CN109390206A - Miniaturized portable mass spectrograph and ion source device for generating water body cluster ion - Google Patents
Miniaturized portable mass spectrograph and ion source device for generating water body cluster ion Download PDFInfo
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Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
Abstract
本发明公开了一种用于产生水团簇离子的离子源装置，从对整个喷雾过程起决定性作用的溶液参数方向入手，在电喷雾离子源本身没有加热装置的前提下，从石英毛细管喷雾出口切面和喷雾出口所处的环境两个角度出发，采用毛细管切面平整度高和光滑无毛疵，对液滴的体积进行控制，生成稳定的喷雾，从而有效的进行去溶剂化过程；采用质谱仪进样级腔体，防止外界环境(风，空气中的灰尘等)对离子喷雾强度的影响和干扰。两种措施对提高电喷雾效率，降低仪器检测限起到了一定的效果。本装置结构简单、体积小，在检测过程中能够保持稳定，还具有较高的灵敏度和稳定性，出雾口高度和距离调节方便。本发明还公开了一种应用上述离子源装置的小型化便携式质谱仪。
The invention discloses an ion source device for generating water cluster ions. Starting from the direction of solution parameters that play a decisive role in the entire spraying process, on the premise that the electrospray ion source itself has no heating device, it sprays from the outlet of a quartz capillary tube. From the perspective of the cut surface and the environment where the spray outlet is located, the capillary cut surface with high flatness and smoothness without blemishes is used to control the volume of droplets to generate a stable spray, so as to effectively carry out the desolvation process; mass spectrometers are used. The injection-level cavity prevents the influence and interference of the external environment (wind, dust in the air, etc.) on the ion spray intensity. The two measures have a certain effect on improving the efficiency of electrospray and reducing the detection limit of the instrument. The device is simple in structure and small in size, can maintain stability during the detection process, has high sensitivity and stability, and is convenient to adjust the height and distance of the mist outlet. The invention also discloses a miniaturized portable mass spectrometer applying the above-mentioned ion source device.
Description
Technical field
The present invention relates to spectrometer system technical fields, are related to one kind and are integrated in the mass spectrometric electron spray of Miniaturized portable
Ionize source device more particularly to a kind of for generating the ion source device of water body cluster ion.
Background technique
Mass spectrometric analysis method has very high sensitivity in species analysis and detection, is most widely used point in the world
One of analysis technology.Currently, mass spectrograph has become the indispensable analysis instrument in many fields, and in pharmacy, life science, environment prison
Many hot fields such as survey and protection, food safety, drug-testing, frontier defense safety check, space flight and military technology play more next
More important role.The mass spectrometer of complete set is generally by ion source, ion hop, mass analyzer, detector, true
The parts such as empty set system, circuit control and data collection system form.Mass spectrograph has very high in species analysis and Components identification
Sensitivity and resolution ratio, basic functional principle is: detected substance being ionized into ion first, passes through electric field or magnetic field
Ion is separated by the size of mass-to-charge ratio (m/z), these are then detected by isolated ion by ion detector, thus
Obtain mass spectrogram；By the analysis to mass spectrogram, the chemical component, structure and content information of tested substance can be obtained.
In a mass spectrometer, the component that substance ionizes is referred to as ion source, quality point is referred to as to the component that ion carries out quality analysis
Parser, ion source and mass analyzer are mass spectrometric two critical components of composition.
In mass spectrometric development course, ion source is played a very important role.Quality analysis is being carried out to substance
Before, it is necessary to neutral substance be first ionized into ion.Come in the past few decades, many ionization sources continue to bring out, including laser splash
(LS), electron impact ion source (EI), chemical ionization source (CI), laser gasification source (LV), electrospray ionisation source (ESI), matrix
Assisted Laser Desorption ionization source (MALDI), directly analysis (DART) in real time, swash at field-ionization/field desorption ionization source (FI/FD)
Photodesorption source (LD), fast atom bombardment source (FAB), atmosphere pressure chemical ion source (APCI) etc., these ion sources are functionally each
Have a chief, but it is most of still need under vacuum conditions using or need to pre-process sample before the assay, no
Analysis continuous, in real time, high-throughput is carried out conducive to solid sample.Obtain within 2002 the electrospray ionisation source skill of Nobel chemistry Prize
Art is to develop a kind of more rapid normal pressure Soft ionization techniques in recent years, is transported for the first time by John B.Fenn the eighties in last century
It uses on mass spectrum, being particular in that while introduce highly polar non-volatile compounds solution for it can make analyte
Ionization, usually can be used as the research of biomolecule and multi-charge cluster ions.
Current some novel electric spray ion source interfaces also occur successively, for example, paper base electron spray, carbon fiber sprayer,
Wooden tip electron spray, multichannel electric spray ion source, cold spray ionization, electron spray parsing ionization (DESI), electron spray
Extraction ionization (EESI) technology etc., many important developments of these ionization techniques based on electron spray are all derived from
The pioneering work of John B.Fenn.In electrospray ionisation source (ESI), sample is dissolved in water first and others are molten
In agent, apply the high voltage of thousands of volts between the capillary outlet end and counter electrode of conveying sample solution, it will be in capillary
Pipe exports to form coniform liquid cone, under the action of strong electrical field, causes the separation of positive and negative ion, generation has high charge
Taylor cone, it is spraying so as to stablize.The big electrically charged sample ions drop sprayed due to solvent vaporization, with liquid
Drop volume is gradually reduced, and the charge density of drop has been more than the surface tension limit, the division that drop will be caused spontaneous, finally
Cause ion to be evaporated from charged drop, generates the ion of single charge or multi-charge.In sample ions forming process,
If ion cluster cannot sufficiently vaporize separation, the Ionization Efficiency of sample will be reduced.In many commercial instruments, mostly it is
Its sensitivity is improved by the method for winding heating tape to the heating of auxiliary gas or outside ion transport device, although these methods
Can raising ion source in various degree sensitivity, but or it is excessively complicated, or equipment instrument is significantly increased and is unfavorable for
The Miniaturization Research of mass spectrometer.
Therefore, a kind of electrospray ionisation source device how is obtained, structure is simple and small in size, generates ionspray intensity
Stablize, is suitable for the main trend of miniaturization, it has also become one of the focus of each line research staff's extensive concern in industry.
Summary of the invention
In view of this, the present invention provides a kind of for generating the ion source device of water body cluster ion, structure is simple, volume
It is small, it is able to maintain stabilization in the detection process, sensitivity also with higher and stability, height and distance are easy to adjust.
The present invention also provides a kind of Miniaturized portable mass spectrographs using above-mentioned ion source device.
To achieve the above object, the invention provides the following technical scheme:
It is a kind of for generating the ion source device of water body cluster ion, including sequentially connected liquid-supplying system, the first capillary,
Second liang of logical adapter and the second capillary further include high voltage loading mechanism；
The spray outlet of second capillary is smooth cutting end face.
Preferably, second liang of logical adapter is metal material；The high voltage loading mechanism includes two-way, the first via
Second liang of logical adapter is loaded on, the second tunnel loads on the outlet end of second capillary.
Preferably, the first via includes conducting wire, and the conducting wire is wrapped on described second two logical switching head surface；
Second tunnel includes metal tube, and second capillary passes through in the inner hole of the metal tube, and described
The outlet end of two capillaries is contacted with the metal tube.
It preferably, further include mass spectrograph sample introduction grade cavity, the spray outlet of second capillary is mounted on the mass spectrum
In instrument sample introduction grade cavity.
Preferably, the spray outlet position-adjustable of second capillary is mounted on the mass spectrograph sample introduction grade cavity
In.
It preferably, further include the mounting base being arranged on the mass spectrograph sample introduction grade cavity, the second capillary setting
In the mounting base.
Preferably, the liquid-supplying system includes sequentially connected syringe pump, syringe, syringe needle and first liang of logical adapter.
A kind of Miniaturized portable mass spectrograph, including electrospray ionisation source and ion transfer line, the electrospray ionisation source
To be above-mentioned for generating the ion source device of water body cluster ion.
Preferably, high voltage power supply, the height electricity of the ion source device are integrated in the circuit system of the ion transfer line
Pressure loading mechanism is connected to the high voltage power supply.
It can be seen from the above technical scheme that compared with prior art, the present invention is directed to current electrospray ionisation source
It (ESI) is sensitive by improving its to the method for assisting gas heating or winding heating tape outside ion transport device mostly in
Degree, but there are equipment excessively complexity or equipment instrument is significantly increased, it is unfavorable for the defect of Miniaturization Research；The invention proposes one
Kind is simply to generate the ion source device of water body cluster ion, from the solution parameter to play a decisive role to entire spray process
Direction is started with, under the premise of electric spray ion source itself is without heating device, from quartz capillary spray outlet section and spray
Locating two angles of environment in mist outlet are set out, using capillary section flatness height and Glabrous defect, to the volume of drop
Controlled, generate it is stable be sprayed, thus effectively carry out desolvation process；Using mass spectrograph sample introduction grade cavity, prevent
Influence and interference of the external environment (wind, the dust etc. in air) to ionspray intensity.Two kinds of measures are imitated to electron spray is improved
Rate, lowering apparatus detection limit play certain effect.Provided by the present invention for generating the ion source device of water body cluster ion,
It is simple with structure, sensitivity and high stability, it is easy to adjust the features such as.The experimental results showed that using the embodiment of the present invention
The ion source device of offer, can generate it is stable be sprayed, high sensitivity, lowering apparatus detection limit.The present invention also provides
A kind of Miniaturized portable mass spectrograph using above-mentioned ion source device.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is provided in an embodiment of the present invention for generating the structural schematic diagram of the ion source device of water body cluster ion；
Fig. 2 is mass spectrograph laboratory sample test chart provided in an embodiment of the present invention.
Wherein, 1 is syringe pump, and 2 be syringe, and 3 be the syringe needle of syringe, and 4 be first liang of logical adapter, and 5 be first mao
Tubule, 6 be second liang of logical adapter, and 7 deck to fix second liang of logical adapter on mass spectrograph sample introduction grade cavity, 8 be conducting wire,
9 be the second capillary, and 10 be screw, and 11 be mounting base, and 12 be the metal tube being fixed on inside mounting base, and 13 be ion transfer line
Sampling spiroid, 14 be mass spectrograph sample introduction grade cavity, and 15 be nested heating copper billet in ion transfer line, and 16 be high voltage power supply.
Specific embodiment
Core of the invention is to disclose a kind of for generating the ion source device of water body cluster ion, and structure is simple, body
Product is small, is able to maintain stabilization in the detection process, sensitivity also with higher and stability, height and distance are easy to adjust.
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Provided in an embodiment of the present invention for generating the ion source device of water body cluster ion, core improvement is, wraps
Sequentially connected liquid-supplying system, 5, second liang of logical adapters 6 of the first capillary and the second capillary 9 are included, further includes that high voltage adds
Mounted mechanism；The internal diameter of second liang of logical adapter 6 is adapted with the outer diameter of the outer diameter of the first capillary 5 and the second capillary 9 respectively；
The spray outlet of second capillary 9 is smooth cutting end face, is as obtained by cutting mode.
It can be seen from the above technical scheme that provided in an embodiment of the present invention for generating the ion source of water body cluster ion
Device is started with from the solution parameter direction to play a decisive role to entire spray process, in electric spray ion source itself without adding
Under the premise of thermal, from the second capillary pipe spray export structure, using capillary section flatness height and Glabrous
Defect controls the volume of drop, generate it is stable be sprayed, to effectively carry out desolvation process, while sensitivity
Height, the detection limit of lowering apparatus, structure are simple；The atomizing nozzle (such as nozzle needle form) of small size is although can also generate sample ions spray
Mist, but since atomizing nozzle is smaller, be easy to make mass signal intensity gradually die down by sample blocking；This programme overcomes such
Problem, atomizing nozzle are realized by cutting mode, and influence of the flatness of notch to ionspray is very big, and the notch the smooth more holds
Easily ionizable, it is significant to solve to hang drop phenomenon；And ion source device itself can effectively reduce body without the device of carrier gas or heating
Product, by the heating device of mass spectrometer ion transfer line itself, equally can be improved the ability of solvation.
Preferably, second liang of logical adapter 6 is metal material；High voltage loading mechanism includes two-way, first via load
In second liang of logical adapter 6, so that effect is on the capillary, the second tunnel loads on the outlet end of the second capillary 9, to provide more
Reasonable electric-force gradient optimizes ionization effect.
In the specific embodiment that this programme provides, the first via includes conducting wire 8, which is wrapped in second two logical turn
High pressure is loaded on the metal surface of connector 6, and available insulating tape is fixed；By using insulation outside the conducting wire 8 for applying high pressure
Adhesive tape is fastened, and avoids high pressure from being exposed to outside, more stable and safe, structure is referred to lead shown in Fig. 1 to facilitate
Electricity, safety operation, convenient for operating and be embodied as preferred embodiment；The length of the conducting wire is not particularly limited in the present invention, with this
Conventional length known to the technical staff of field, those skilled in the art can be according to detection case, mass spectrograph model and inspections
It surveys and requires to be selected and adjusted, the length of conducting wire of the present invention is preferably 10~15cm；
Second tunnel includes metal tube 12, and the second capillary 9 passes through in the inner hole of metal tube 12, and the second capillary 9 goes out
Mouth end is contacted with metal tube 12；Then the load of the second road high voltage is on the metal tube 12 for exporting end in contact with the second capillary 9.Such as
Shown in Fig. 1, in the present embodiment in the mounting base 11 (being here peek, that is, polyether-ether-ketone cylindrical body) of the second capillary 9 there are two
Metal interface, one is for being connected with high-voltage conducting wires 8, the second is metal tube 12, for the second capillary 9 from metal tube 12
It is passed through in inner hole, metal tube 12 is fixed on inside peek cylindrical body mounting base 11.
It is provided in an embodiment of the present invention for generating water body cluster ion for the operability and stability for improving single unit system
Ion source device, it is also preferable to include mass spectrograph sample introduction grade cavity 14, the mass spectrograph sample introduction grade cavity 14 and mass spectrograph ion are passed
Defeated grade cavity is connected, and the spray outlet of the-the second capillary of ionspray end 9 of ion source device is mounted on mass spectrograph sample introduction grade
In cavity 14.Different from previous electrospray ionisation source, the present apparatus adds the cavity with observation window outside spray outlet, effectively
Reduce the influence of ambient enviroment (wind, dust etc.) to ionspray, increases ionic strength and stability, and the cavity and matter
Spectrometer ion transmitting stage cavity is attached, and is realized the ion source device and is integrated on spectrometer system, is suitable for portable
Mass spectrograph.Second two logical adapter 6 is fixed on mass spectrograph sample introduction grade cavity 14 by deck 7.
Further, the spray outlet position-adjustable of the second capillary 9 is mounted in mass spectrograph sample introduction grade cavity 14, with
The spray outlet of adjustable ion source device and the angle and distance of ion transfer line entrance, the device pass spraying and ion
The adjusting of the distance between defeated line and angle is more convenient, to reduce influence of the ambient enviroment to the ionspray of generation, mentions
Macroion spraying stability and intensity.
It is provided in an embodiment of the present invention for generating the ion source device of water body cluster ion, further include setting mass spectrograph into
Mounting base 11 on sample grade cavity 14, the second capillary 9 are arranged in mounting base 11.Its structure is referred to shown in Fig. 1, installation
11 (being here peek cylindrical body) of seat are fixed on 14 upper end of mass spectrograph sample introduction grade cavity by screw 10；It can be adjusted by screw 10
Save peek cylindrical body 11 angle and height, and then realize change 9 spray outlet of the second capillary position, it can adjust from
The spray outlet of source arrangement and the angle and distance of ion transfer line entrance, adjust and are more convenient, and make the ionspray generated more
Stablize.Certainly, the installation of the second capillary 9 is fixed and position-adjustable can also be realized using other structures, no longer superfluous herein
It states.
Specifically, liquid-supplying system includes sequentially connected syringe pump 1, syringe 2, syringe needle 3 and first liang of logical adapter 4.
Syringe pump 1 therein can be according to 2 capacity regulating sample introduction flow velocity of syringe；Syringe 2 is fixed on syringe pump 1, and first liang logical
Adapter 4 is used for the connection of syringe needle 3 and the first capillary 5.The internal diameter of first liang of logical adapter 4 respectively with syringe needle
The outer diameter of first 3 outer diameter and the first capillary 5 is adapted.
Syringe pump is not particularly limited in the present invention, with well known to those skilled in the art for micro- with syringe cooperation
Syringe pump is measured, those skilled in the art can select and adjust according to detection case, mass spectrograph model and testing requirements
It is whole.In the present embodiment, the micro-injection pump preferably acts on the syringe of ion source device, and its role is to be capable of forming
Continuous-stable, flux controllable liquid-supplying system, in other embodiments, ion source device can also using other devices effect with
Syringe, to facilitate injection, safety operation, be capable of forming continuous-stable, flux controllable liquid-supplying system as preferred embodiment.This hair
The bright flow-control scope to the micro-injection pump is not particularly limited, with the micro note of routine well known to those skilled in the art
Penetrate the flow-control scope of pump, those skilled in the art can according to detection case, mass spectrograph model and testing requirements into
Row selection and adjustment, the flow-control scope of micro-injection pump of the present invention is preferably 0.1 μ l/hr~423ml/hr, more excellent
It is selected as 1 μ l/hr~300ml/hr, more preferably 10 μ l/hr~200ml/hr, more preferably 0.1~100ml/hr, most preferably
1~10ml/hr.
The syringe is not particularly limited in the present invention, with well known to those skilled in the art for mass spectrograph sample introduction
Syringe, those skilled in the art can select and adjust according to detection case, mass spectrograph model and testing requirements,
Syringe of the present invention is preferably mass spectrograph syringe, more preferably atmospheric pressure interface mass spectrograph syringe.
Further, inserted mode, two logical adapters two are connected as between two logical adapters (4,6) and capillary (5,9)
End is a male connector respectively, and centre is a nut connector, and capillary is inserted directly into two logical adapter one end
In the bushing pipe of male connector, male connector and nut connector are twisted into mode using hand and tightened, other end connection
Mode is identical, and connector is made to become " integral type ", the connecting line of good seal ne-leakage is formed, suitable for reality steady in a long-term
It tests.Preferably, first liang of logical adapter 4 and second liang of logical adapter 6 are metal material such as stainless steel.First capillary 5
For peek capillary, the second capillary 9 is quartz capillary.
The embodiment of the invention provides a kind of Miniaturized portable mass spectrographs, including electrospray ionisation source and ion transmission
Line, core improvement are that electrospray ionisation source is above-mentioned for generating the ion source device of water body cluster ion.This programme
Especially it regard the second capillary of vitreous silica 9 as sample introduction pintle-type nozzle, the second capillary of vitreous silica 9 uses the side of flat cut
The section smoothness of formula, ionspray outlet end has a great impact to sample ionization efficiency and ionic strength, section are more flat
Whole, Ionization Efficiency and ionic strength are higher, and solution can effectively be avoided at nozzle to hang drop phenomenon, desolvation significant effect,
It can be improved the sensitivity of electric spray ion source；And ion source device itself is without the device of carrier gas or heating, and it can be effective
Reduce volume and the ability of solvation equally can be improved by the heating device of mass spectrometer ion transfer line itself.It can manage
Solution, mass spectrometer further includes the parts such as mass analyzer, detector, vacuum system, circuit control and data collection system.
In order to advanced optimize above-mentioned technical solution, high voltage power supply 16 is integrated in the circuit system of ion transfer line,
The high voltage loading mechanism of ion source device is connected to high voltage power supply 16.It is that cooperation makes in view of ion source device and ion transfer line
, then power supply is not separately provided in ion source device, but utilizes the high-voltage electricity integrated in ion transfer line circuit system
Source 16 is conducive to simplify structure, realizes miniaturization.
The anode of high voltage power supply of the present invention is in contact with metal tube 12.The present invention is to the high voltage power supply without spy
It does not limit, with high voltage power supply well known to those skilled in the art, those skilled in the art can be according to detection case, mass spectrum
Instrument model and testing requirements are selected and are adjusted.The voltage range of the high voltage power supply is not particularly limited in the present invention, this
Field technical staff can select and adjust according to detection case, mass spectrograph model and testing requirements, height of the present invention
The operating voltage of voltage source 16 is preferably 0kV~+4.5kV.Ion source device high pressure of the present invention is provided by eastern literary high-pressure modular, should
High-pressure modular is integrated in mass spectrograph circuit system, and entire spectrometer system has the characteristics that small in size and stable.
The mode of the contact is not particularly limited in the present invention, in a manner of conductive contact well known to those skilled in the art
, those skilled in the art can select and adjust according to detection case, mass spectrograph model and testing requirements, of the invention
The contact preferably includes to be inserted into, is embedded in, is caught in, bonding and one of solder bond or a variety of.
This programme structure is described further combined with specific embodiments below:
The present invention provides a kind of for generating the ion source device of water body cluster ion, comprising: syringe pump 1, the injection
Pump 1 can be according to syringe capacity regulating sample introduction flow velocity；Syringe 2,2 capacity of syringe are 250ul, and syringe is fixed on
On syringe pump 1, syringe needle 3 leads to adapter 4 one with stainless steel two and connect；Two adapters, first liang of logical adapter 4 one therein
A connection for syringe 2 and the first capillary of peek material 5, second liang of logical adapter 6 is for the first capillary 5 and quartz
The connection of second capillary 9；The internal diameter of first capillary 5 be 0.01~0.5mm, outer diameter be 0.55~1.2mm, length be 40~
50cm；High voltage power supply 16,16 operating voltage of high voltage power supply are 0~+4.5kV, and You Dongwen high-pressure modular provides, the high pressing mold
Block is integrated in mass spectrograph circuit system, and entire spectrometer system has the characteristics that small in size and stable；The electricity of high voltage power supply 16
Pressure is wrapped on second liang of logical 6 metal surface of adapter by conducting wire 8 all the way and loads high pressure, another way load with the second capillary
Pipe 9 exports on the metal tube 12 of end in contact；Mounting base 11 is here peek cylindrical body, is fixed on mass spectrograph sample introduction by screw 10
Grade cavity 14 upper end, there are two metal interfaces in mounting base 11, one is for being connected with high-voltage conducting wires 8, the second is metal tube
12, it is passed through in the inner hole of metal tube 12 for the second capillary 9, passes through the angle and height of the adjustable mounting base 11 of screw 10
Degree, it can adjust the spray outlet of ion source device and the angle and distance of ion transfer line entrance, adjust and be more convenient, make to produce
Raw ionspray is more stable；The internal diameter of second capillary 9 is 0.01~0.15mm, and outer diameter is 0.1~1.2mm, length 20
~30cm, 9 one end of the second capillary are connected with second two logical adapter 6, and 9 other end of the second capillary is from mounting base 11
It is passed through in 12 inner hole of metal tube, and keeps suitable height and distance with mass spectrometric ion transfer line entrance sampling spiroid 13；Matter
Spectrometer sample introduction grade cavity 14, the mass spectrograph sample introduction grade cavity 14 is atmospheric pressure environment, with mass spectrograph ion transmitting stage cavity phase
Even, mass spectrograph sample introduction grade chamber can prevent influence of the external environment (wind, the dust etc. in air) to ionspray intensity and dry
It disturbs.
For a further understanding of the present invention, below with reference to course of work embodiment to Miniaturized portable provided by the invention
Mass spectrograph is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment uses the rectilinear ion trap mass spectrometry of above-mentioned ion source device and independent research, is referring to Fig. 1, Fig. 1
The structural schematic diagram of the ion source device provided in an embodiment of the present invention for being used to generate water body cluster ion.As shown in Fig. 2, using upper
When stating ion source device analysis sample, the solution of system to be studied is prepared first, in the present embodiment, by polypropylene glycol PPG sample
It is dissolved in acetonitrile, in the solvent that water volume ratio is CH3CN:H2O=1:3, is made into the PPG solution that concentration is 0.1mmol/L, equally,
Draw a certain amount of solution with syringe 2, be placed on micro-injection pump 1, the sample introduction velocity interval of micro-injection pump 1 be 20 μ L/h~
60 μ L/h are oppositely arranged the axial direction of the outlet of ion source device and mass spectrograph injection port sampling spiroid 13 is angled, into
Sample mouth is the aperture that a diameter is 0.25mm, connection atmospheric pressure and first order vacuum cavity, and the two distance is in 0.5cm~2cm
Between optimize adjusting.Using above-mentioned ion source device, the conducting wire of high voltage power supply is used on second liang of stainless steel logical adapter 6
8 windings apply high voltages, in experimentation, are adjusted, are melting between+1800V~+4500V positive voltage as needed
The aerosol spray that can produce fine droplet at 9 end nozzle of quartzy second capillary, passes through mass spectrometer vacuum interface unit
Deliver droplets on introducing difference vacuum system.Vacuum interface is mainly sampled using metal capillary transmission line, usually to transmission
Line nesting heating copper billet is heated to achieve the purpose that desolvation.Temperature control system is configured on transmission line, temperature can
Can be adjusted between 0 degree~200 degree according to experiment demand.PPG sample is detected using the structure of embodiment,
Measure mass spectrogram.Referring to fig. 2, Fig. 2 is the sample test figure of integral experiment device provided in an embodiment of the present invention.As shown in Fig. 2,
It can be found that 58, glycol polymers interval mass number, measurement result signal is stronger, and resolution ratio is higher, illustrates that the present invention can have
Effect applies in ion trap mass spectrometer.
In conclusion the embodiment of the invention discloses a kind of for generating the ion source device of water body cluster ion, to whole
The solution parameter direction that a spray process plays a decisive role is started with, in the premise of the not no heating device of electric spray ion source itself
Under, two angles of environment locating for the quartz capillary spray outlet section and spray outlet are flat using capillary section
Whole degree is high and Glabrous defect, controls the volume of drop, generate it is stable be sprayed, to effectively carry out desolvation
Process；Using mass spectrograph sample introduction grade cavity, influence of the external environment (wind, the dust etc. in air) to ionspray intensity is prevented
And interference.Two kinds of measures play certain effect to electron spray efficiency, lowering apparatus detection limit is improved.This programme apparatus structure
Simply, small in size, be able to maintain stabilization in the detection process, sensitivity also with higher and stability, fog outlet height and
Apart from easy to adjust.The embodiment of the invention also discloses a kind of Miniaturized portable mass spectrographs using above-mentioned ion source device.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (9)
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5439578A (en) * | 1993-06-03 | 1995-08-08 | The Governors Of The University Of Alberta | Multiple capillary biochemical analyzer |
| JP2003130848A (en) * | 2002-07-29 | 2003-05-08 | Hitachi Ltd | Method and apparatus for mass spectrometry of solutions |
| WO2003065405A1 (en) * | 2002-01-31 | 2003-08-07 | Hitachi High-Technologies Corporation | Electro-spray ionization mass spectrometer and method therefor |
| US20050258360A1 (en) * | 2004-05-21 | 2005-11-24 | Whitehouse Craig M | Charged droplet sprayers |
| CN1777478A (en) * | 2003-04-22 | 2006-05-24 | 纳幕尔杜邦公司 | Liquid dispersion device |
| CN102820201A (en) * | 2012-09-02 | 2012-12-12 | 王利兵 | Coaxial nested type multi-mode ion source |
| US20120312979A1 (en) * | 2011-06-03 | 2012-12-13 | Purdue Research Foundation (Prf) | Enclosed desorption electrospray ionization probes and method of use thereof |
| CN103545166A (en) * | 2013-11-04 | 2014-01-29 | 清华大学深圳研究生院 | Portable electrospray ion source device and mass spectrometer |
| CN103972019A (en) * | 2014-05-12 | 2014-08-06 | 清华大学 | Non-contact direct-current induction electrospray ionization device and method |
| WO2015040384A1 (en) * | 2013-09-23 | 2015-03-26 | Micromass Uk Limited | Probe assembly for attaching a chromatography device to a mass spectrometer |
| CN105181781A (en) * | 2009-05-01 | 2015-12-23 | 株式会社岛津制作所 | Ion analysis apparatus for conducting differential ion mobility analysis and mass analysis and the method of use |
| CN106683973A (en) * | 2017-01-17 | 2017-05-17 | 中国科学技术大学 | Electrospray ionization source device and system for mass spectrometers |
| CN207068794U (en) * | 2017-08-04 | 2018-03-02 | 中国科学技术大学 | Miniaturized portable mass spectrograph and the ion source device for producing water body cluster ion |
| CN112466961A (en) * | 2020-11-19 | 2021-03-09 | 晶科绿能(上海)管理有限公司 | Solar cell and method for manufacturing same |
-
2017
- 2017-08-04 CN CN201710660257.3A patent/CN109390206A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5439578A (en) * | 1993-06-03 | 1995-08-08 | The Governors Of The University Of Alberta | Multiple capillary biochemical analyzer |
| WO2003065405A1 (en) * | 2002-01-31 | 2003-08-07 | Hitachi High-Technologies Corporation | Electro-spray ionization mass spectrometer and method therefor |
| JP2003130848A (en) * | 2002-07-29 | 2003-05-08 | Hitachi Ltd | Method and apparatus for mass spectrometry of solutions |
| CN1777478A (en) * | 2003-04-22 | 2006-05-24 | 纳幕尔杜邦公司 | Liquid dispersion device |
| US20050258360A1 (en) * | 2004-05-21 | 2005-11-24 | Whitehouse Craig M | Charged droplet sprayers |
| CN105181781A (en) * | 2009-05-01 | 2015-12-23 | 株式会社岛津制作所 | Ion analysis apparatus for conducting differential ion mobility analysis and mass analysis and the method of use |
| US20120312979A1 (en) * | 2011-06-03 | 2012-12-13 | Purdue Research Foundation (Prf) | Enclosed desorption electrospray ionization probes and method of use thereof |
| CN102820201A (en) * | 2012-09-02 | 2012-12-12 | 王利兵 | Coaxial nested type multi-mode ion source |
| WO2015040384A1 (en) * | 2013-09-23 | 2015-03-26 | Micromass Uk Limited | Probe assembly for attaching a chromatography device to a mass spectrometer |
| CN103545166A (en) * | 2013-11-04 | 2014-01-29 | 清华大学深圳研究生院 | Portable electrospray ion source device and mass spectrometer |
| CN103972019A (en) * | 2014-05-12 | 2014-08-06 | 清华大学 | Non-contact direct-current induction electrospray ionization device and method |
| CN106683973A (en) * | 2017-01-17 | 2017-05-17 | 中国科学技术大学 | Electrospray ionization source device and system for mass spectrometers |
| CN207068794U (en) * | 2017-08-04 | 2018-03-02 | 中国科学技术大学 | Miniaturized portable mass spectrograph and the ion source device for producing water body cluster ion |
| CN112466961A (en) * | 2020-11-19 | 2021-03-09 | 晶科绿能(上海)管理有限公司 | Solar cell and method for manufacturing same |
Non-Patent Citations (2)
| Title |
|---|
| 李建强;周瑜芬;丁健桦;杨水平;陈焕文;: "运动场地游离甲苯-2, 4二异氰酸酯的直接电喷雾萃取电离质谱分析", 分析化学, no. 09 * |
| 李建强;周瑜芬;丁健桦;杨水平;陈焕文;: "运动场地游离甲苯-2, 4二异氰酸酯的直接电喷雾萃取电离质谱分析", 分析化学, no. 09, 15 September 2008 (2008-09-15) * |
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