CN101620974A - Device for eliminating bubbles in mass spectrum electron-spray ion source - Google Patents
Device for eliminating bubbles in mass spectrum electron-spray ion source Download PDFInfo
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- CN101620974A CN101620974A CN200910055146A CN200910055146A CN101620974A CN 101620974 A CN101620974 A CN 101620974A CN 200910055146 A CN200910055146 A CN 200910055146A CN 200910055146 A CN200910055146 A CN 200910055146A CN 101620974 A CN101620974 A CN 101620974A
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Abstract
The invention provides a device for eliminating bubbles in a mass spectrum electron-spray ion source and the influence of a sample on eliminating gases in the electron-spray ionizing process. The device comprises a base part, a concave part, a hydrophilic microchannel and a connecting piece, wherein the concave part is arranged on the base part; the hydrophilic microchannel is arranged on the base part and is communicated with the concave part; one end of the connecting piece is communicated with a liquid chromatogram fraction, and the other end of the connecting piece is communicated with the concave part. The invention can obtain a high-quality spectrogram, especially when using gases are used as a blank medium to retain the separation effect of a liquid chromatogram, the device can realize on-line gas elimination during electron-spray, not only retain functions of the gas separation liquid chromatogram fraction, but also enable the electron-spray to be continuous, thereby enhancing the quality of the electron-spray, making the quality of the spectrogram be higher, and being convenient for sequent identification and further analysis.
Description
Technical field
The present invention relates to a kind of treatment technology of electric spray ion source, the mass spectrum electron-spray ion source of saying so is more specifically removed the device of bubble.
Background technology
Mass spectral electron spray technology is a kind of soft ionization technology, the earliest by propositions such as Fenn.It uses strong electrostatic field to carry out ionization, and electron spray is often referred to the interface arrangement of liquid chromatogram and mass spectrometry.Solvent bank ionic or the polar sample molecular flow is crossed capillary, add a high voltage electric field in exit capillaceous, under the effect of Coulomb force, sample molecule can be sprayed in exit capillaceous, be atomized into the tiny droplet that has electric charge, be successfully used to the interface and the ionization apparatus of liquid chromatography mass combined instrument (LC/MS) and Capillary Electrophoresis GC-MS (CE/MS) now.
Electron spray ionisation (ESI) principle can be described by the electric charge relic model, the charged drop evaporation, and drop diminishes, and the electrostatic charge density that repels each other in the drop surface increases.When droplet evaporation to a certain degree, the Coulomb repulsion on drop surface makes the drop blast.The little charged drop that produces continues this process.Along with the hydrone of drop evaporates gradually, the protein molecular of the protonated and deprotonation of pacing up and down of just can gaining freedom.At the multi-charge state that electron spray ionisation produced, Fenn is interpreted as the multi-charge state molecular mass is repeatedly independently measured, and the averaging method of separating based on simultaneous equations, acquisition is to the correct appraisal of molecular mass, solved the problem of multiple-charged ion information, make protein molecular mass measurement precision obtain to improve greatly, and successfully to have measured molecular weight first in 1988 be the protein molecule of 40kD, accuracy reaches 99.99%.
Kebarle and Tang have analyzed sample at electrospray ionization mass spectrum (ESI-MS) ionization process.They think in the electrospray interface that the process from the generation of sample ions to analyzed detection can be divided into 4 steps: 1. sample solution enters the electron spray syringe needle spraying that adds high pressure and forms the drop that the surface has electric charge; 2. along with the volatilization of cushioning liquid, the charge density on drop surface increases.When the charge density on drop surface increased to the Rayleigh stability limit, promptly the electrostatic repulsion on drop surface was greater than the drip gauge surface tension, and drop is fragmented into littler drop.This process is carried out repeatedly, up to forming very little drop; 3. under the electrostatic repulsion effect, sample ions spins off from drop very little, that charge density is high and enters gas phase; 4. sample ions enters mass spectrum and carries out analyzing and testing.
Development along with proteomics, utilize liquid chromatogram to separate and identify that albumen has become the main flow analytical method that proteomics is separated evaluation with mass spectrometry, and in LC-MS (LC-MS), liquid chromatogram/electrospray ionization mass spectrum (LC-ESI-MS) is the important means of big Molecular Identification such as albumen.The influencing factor of this method spectrogram of LC-ESI-MS quality is a lot, remove the influence of instrument, the influencing factor of electron spray itself is just a lot, for example whether contains bubble, employed voltage or the like in employed buffering salt, the solution in the pH value of solution, the solution.
In order to obtain the spectrogram of better LC-MS, people study improved method always, for example the solution pH value is preferably near the isoelectric point of albumen, best PH is in acidity for the albumen of the unknown, can not use in the solution as buffering salts such as phosphate, use film sample introduction improves the suffertibility to buffer salt; Rule of thumb value is adjusted employed spray voltage, and for the bubble of removing in the solution, people just use the automatic deaerating machine that solvent is outgased before liquid chromatogram is carried out sample separation at present, do not carry out degassing processing in the electron spray stage.
We know the design problem owing to instrument itself, or the character problem of sample, separate some small bubbles of meeting existence in the later unavoidable solution in liquid chromatogram, and the existence of these bubbles will make the spectrogram quality of electro-spray ionization descend to some extent.Especially ought utilize bubble as separating the separating effect that medium keeps liquid chromatogram, when increasing mass spectral analysis time, the existence of gas descends the effect of electron spray, for example when carrying out the tandem analysis, daughter ion then can't detect if be distributed in the bubble section, cause the reduction of spectrogram quality to a certain extent, influenced the evaluation of macromolecular substances such as albumen to a certain extent.
As shown in Figure 5, stainless steel two logical 1 is seated on the operating platform 4 in the existing electrospray device, play the effect that connects liquid chromatogram cut 3 and nozzle needle 2,2 one capillaries of nozzle needle have most advanced and sophisticated, normally internal diameter is 50um, but the tip approximately is about 10um, and capillary is diminishing.Apply voltage in the time of on the tip and carry out electron spray, and then analyze in the mass spectrum 5.
But this electron spray can not solve in liquid chromatogram after separating solution and contain the problem of bubble, thereby causes the reduction of spectrogram quality to a certain extent, has influenced the evaluation of macromolecular substances such as albumen to a certain extent.
Given this, be necessary to provide a kind of device of mass spectrum electron-spray ion source removal bubble to address the above problem.
Summary of the invention
The present invention relates to remove in the mass spectrum electron-spray ion source device of bubble.Be used for solving the problem that contains bubble at liquid chromatogram after separating solution electron spray spectrogram problem of low quality when especially utilizing gas as reservation liquid chromatogram separating effect.
In order to address the above problem, the present invention adopts following technical scheme: a kind of mass spectrum electron-spray ion source is removed the device of bubble, this device comprises base portion, be arranged at recess on the base portion, be arranged on the base portion and the hydrophily microchannel and the end that are communicated with recess are communicated with the connector that the other end is communicated with recess with the liquid chromatogram cut.
As one of preferred version of the present invention, described base portion material is a metal, and described recess is a through hole, and described hydrophily microchannel cross-sectional area is identical.
As one of preferred version of the present invention, described base portion material is a metal, and described recess is a through hole, described hydrophily microchannel cross-sectional area from recess to reducing successively away from the recess direction.
As one of preferred version of the present invention, the micro-fluidic chip that described base portion is made for dimethyl silicone polymer PDMS, described hydrophily microchannel cross-sectional area from recess to reducing successively away from the recess direction.
As one of preferred version of the present invention, the micro-fluidic chip that described base portion is made for dimethyl silicone polymer PDMS, described hydrophily microchannel cross-sectional area is identical.
As one of preferred version of the present invention, described base portion comprises the tip, and this base shape is the pen nib shape, realizes electron spray at the last voltage that applies.
As one of preferred version of the present invention, described through-hole diameter is 1-3mm, and described hydrophily microchannel is long to be 1-10cm.
As one of preferred version of the present invention, the described hydrophily microchannel other end is communicated with mass spectral electron spray nozzle needle by jockey.
As one of preferred version of the present invention, the described hydrophily microchannel other end is by being communicated with mass spectral electron spray nozzle needle, and this electron spray nozzle needle is the capillary nozzle needle.
As one of preferred version of the present invention, the described hydrophily microchannel other end is provided with the tip and is used to be applied in voltage and carries out electron spray.
The present invention can obtain high-quality spectrogram, especially when using gases keeps the separating effect of liquid chromatogram as blank medium, use this covering device can be when realizing electron spray the online gas of removing, the function that had both kept gas separations liquid chromatogram cut, can make spraying continuously again, the electron spray quality is improved, and the spectrogram quality is higher, is convenient to follow-up evaluation and further analysis.
Description of drawings
Fig. 1 is for removing the device one example structure schematic diagram of bubble in the mass spectrum electron-spray ion source of the present invention;
Fig. 2 is the structural representation of base portion in the device of removing bubble in the mass spectrum electron-spray ion source of the present invention;
Fig. 3 is for removing another example structure schematic diagram of device of bubble in the mass spectrum electron-spray ion source of the present invention;
Fig. 4 is for removing the another example structure schematic diagram of device of bubble in the mass spectrum electron-spray ion source of the present invention;
Fig. 5 is existing mass spectrum electron-spray apparatus structure schematic diagram.
Embodiment
Further specify concrete implementation step of the present invention below in conjunction with accompanying drawing.
Embodiment one
As shown in Figure 1, a kind of mass spectrum electron-spray ion source is removed the device of bubble, this device comprises base portion, be arranged at through hole 13 on the base portion, be arranged on the base portion and the hydrophily microchannel 14 that is communicated with through hole 13 and an end are communicated with the connector 10 that the other end is communicated with through hole 13 with liquid chromatogram cut (comprising bubble 11 and liquid 12).
Described base portion equally has the structure of tip (taylor cone) and microchannel by the similar pen nib that a sheet metal is processed into as shown in Figure 1, in the middle of the sheet metal diameter being arranged is the through hole of 1-3mm, this through hole 13 is communicated with a length and is approximately 1-10cm, diameter is tapered to the microchannel (described hydrophily microchannel 14 cross-sectional areas from through hole 13 to reducing successively away from the through hole direction) of 10um from 100um, as shown in Figure 2, this microchannel also can be the identical duct of internal diameter.Sheet metal is through handling, and plating iraurite in surface is processed into hydrophilic surface with microchannel 14.With bubble at interval the capillary of liquid chromatogram component be connected to through hole 13 places of sheet metal by connector 10 because the capillarity of hydrophily microchannel 14, gas 11 is from through hole 13 volatilizations, liquid 12 imports the hydrophily microchannels.The surface of base portion and microchannel intersection are two straight lines, and the extension of two straight lines can be intersected in the direction away from through hole 13.During use, sheet metal (base portion) is placed on the workbench, adds directly that on the tip of sheet metal (base portion) voltage just can carry out electro-spray ionization.
Embodiment two
As shown in Figure 3, a kind of mass spectrum electron-spray ion source is removed the device of bubble, this device comprises base portion, be arranged at recess on the base portion, be arranged on the base portion and the hydrophily microchannel 24 and the end that are communicated with recess are communicated with the connector 20 that the other end is communicated with recess with liquid chromatogram cut (comprising bubble 22 and liquid 21).
Described base portion is the micro-fluidic chip 23 that PDMS (dimethyl silicone polymer) makes, on this micro-fluidic chip 23 design one sliver transvers section area from recess to the microchannel 24 that reduces successively away from the recess direction, this microchannel also is provided with tip (taylor cone), these microchannel 24 cross sections are part circle or " V " type, described microchannel 24 surfaces are processed into hydrophilic surface through peroxidating.The upper surface of micro-fluidic chip 23 and microchannel intersection are two straight lines, and the extension of two straight lines can be intersected in the direction away from recess.The liquid 21 that has a bubble 22 microchannel 24 of flowing through is because the hydrophilic interaction of liquid and microchannel makes bubble 22 be extruded microchannel, thereby reaches the effect of discharge gas.After gas gone out, on the tip of micro-fluidic chip Front-end Design, apply voltage, carry out electron spray.
Embodiment three
As shown in Figure 4, a kind of mass spectrum electron-spray ion source is removed the device of bubble, this device comprises base portion, be arranged at recess on the base portion, be arranged on the base portion and the hydrophily microchannel 37 and the end that are communicated with recess are communicated with the connector 30 that the other end is communicated with recess with liquid chromatogram cut (comprising bubble 32 and liquid 31).Described base portion is the micro-fluidic chip 33 that PDMS (dimethyl silicone polymer) makes, this micro-fluidic chip 33 is placed on the three-dimensional manipulating platform 34, internal diameter of design is about the microchannel 37 about 5-10um on this micro-fluidic chip 33, these microchannel 37 cross sections are the part circular section, described hydrophily microchannel cross-sectional area equalization; Also can be the equal V-type cross section of cross-sectional area, described microchannel 37 surfaces are processed into hydrophilic surface through peroxidating.The liquid 31 that has a bubble 32 microchannel 37 of flowing through is because the hydrophilic interaction of liquid and microchannel makes bubble 32 be extruded microchannel, thereby reaches the effect of discharge gas.The upper surface of micro-fluidic chip 33 is two parallel straight lines with microchannel 37 intersection.After gas gone out, link to each other with mass spectral electron spray nozzle needle and carry out electro-spray ionization by coupling assembling (for example stainless steel two is logical) at the front end of micro-fluidic chip.This electron spray nozzle needle is the capillary nozzle needle, for example quartz capillary or stainless steel capillary.If the diameter of capillary nozzle needle and microchannel 37 are complementary, also can not adopt coupling assembling, directly nozzle needle is placed on microchannel 37 and carries out electro-spray ionization.F1 represents bubble eliminating direction among the figure, and force direction interacts between the F2 express liquid.
The present invention can obtain high-quality spectrogram, especially when using gases keeps the separating effect of liquid chromatogram as blank medium, use this covering device can when electron spray, simply remove gas, the function that had both kept gas separations liquid chromatogram cut, can make spraying continuously again, the electron spray quality is improved, and the spectrogram quality is higher, is convenient to follow-up evaluation and further analysis.
The foregoing description is the unrestricted technical scheme of the present invention in order to explanation only.Any technical scheme that does not break away from spirit and scope of the invention all should be encompassed in the middle of the patent claim of the present invention.
Claims (10)
1. a mass spectrum electron-spray ion source is removed the device of bubble, it is characterized in that: this device comprises base portion, be arranged at recess on the base portion, be arranged on the base portion and the hydrophily microchannel and the end that are communicated with recess are communicated with the connector that the other end is communicated with recess with the liquid chromatogram cut.
2. remove the device of bubble as the described mass spectrum electron-spray ion source of right 1, it is characterized in that: described base portion material is a metal, and described recess is a through hole, described hydrophily microchannel cross-sectional area from recess to reducing successively away from the recess direction.
3. remove the device of bubble as right 1 described mass spectrum electron-spray ion source, it is characterized in that: described base portion material is a metal, and described recess is a through hole, and described hydrophily microchannel cross-sectional area is identical.
4. remove the device of bubble as the described mass spectrum electron-spray ion source of right 1, it is characterized in that: the micro-fluidic chip that described base portion is made for dimethyl silicone polymer PDMS, described hydrophily microchannel cross-sectional area from recess to reducing successively away from the recess direction.
5. remove the device of bubble as right 1 described mass spectrum electron-spray ion source, it is characterized in that: the micro-fluidic chip that described base portion is made for dimethyl silicone polymer PDMS, described hydrophily microchannel cross-sectional area is identical.
6. remove the device of bubble as right 2 described mass spectrum electron-spray ion sources, it is characterized in that: described base portion comprises the tip, and this base shape is the pen nib shape, realizes electron spray at the last voltage that applies.
7. remove the device of bubble as right 2 described mass spectrum electron-spray ion sources, it is characterized in that: described through-hole diameter is 1-3mm, and described hydrophily microchannel is long to be 1-10cm.
8. remove the device of bubble as right 5 described mass spectrum electron-spray ion sources, it is characterized in that: the described hydrophily microchannel other end is communicated with mass spectral electron spray nozzle needle by jockey.
9. remove the device of bubble as right 5 described mass spectrum electron-spray ion sources, it is characterized in that: the described hydrophily microchannel other end is communicated with mass spectral electron spray nozzle needle, and this electron spray nozzle needle is the capillary nozzle needle.
10. remove the device of bubbles as the described mass spectrum electron-spray ion sources of right 4, it is characterized in that: the described hydrophily microchannel other end is provided with the tip and is used to be applied in voltage and carries out electron spray.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910055146A CN101620974A (en) | 2009-07-21 | 2009-07-21 | Device for eliminating bubbles in mass spectrum electron-spray ion source |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910055146A CN101620974A (en) | 2009-07-21 | 2009-07-21 | Device for eliminating bubbles in mass spectrum electron-spray ion source |
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| CN101620974A true CN101620974A (en) | 2010-01-06 |
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| CN200910055146A Pending CN101620974A (en) | 2009-07-21 | 2009-07-21 | Device for eliminating bubbles in mass spectrum electron-spray ion source |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014145692A (en) * | 2013-01-30 | 2014-08-14 | Hitachi High-Technologies Corp | Mass spectrometry and mass spectrometer |
| CN108666201A (en) * | 2017-12-31 | 2018-10-16 | 宁波华仪宁创智能科技有限公司 | Incude Nanoliter electrospray ion source and its working method |
-
2009
- 2009-07-21 CN CN200910055146A patent/CN101620974A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014145692A (en) * | 2013-01-30 | 2014-08-14 | Hitachi High-Technologies Corp | Mass spectrometry and mass spectrometer |
| GB2525344B (en) * | 2013-01-30 | 2018-10-10 | Hitachi High Tech Corp | Method and device for mass spectrometry |
| CN108666201A (en) * | 2017-12-31 | 2018-10-16 | 宁波华仪宁创智能科技有限公司 | Incude Nanoliter electrospray ion source and its working method |
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Application publication date: 20100106 |