph, to be analyzed by mass spectrometry；
Step 4, adjustment chip substrate position, laser parameter or high-voltage dc pulse power parameter, carry out lower battery of tests.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910280595.3A CN110060916A (en) | 2019-04-09 | 2019-04-09 | A kind of mass spectrometer for the online photochemical reaction research of high-throughput drop |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910280595.3A CN110060916A (en) | 2019-04-09 | 2019-04-09 | A kind of mass spectrometer for the online photochemical reaction research of high-throughput drop |
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|---|---|---|---|---|
| CN102013380A (en) * | 2010-11-12 | 2011-04-13 | 复旦大学 | Pulse laser-assisted spray ion source |
| 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 |
| CN103033556A (en) * | 2012-12-28 | 2013-04-10 | 复旦大学 | Device and mass spectrometry for direct electrospray ionization of sample on microfluidic chip |
| CN103779170A (en) * | 2014-02-25 | 2014-05-07 | 哈尔滨工业大学（威海） | Electro-spray ion source device |
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Application publication date: 20190726 |