CN106384705A - Miniature array based high-throughput nano-liter electrospray analysis system and application thereof - Google Patents
Miniature array based high-throughput nano-liter electrospray analysis system and application thereof Download PDFInfo
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- CN106384705A CN106384705A CN201610753809.0A CN201610753809A CN106384705A CN 106384705 A CN106384705 A CN 106384705A CN 201610753809 A CN201610753809 A CN 201610753809A CN 106384705 A CN106384705 A CN 106384705A
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- funnel
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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
- H01J49/0404—Capillaries used for transferring samples or ions
-
- 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
-
- 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
- H01J49/167—Capillaries and nozzles specially adapted therefor
Abstract
The invention relates to a miniature funnel-shaped sample carrier array based high-throughput nano-liter electrospray mass spectrometry analysis system and an application thereof. The system comprises an electrospray device, a mass spectrometer, a funnel-shaped miniature sample carrier and a bracket, and is characterized in that the funnel-shaped miniature sample carrier is arranged between a capillary tip of the electrospray device and a sample inlet of the mass spectrometer, and the funnel-shaped miniature sample carrier is located on the bracket. The concentration of a sample at the surface of the carrier is high, thereby not only increasing the sensitivity of the system, but also having good practicability, and avoiding a complex parameter optimization process of a sample transferring process. Quick manufacturing of the miniature funnel array can be realized according to an array preparation method provided by the invention. The system provided by the invention is low in cost, simple to operate, and applicable to nano-liter electrospray mass spectrometry analysis for polypeptide/ protein molecules, pesticide molecules, polymers, saccharides and antibiotic molecules.
Description
Technical field
The invention belongs to mass spectral analysis field, particularly to a kind of analysis of high flux Nanoliter electrospray based on miniature array
System and its application.
Background technology
The analysis method of traditional chromatograph-mass spectrometer coupling is by complicated Sample Pretreatment Technique, by object from sample
Extract in product matrix, then by extract after purifying, then carry out Instrumental Analysis.Conventional extracting process includes solid phase
Extraction, liquid-liquid extraction, SPME, the technology such as magnetic extraction, in the sample handling processes based on such technology, due to past
Toward will be through multi step strategy, using substantial amounts of organic reagent, can be to environment；Additionally, for small samples, complicated
Processing procedure often cause the problems such as loss of object or cross pollution etc. in sample or sample, for analysis result
The degree of accuracy have large effect, and test, waste of manpower and material resources longer with the time.
Method based on mass spectrum Direct Analysis is relatively easy, can effectively improve analysis efficiency, such as desorption electrospray skill
Art and extraction electron spray etc..But traditional reflective desorption electrospray technical pattern parameter is complicated, and different types of sample
Product require different for structural parameters；Transmission-type desorption electrospray adopts network structure load sample although operation is relatively easy,
But have that sample surfaces concentration is low and the shortcomings of jitter it is necessary to the new technology of exploitation goes the sample improving surface to divide
The concentration of son.Although the relatively conventional electrospray techniques of Nanoliter electrospray Direct Analysis technology are few for sample size demand,
Sample transfer and complex disposal process, can the loss with sample and possible cross pollution, and high flux relatively difficult to achieve divides
Analysis.Therefore, it is badly in need of setting up a kind of ion source device of the direct mass spectral analysis of suitable small samples, realize quick analysis.
Content of the invention
The purpose of the present invention is exactly to solve the above problems, providing one kind to be based on miniature funnel array nanoliter level electron spray
Mass spectrometric analysis method.The present invention makes funnel device by micropin on film surface and carries out Fuel spray, using it to polypeptide, albumen
Matter, and enzymolysis sample analyzed.
Its general principle is as follows：The fluid sample of small size is applied directly to the miniature funnel (micro- funnel) of sample holder
In, by mass spectrum injection port arrange load high voltage (- 4.5kV), produce once spray, and in sample holder funnel by
Gradually accumulate, form high electric charge liquid film, the analysans of liquid film continued dissolution and extraction funnel surface deposition, in the impact of electric field
Under, move to mass spectrum injection port direction, form secondary spraying in aperture, charged ion enters mass spectrum, collection obtains spectrogram (as schemed
Shown in 1).This device sample is high in loader surface concentration, not only increases the sensitivity of system, and has preferable practicality
Property, it is to avoid complicated parameter optimisation procedure and sample transfer process, by the array preparation method of invention, it is possible to achieve micro- leakage
The quick Fabrication of bucket array, low cost, simple to operate it is adaptable to polypeptides/proteins molecule, pesticide molecule, polymer and sugar
The Nanoliter electrospray mass spectral analysis of class and antibiotic molecule.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, bag
Include：Electrospray device, mass spectrograph, funnel-form minute sample carrier/funnel-form minute sample carrier array, support；Institute
State and between the capillary tip of electron spray and mass spectrograph injection port, be provided with funnel-form minute sample carrier/miniature sample of funnel-form
Product carrier array, described funnel-form minute sample carrier/funnel-form minute sample carrier array is located on described support；
Wherein, described funnel-form minute sample carrier array is by being evenly spaced in same plane in the way of annular array
On described miniature funnel-form sample holder composition.
Preferably, described funnel-form minute sample carrier (micro- funnel) central point and mass spectrum injection port are apart from S1, institute
State funnel-form minute sample carrier central point with described nozzle needle (capillary tip) apart from S2, wherein, S1/S2=3～3.2：
5～5.1.
In an above-mentioned spray process, need in capillary to load solvent, but sample, in funnel, extracts 1mL molten
Agent (methanol/water=1：1 mode) it is also possible to adjust the type of solvent as needed.
Preferably, the diameter in described funnel-form minute sample carrier aperture is less than<200μm.
Heretofore described " diameter in funnel-form minute sample carrier aperture " refers to：" the relatively fine portion of micro- funnel bottle neck
The port diameter of part ".
Preferably, the axial line of described funnel-form minute sample carrier and the center line of mass spectrograph injection port are positioned at same
On straight line.
Preferably, the aperture highlight of described funnel-form minute sample carrier is located at mass spectrograph injection port side；
Preferably, the sample size of described funnel-form minute sample carrier is 50～60nL.
Present invention also offers a kind of miniature funnel-form sample carrying of Electrospray Ionization Mass Spectrometry of upgrading for high-throughput nano
Device, described funnel-form minute sample carrier is funnel-form, is arranged at high-throughput nano upgrading Electrospray Ionization Mass Spectrometry by support
Between the capillary tip of the electron spray of device and mass spectrograph injection port.
Preferably, the diameter in described funnel-form minute sample carrier aperture is less than<200μm；
Preferably, described funnel-form minute sample carrier central point and mass spectrum injection port are apart from S1, described funnel-form
Minute sample carrier central point and described nozzle needle (capillary tip) are apart from S2, wherein, S1/S2=3～3.2：5～5.1.
Present invention also offers a kind of miniature funnel-form sample carrying of Electrospray Ionization Mass Spectrometry of upgrading for high-throughput nano
The preparing instrument of device, including：Horizontally movable platform I, membrane support, vertically moving platform II, punching needle, stepper motor with
And controller is it is characterised in that described membrane support is arranged on described platform I, the top of described platform I is provided with described platform
II, described platform II is provided with described punching needle, described punching needle axial line is intersected with described platform I and perpendicular to described flat
Platform I；During work, horizontal and vertical movement is carried out respectively by described stepper motor and controller control platform I and platform II.
Preferably, the bottom of described membrane support is additionally provided with the metal tube of hollow.
Present invention also offers the preparation method of above-mentioned miniature funnel-form sample holder, including：
1) film substrate is fixed on membrane support, is mounted directly on platform I；Punching needle is arranged on platform II；
2) pass through controller control platform I, the movement of platform II, realize the separation of micro- funnel and the punching press depth of punching needle
Degree regulation and control；
3) metal tube of hollow is set in the bottom of film substrate, to dock generation funnel-form sample holder.
Present invention also offers a kind of high-throughput nano upgrading electron spray matter based on miniature funnel-form sample holder array
Analysis of spectrum device detection method, including：
1), before collection mass spectrum, after Sample Dilution or process, using sample introduction needle, sample is placed in funnel-form minute sample
In carrier, to be analyzed；
2) funnel-form minute sample carrier is docked with mass spectrograph；
3) sample collection being carried out using mass spectrograph and analysis.
Preferably, the sample size of described sample is 50～60nL.
Beneficial effects of the present invention
(1) present invention is by the use of micro- funnel array as the carrier of nano-upgrading sample.Solve small size complex matrices sample
A difficult problem for the quick analysis of trace object in product.Contrast traditional nanoliter level sprayer unit, have simple to operate, with low cost
The features such as, the traditional desorption electrospray technology of contrast, there is signal stabilization, the duration is long, sensitivity is high, it is excellent that expanding type is strong etc.
Point is it is adaptable to the mass spectral analysis of polypeptides/proteins molecule, pesticide molecule, polymer and carbohydrate molecule.
(3) apparatus of the present invention structure is simple and convenient to operate, detection efficiency is high, practical it is easy to promote.
Brief description
The miniature funnel of Fig. 1 direct electrospray device system schematic；
Wherein, 1. it is grounded the 2. spraying micro- funnels of solvent 3. peristaltic pump, 4. capillary nozzle needle, 5. main jet mist, 6. sample bearing plate 7.
8. time level spraying 9. mass spectrum injection ports；
Fig. 2 miniature funnel array；
Fig. 3 miniature funnel array producing device；
Wherein, a. camera b. stepper motor c. punching needle d. array bracket e. thimble f. stepper motor；
The application of Fig. 4 micro-solid phase extraction array Nanoliter electrospray analysis method：The mass spectrogram of (a) 500fmol lysozyme；
The mass spectrogram of (b) 1pmol carbonic anhydrase；The mass spectrogram of (c) 500fmol bovine serum albumin(BSA)；
The application of Fig. 5 micro-solid phase extraction array Nanoliter electrospray analysis method：The mass spectrogram of (a) bovine insulin B chain；
The mass spectrogram of (b) cytochrome c；
The application of Fig. 6 micro-solid phase extraction array Nanoliter electrospray analysis method：The mass spectrogram of (a) Clenbuterol；(b) horse
Draw the mass spectrogram of sulphur phosphorus, the mass spectrogram of (c) maltotriose, the mass spectrogram of (d) PEG-6000.
The Ofloxacin mass spectrogram of Fig. 7 miniature array Nanoliter electrospray analysis method collection.
Fig. 8 miniature array Nanoliter electrospray is compared with polypeptide (SubP) signal of traditional desorption electrospray.
Specific embodiment
By the following examples feature of present invention and other correlated characteristic are described in further detail, in order to the same industry
The understanding of technical staff：
Embodiment 1
One kind is based on miniature funnel direct Electrospray Ionization Mass Spectrometry method.Described device is by a platform, membrane support d, the Chinese
Pin c, stepper motor b, f and controller and mass spectrum composition.The design procedure of device is as follows：
(1) the spraying analysis source preparation method based on film funnel type sample holder is as follows：Flexible tacky film is fixed
On plastic stent d, it is mounted directly in a two-dimentional mobile automatic platform, is provided simultaneously with a level adjustment system.
Punching press Chinese pin c is arranged on the platform vertically moving, and motor platform passes through a homemade software program and controls, and realizes its micro- leakage
The separation of bucket and the press depth controlling punching needle c.Flexible tacky film may be deformed in manufacturing process, lead to micro- leakage
There is difference in bucket.In order to ensure the uniformity of the opening of punching needle c preparation, the metal tube/thimble e of hollow is placed in bottom for right
Connect flexible membrane funnel.
(2) source-mass spectrum docking is analyzed in the spraying based on film funnel type sample holder：Device is propped up by a platform, sample
Frame and spraying system are constituted.After completing sample transfer, miniature film load SPE cell system is positioned on trestle table.Using
Manual linear mobile station and two axle electric platforms are for adjusting and calibrating distance and the position of abstraction pool opening and mass spectrum injection port 9
Put.Spraying system nozzle needle 4 is made up of (interior through 50 μm, 150 μm of external diameter) quartz capillary.It is connected to three-dimensional may move to put down
Platform is adjusting its position.Peristaltic pump 3 is connected to quartz capillary for producing spraying.At nozzle needle 4 spraying, external camera is used for supervising
Depending on ionogenic spray condition, and guarantee stability and the continuation once sprayed.
(3) Mass Spectrometry Conditions：Using Fourier's series ICR.Using electron spray, flow rate set is
30uL/hr's, it is respectively adopted both positive and negative pattern and is ionized, capillary voltage is set to 3kV, the temperature of transfer capillary is
220℃.Parent ion selection is carried out using front end quadrupole rod, quality width is set to 5m/z, ion assemble index is set to 1-2s.Adopt
Carry out data acquisition with broadband mode, mass range is set to 50-1000.
1st, instrument and reagent
All of reagent is purchase, processes using the row that advances is further.Experiment (is included with protein/polypeptide
Angiotensin II,Insulin chain B oxidized,Ubiquitin,Cytochrome c,Lysozyme,
Carbonic anhydrase, Bovine serum albumin (BSA)) and trypsase buy in Sigma Aldrich
(St.Louis, MO, USA). acetic acid and ammonium hydrogen carbonate are bought in Riedel-de Han (Seelze, Germany) .HPLC rank
Methyl alcohol by Labscan (Bangkok, Thailand) provide .Parafilm " M " film (Pechiney Plastic
Packaging, Chicago, IL, USA) it is used as the making material .FTICR-MS (4.7Tesla that miniature film loads SPE pond
APEX III and 9.4Tesla Solarix, Bruker Instrument Inc., Billerica, MA) sample collection that carries out
And analysis, sample carries out transfer processing using (Model 7000.5KH SYR, Hamilton Company, Switzerland).
2nd, preparation of samples
Sample storing liquid is by water or methanol-water (1:1 volume ratio) configuration, before experiment, it is diluted to corresponding as needed
Concentration.Enzymolysis experiment is by solubilising protein/polypeptide in the ammonium bicarbonate soln of 100mM.Trypsase is dissolved in 50mM's
In acetic acid.According to 1:50 ratios mix two kinds of solution, as 37 DEG C of constant temperature overnight.The acetic acid that enzymolysis process passes through to add 10% is molten
Liquid terminates.The mixed liquor ultimate density of protein/polypeptide is 100 μM.Further diluted again before experiment.The sample of 50nL leads to
Cross sample introduction needle be placed in be analyzed in array micro funnel 7；Other Sample Dilutions, to desired concn, are loaded directly into entering in array
Row mass spectral analysis.
3rd, the spraying analysis source-mass spectrum based on film funnel type sample holder is to interview Summary.
4th, mass spectrometer system
Using FTICR-MS (4.7Tesla APEX III and 9.4Tesla Solarix, Bruker Instrument
Inc., Billerica, MA) sample collection that carries out and analysis.It is typically configured to N2(250 DEG C of at～150to) is used for adding
Thermo-capillary and auxiliary go spray droplet solvation.The ion producing enters mass analyzer after accumulating 1-2s in sextupole bar.
Data acquisition is added up to the signal of 5-20 time.
5th, apply
Micro-solid phase extraction array-direct ion mass spectrometric analysis method is combined at biological point using 9.4T FTICR-MS
Son analysis application aspect is studied.Mass spectrogram as Fig. 4 (a) 500fmol lysozyme；The mass spectrum of (b) 1pmol carbonic anhydrase
Figure；The mass spectrogram of (c) 500fmol bovine serum albumin(BSA)；Fig. 5 micro-solid phase extraction array Nanoliter electrospray analysis method should
With：The mass spectrogram of (a) bovine insulin B chain；The mass spectrogram of (b) cytochrome c；Fig. 6 micro-solid phase extraction array Nanoliter electrospray
The application of analysis method：The mass spectrogram of (a) Clenbuterol；The mass spectrogram of (b) malathion, the mass spectrogram of (c) maltotriose,
The mass spectrogram of (d) PEG-6000.It can be seen that this device can apply to pesticide molecule, polymer molecule and polypeptide/albumen
The mass spectral analysis of the biomolecule such as matter.
Embodiment 2
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, bag
Include：Electrospray device, mass spectrograph, funnel-form minute sample carrier (micro- funnel) 7, support (sample bearing plate) 6；In described electricity
The capillary (capillary nozzle needle) 4 of spraying is most advanced and sophisticated to be provided with funnel-form minute sample carrier 7 and mass spectrograph injection port 9 between,
Described funnel-form minute sample carrier 7 is located on described support 6.
Embodiment 3
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, bag
Include：Electrospray device, mass spectrograph, funnel-form minute sample carrier (micro- funnel) 7, support (sample bearing plate) 6；In described electricity
The capillary (capillary nozzle needle) 4 of spraying is most advanced and sophisticated to be provided with funnel-form minute sample carrier 7 and mass spectrograph injection port 9 between,
Described funnel-form minute sample carrier 7 is located on described support 6.
Described funnel-form minute sample carrier 7 central point and mass spectrum injection port 9 are apart from S1, the miniature sample of described funnel-form
Product carrier 7 central point and described nozzle needle (capillary tip) 4 are apart from S2, wherein, S1/S2=3～3.2：5～5.1.
Embodiment 4
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, bag
Include：Electrospray device, mass spectrograph, funnel-form minute sample carrier (micro- funnel) 7, support (sample bearing plate) 6；In described electricity
The capillary (capillary nozzle needle) 4 of spraying is most advanced and sophisticated to be provided with funnel-form minute sample carrier 7 and mass spectrograph injection port 9 between,
Described funnel-form minute sample carrier 7 is located on described support 6.
The diameter in described funnel-form minute sample carrier 7 aperture is less than<200μm.
Embodiment 5
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, bag
Include：Electrospray device, mass spectrograph, funnel-form minute sample carrier (micro- funnel) 7, support (sample bearing plate) 6；In described electricity
The capillary (capillary nozzle needle) 4 of spraying is most advanced and sophisticated to be provided with funnel-form minute sample carrier 7 and mass spectrograph injection port 9 between,
Described funnel-form minute sample carrier 7 is located on described support 6.
The axial line of described funnel-form minute sample carrier 7 is located at same straight line with the center line of mass spectrograph injection port 9
On.
Embodiment 6
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, bag
Include：Electrospray device, mass spectrograph, funnel-form minute sample carrier (micro- funnel) 7, support (sample bearing plate) 6；In described electricity
The capillary (capillary nozzle needle) 4 of spraying is most advanced and sophisticated to be provided with funnel-form minute sample carrier 7 and mass spectrograph injection port 9 between,
Described funnel-form minute sample carrier 7 is located on described support 6.
The aperture highlight of described funnel-form minute sample carrier 7 is located at mass spectrograph injection port 9 side.
Embodiment 7
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, bag
Include：Electrospray device, mass spectrograph, funnel-form minute sample carrier (micro- funnel) 7, support (sample bearing plate) 6；In described electricity
The capillary (capillary nozzle needle) 4 of spraying is most advanced and sophisticated to be provided with funnel-form minute sample carrier 7 and mass spectrograph injection port 9 between,
Described funnel-form minute sample carrier 7 is located on described support 6.
The sample size of described funnel-form minute sample carrier 7 is 50～60nL.
Embodiment 8
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, bag
Include：Electrospray device, mass spectrograph, funnel-form minute sample carrier array, support (sample bearing plate) 6；In described electron spray
Capillary (capillary nozzle needle) 4 most advanced and sophisticated be provided with funnel-form minute sample carrier array, institute and mass spectrograph injection port 9 between
State funnel-form minute sample carrier array to be located on described support 6；
Wherein, described funnel-form minute sample carrier array is by being evenly spaced in same plane in the way of annular array
On described miniature funnel-form sample holder 7 form.
Embodiment 9
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, bag
Include：Electrospray device, mass spectrograph, funnel-form minute sample carrier array, support (sample bearing plate) 6；In described electron spray
Capillary (capillary nozzle needle) 4 most advanced and sophisticated be provided with funnel-form minute sample carrier array, institute and mass spectrograph injection port 9 between
State funnel-form minute sample carrier array to be located on described support 6；
Described funnel-form minute sample carrier array center point and mass spectrum injection port 9 are apart from S1, described funnel-form micro-
Type sample holder array center point and described nozzle needle (capillary tip) 4 are apart from S2, wherein, S1/S2=3～3.2：5～
5.1.
Embodiment 10
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, bag
Include：Electrospray device, mass spectrograph, funnel-form minute sample carrier array, support (sample bearing plate) 6；In described electron spray
Capillary (capillary nozzle needle) 4 most advanced and sophisticated be provided with funnel-form minute sample carrier array, institute and mass spectrograph injection port 9 between
State funnel-form minute sample carrier array to be located on described support 6；
In described funnel-form minute sample carrier array, the diameter in each aperture is smaller than<200μm.
Embodiment 11
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, bag
Include：Electrospray device, mass spectrograph, funnel-form minute sample carrier array, support (sample bearing plate) 6；In described electron spray
Capillary (capillary nozzle needle) 4 most advanced and sophisticated be provided with funnel-form minute sample carrier array, institute and mass spectrograph injection port 9 between
State funnel-form minute sample carrier array to be located on described support 6；
The axial line of described funnel-form minute sample carrier array is located at always with the center line of mass spectrograph injection port 9
On line.
Embodiment 12
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, bag
Include：Electrospray device, mass spectrograph, funnel-form minute sample carrier array, support (sample bearing plate) 6；In described electron spray
Capillary (capillary nozzle needle) 4 most advanced and sophisticated be provided with funnel-form minute sample carrier array, institute and mass spectrograph injection port 9 between
State funnel-form minute sample carrier array to be located on described support 6；
Each aperture highlight of described funnel-form minute sample carrier array is all located at mass spectrograph injection port 9 side.
Embodiment 13
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, bag
Include：Electrospray device, mass spectrograph, funnel-form minute sample carrier array, support (sample bearing plate) 6；In described electron spray
Capillary (capillary nozzle needle) 4 most advanced and sophisticated be provided with funnel-form minute sample carrier array, institute and mass spectrograph injection port 9 between
State funnel-form minute sample carrier array to be located on described support 6；
In described funnel-form minute sample carrier array, the sample size of each micro- funnel 7 is all 50～60nL.
Embodiment 14
A kind of miniature funnel-form sample holder of Electrospray Ionization Mass Spectrometry of upgrading for high-throughput nano, described funnel-form is micro-
Type sample holder 7 is funnel-form, is arranged at high-throughput nano upgrading Electrospray Ionization Mass Spectrometry dress by support (sample bearing plate) 6
Between capillary (capillary nozzle needle) 4 tip of the electron spray put and mass spectrograph injection port 9.
Embodiment 15
A kind of miniature funnel-form sample holder of Electrospray Ionization Mass Spectrometry of upgrading for high-throughput nano, described funnel-form is micro-
Type sample holder 7 is funnel-form, is arranged at high-throughput nano upgrading Electrospray Ionization Mass Spectrometry dress by support (sample bearing plate) 6
Between capillary (capillary nozzle needle) 4 tip of the electron spray put and mass spectrograph injection port 9.
The diameter in described funnel-form minute sample carrier 7 aperture is less than<200μm；
Embodiment 16
A kind of miniature funnel-form sample holder of Electrospray Ionization Mass Spectrometry of upgrading for high-throughput nano, described funnel-form is micro-
Type sample holder 7 is funnel-form, is arranged at high-throughput nano upgrading Electrospray Ionization Mass Spectrometry dress by support (sample bearing plate) 6
Between capillary (capillary nozzle needle) 4 tip of the electron spray put and mass spectrograph injection port 9.
Described funnel-form minute sample carrier 7 central point and mass spectrum injection port 9 are apart from S1, the miniature sample of described funnel-form
Product carrier 7 central point and described nozzle needle (capillary tip) 4 are apart from S2, wherein, S1/S2=3～3.2：5～5.1.
Embodiment 17
A kind of preparing instrument of the miniature funnel-form sample holder for high-throughput nano upgrading Electrospray Ionization Mass Spectrometry, bag
Include：Horizontally movable platform I, membrane support (array bracket) d, vertically moving platform II, punching needle c, stepper motor b, f
And controller, described membrane support d is arranged on described platform I, and the top of described platform I is provided with described platform II, described
Described punching needle c is provided with platform II, described punching needle c-axis heart line is intersected with described platform I and perpendicular to described platform I；
During work, horizontal and vertical movement is carried out respectively by described stepper motor b, f and controller control platform I and platform II.
Embodiment 18
A kind of preparing instrument of the miniature funnel-form sample holder for high-throughput nano upgrading Electrospray Ionization Mass Spectrometry, bag
Include：Horizontally movable platform I, membrane support (array bracket) d, vertically moving platform II, punching needle c, stepper motor b, f
And controller, described membrane support d is arranged on described platform I, and the top of described platform I is provided with described platform II, described
Described punching needle c is provided with platform II, described punching needle c-axis heart line is intersected with described platform I and perpendicular to described platform I；
During work, horizontal and vertical movement is carried out respectively by described stepper motor b, f and controller control platform I and platform II.
The bottom of described membrane support d is additionally provided with metal tube (thimble) e of hollow.
Embodiment 19
A kind of preparation method of miniature funnel-form sample holder, including：
1) film substrate is fixed on membrane support d, is mounted directly on platform I；Punching needle c is arranged on platform II；
2) pass through controller control platform I, the movement of platform II, realize the separation of micro- funnel and the punching press of punching needle c
Depth regulates and controls；
3) metal tube (thimble) e of hollow is set in the bottom of film substrate, to dock generation funnel-form sample holder.
Embodiment 20
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device detection based on miniature funnel-form sample holder array
Method, including：
1), before collection mass spectrum, after Sample Dilution or process, using sample introduction needle, sample is placed in funnel-form minute sample
In carrier, to be analyzed；
2) funnel-form minute sample carrier is docked with mass spectrograph；
3) sample collection being carried out using mass spectrograph and analysis.
Embodiment 21
A kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device detection based on miniature funnel-form sample holder array
Method, including：
1), before collection mass spectrum, after Sample Dilution or process, using sample introduction needle, sample is placed in funnel-form minute sample
In carrier, to be analyzed；
2) funnel-form minute sample carrier is docked with mass spectrograph；
3) sample collection being carried out using mass spectrograph and analysis.
Wherein, the sample size of described sample is 50～60nL.
Finally it should be noted that the foregoing is only the preferred embodiments of the present invention, it is not limited to this
Bright, although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it is still
Technical scheme described in previous embodiment can be modified, or to wherein partly carrying out equivalent.All at this
Within bright spirit and principle, any modification, equivalent substitution and improvement made etc., should be included in protection scope of the present invention
Within.Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not to the scope of the present invention
Restriction, one of ordinary skill in the art should be understood that, on the basis of technical scheme, those skilled in the art are not required to
Various modifications that creative work to be paid can be made or deformation are still within protection scope of the present invention.
Claims (10)
1. a kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device based on miniature funnel-form sample holder array, including：
Electrospray device, mass spectrograph, funnel-form minute sample carrier/funnel-form minute sample carrier array, support, its feature exists
In being provided with funnel-form minute sample carrier/funnel between the capillary tip and mass spectrograph injection port of described electron spray
Shape minute sample carrier array, described funnel-form minute sample carrier/funnel-form minute sample carrier array is located at institute
State on support；
Wherein, described funnel-form minute sample carrier array is evenly spaced on same plane by the way of annular array
Described miniature funnel-form sample holder composition.
2. device as claimed in claim 1 is it is characterised in that described funnel-form minute sample carrier central point is entered with mass spectrum
Sample mouth apart from S1, described funnel-form minute sample carrier central point and described capillary tip apart from S2, wherein, S1/S2
=3～3.2：5～5.1.
3. device as claimed in claim 1 is it is characterised in that the diameter in described funnel-form minute sample carrier aperture is less than
<200μm.
4. device as claimed in claim 1 is it is characterised in that the axial line of described funnel-form minute sample carrier and mass spectrum
The center line of instrument injection port is located along the same line.
5. device as claimed in claim 1 is it is characterised in that the aperture highlight position of described funnel-form minute sample carrier
In mass spectrograph injection port side；
Or the sample size of described funnel-form minute sample carrier is 50～60nL.
6. a kind of for high-throughput nano upgrade Electrospray Ionization Mass Spectrometry miniature funnel-form sample holder it is characterised in that institute
Stating funnel-form minute sample carrier is funnel-form, is arranged at high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device by support
Between the capillary tip of electron spray and mass spectrograph injection port.
7. carrier as claimed in claim 6 is it is characterised in that the diameter in described funnel-form minute sample carrier aperture is little
In<200μm；
Or described funnel-form minute sample carrier central point with mass spectrum injection port apart from S1, described funnel-form minute sample holds
Carry device central point with described capillary tip apart from S2, wherein, S1/S2=3～3.2：5～5.1.
8. the preparing instrument of the miniature funnel-form sample holder described in claim 6 or 7 is it is characterised in that include：Can level move
Dynamic platform I, membrane support, vertically moving platform II, punching needle, stepper motor and controller are it is characterised in that described
Membrane support is arranged on described platform I, and the top of described platform I is provided with and described platform II, and described platform II is provided with
Described punching needle, described punching needle axial line is intersected with described platform I and perpendicular to described platform I；During work, by described step
Stepper motor and controller control platform I and platform II carry out horizontal and vertical movement respectively.
9. adopt the method for the funnel-form minute sample carrier of preparing instrument preparation described in claim 8 it is characterised in that wrapping
Include：
1) film substrate is fixed on membrane support, is mounted directly on platform I；Punching needle is arranged on platform II；
2) controller control platform I, the movement of platform II are passed through, the press depth of the separation and punching needle of realizing micro- funnel is adjusted
Control；
3) metal tube of hollow is set in the bottom of film substrate, to dock generation funnel-form sample holder.
10. a kind of high-throughput nano upgrading Electrospray Ionization Mass Spectrometry device detection side based on miniature funnel-form sample holder array
Method is it is characterised in that include：
1) before collection mass spectrum, after Sample Dilution or process, using sample introduction needle, sample is placed in funnel-form minute sample and carries
In device, to be analyzed；
2) funnel-form minute sample carrier is docked with mass spectrograph；
3) sample collection being carried out using mass spectrograph and analysis.
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| CN201610753809.0A CN106384705B (en) | 2016-08-29 | 2016-08-29 | A kind of high-throughput Nanoliter electrospray analysis system and its application based on miniature array |
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| CN201610753809.0A CN106384705B (en) | 2016-08-29 | 2016-08-29 | A kind of high-throughput Nanoliter electrospray analysis system and its application based on miniature array |
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| CN109541093A (en) * | 2018-10-29 | 2019-03-29 | 山东省分析测试中心 | A kind of pretreatment of nanoliter level mass spectrum sample and sample introduction combined apparatus and its method |
| CN110021516A (en) * | 2019-04-09 | 2019-07-16 | 武汉大学 | A kind of mass spectrometer for high-throughput online photochemical reaction research |
| CN110988102A (en) * | 2019-12-10 | 2020-04-10 | 北京工业大学 | Visual sheath-flow-free single-cell mass spectrometry system |
| CN111413172A (en) * | 2020-04-17 | 2020-07-14 | 山东省分析测试中心 | In-situ enzymolysis-direct mass spectrometry analysis system and analysis method |
| WO2021212920A1 (en) * | 2020-12-08 | 2021-10-28 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Nanoliter spray-fticr-ms analysis method and device for organic matter dissolved in environmental solid sample |
| CN114361005A (en) * | 2020-10-13 | 2022-04-15 | 中国科学院大连化学物理研究所 | Mass spectrometer interface device for nanoliter electrospray ionization |
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| CN110021516A (en) * | 2019-04-09 | 2019-07-16 | 武汉大学 | A kind of mass spectrometer for high-throughput online photochemical reaction research |
| CN110988102A (en) * | 2019-12-10 | 2020-04-10 | 北京工业大学 | Visual sheath-flow-free single-cell mass spectrometry system |
| CN111413172A (en) * | 2020-04-17 | 2020-07-14 | 山东省分析测试中心 | In-situ enzymolysis-direct mass spectrometry analysis system and analysis method |
| CN114361005A (en) * | 2020-10-13 | 2022-04-15 | 中国科学院大连化学物理研究所 | Mass spectrometer interface device for nanoliter electrospray ionization |
| WO2021212920A1 (en) * | 2020-12-08 | 2021-10-28 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Nanoliter spray-fticr-ms analysis method and device for organic matter dissolved in environmental solid sample |
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