CN117269287A - Ink-jet sample injection-capillary electrophoresis-mass spectrum combined device and working method - Google Patents
Ink-jet sample injection-capillary electrophoresis-mass spectrum combined device and working method Download PDFInfo
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- CN117269287A CN117269287A CN202311543174.8A CN202311543174A CN117269287A CN 117269287 A CN117269287 A CN 117269287A CN 202311543174 A CN202311543174 A CN 202311543174A CN 117269287 A CN117269287 A CN 117269287A
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- 238000001819 mass spectrum Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 64
- 238000003860 storage Methods 0.000 claims abstract description 35
- 238000002347 injection Methods 0.000 claims abstract description 33
- 239000007924 injection Substances 0.000 claims abstract description 33
- 239000011521 glass Substances 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 238000007641 inkjet printing Methods 0.000 claims abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001514 detection method Methods 0.000 claims abstract description 15
- 238000005251 capillar electrophoresis Methods 0.000 claims abstract description 14
- 229910000838 Al alloy Inorganic materials 0.000 claims description 19
- 238000000738 capillary electrophoresis-mass spectrometry Methods 0.000 claims description 17
- 239000005388 borosilicate glass Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000000132 electrospray ionisation Methods 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 description 12
- 239000007853 buffer solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000011010 flushing procedure Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000872 buffer Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- -1 H 2 O Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002366 time-of-flight method Methods 0.000 description 1
Classifications
-
- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/447—Systems using electrophoresis
- G01N27/44756—Apparatus specially adapted therefor
-
- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/447—Systems using electrophoresis
- G01N27/44704—Details; Accessories
- G01N27/44743—Introducing samples
-
- 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
Abstract
The invention discloses an inkjet sample injection-capillary electrophoresis-mass spectrum combined device and a working method thereof, wherein the device comprises an inkjet sample injection unit, a capillary electrophoresis unit, a capillary mass spectrum connection unit and a high-voltage power supply unit; the ink-jet sample injection unit comprises an ink-jet printing chip and a first XY moving platform; the capillary electrophoresis unit comprises an XYZ mobile platform and a liquid storage tank, wherein a first platinum wire electrode is inserted into the liquid storage tank, and the inlet end of the capillary penetrates out of the bottom of the liquid storage tank upwards; the capillary mass spectrum connecting unit comprises a T-shaped tee joint, the outlet end of the capillary penetrates through a first interface of the T-shaped tee joint, penetrates out of a second interface on the opposite side and then penetrates into a glass capillary, the outlet of the glass capillary is opposite to the mass spectrum sample inlet, and a third interface of the T-shaped tee joint is connected with a sheath liquid bottle through a second capillary; the high-voltage power supply unit comprises a first high-voltage direct-current power supply and an electrospray high-voltage direct-current power supply. The device can be used for efficient separation and high-sensitivity detection of samples.
Description
Technical Field
The invention relates to the technical field of capillary electrophoresis and mass spectrometry detection, in particular to an inkjet sample injection-capillary electrophoresis-mass spectrometry device and a working method thereof.
Background
In food detection, drug analysis and clinical examination, because of the complex sample components, the analyte usually needs to be used in a device with high separation efficiency, high separation speed and high detection sensitivity. The capillary electrophoresis-mass spectrometer provides high separation efficiency, can effectively provide detection sensitivity and molecular structure information of a detected object, and is widely focused and rapidly developed.
Currently, commercial capillary electrophoresis-mass spectrometers have Agilent CE7100-QTOF and AB Sciex CESI-MS with two types of interfaces, namely sheath fluid interface and non-sheath fluid interface. The use of the sheath fluid interface can ensure that electrospray has a stable electrospray effect, but the high-pressure pump provides sheath fluid force, so that the flow speed is relatively large, the effect of diluting the sample exists, and the detection sensitivity is reduced. While the sheath-less liquid interface approach eliminates the dilution effect, it is more challenging to provide reliable electrospray high pressures.
On the other hand, the capillary electrophoresis-mass spectrometer has a sample injection volume of nano liter, the sample injection technology is usually electric sample injection and pressure sample injection, the electric sample injection equipment and the pressure sample injection equipment are complex and expensive, and the sample injection amount of the low-concentration sample is difficult to realize, so that the sample to be detected is difficult to detect.
Therefore, based on the defects and challenges existing in the existing capillary electrophoresis-mass spectrometry, a high-sensitivity capillary electrophoresis-mass spectrometry device (with a stable electrospray interface with small sample consumption) needs to be developed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an inkjet sample injection-capillary electrophoresis-mass spectrometry combined device and a working method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
an inkjet sampling-capillary electrophoresis-mass spectrum combined device is characterized in that: the device comprises an inkjet sample injection unit, a capillary electrophoresis unit, a capillary mass spectrum connection unit and a high-voltage power supply unit;
the inkjet sampling unit comprises an inkjet printing chip and a first XY moving platform;
the capillary electrophoresis unit comprises an XYZ mobile platform and a liquid storage tank fixed on the XYZ mobile platform, wherein a first platinum wire electrode is inserted into the liquid storage tank, and the inlet end of the capillary of the first capillary penetrates out upwards from the bottom of the liquid storage tank;
the capillary mass spectrum connecting unit comprises a T-shaped tee joint used for connecting a first capillary and a mass spectrum sample injection port, wherein the capillary outlet end of the first capillary penetrates from a first interface of the T-shaped tee joint, penetrates out from a second interface on the opposite side and then penetrates into a glass capillary, the outlet of the glass capillary is opposite to the mass spectrum sample injection port, a third interface of the T-shaped tee joint is connected with a sheath liquid bottle through the second capillary, and the capillary mass spectrum connecting unit is integrally fixed on an aluminum alloy ion source bracket;
the high voltage power supply unit includes a first high voltage direct current power supply and an electrospray high voltage direct current power supply for separation.
Further, a plurality of channels are arranged in the ink-jet printing chip, and each channel is used for storing different samples; the tablet ceramic on the chip can be controlled by changing the driving voltage, the sample injection quantity of the sample can be accurately controlled, and pL sample control can be realized. The first XY moving stage is configured to hold and move the inkjet printing chip in alignment with the capillary inlet end.
Further, a first platinum wire electrode is inserted into the liquid storage tank; the XYZ moving platform is used for fixing and moving the liquid storage pool.
Further, the first capillary is a capillary with a length of 70 cm and an inner diameter of 50 micrometers, and is used for sample separation.
Further, the glass capillary is made of borosilicate glass, has an outer diameter of 1 mm, an inner diameter of 0.75 mm, and a tip of 0.2-0.3 mm for electrospray ionization.
Further, the aluminum alloy ion source support comprises an aluminum alloy support and a second XY moving platform for fixing the T-shaped three-way joint, a digital microscope is fixed on the aluminum alloy support and used for observing the tip end of the glass capillary tube and the mass spectrum sample inlet in real time, and the distance between the tip end of the glass capillary tube and the mass spectrum sample inlet is 4mm.
Further, the sheath fluid bottle is used for providing sheath fluid flow, and a second platinum wire electrode is inserted into the sheath fluid bottle; the second capillary tube had a length of 15 cm and an inner diameter of 50 microns.
Further, the first high-voltage direct current power supply is used for being connected with a first platinum wire electrode in the liquid storage tank and used for providing separation voltage, and the separation voltage is 0-30 kV.
Further, the electrospray high-voltage direct current power supply is used for being connected with a second platinum wire electrode in the sheath liquid bottle and used for driving sheath liquid, and simultaneously, electrospray voltage is provided with 0-5kV.
The working method of the ink-jet sample injection-capillary electrophoresis-mass spectrum combined device comprises the following steps: first capillary pretreatmentThe first capillary, the glass capillary, the second capillary for sheath flow and the T-shaped three-way joint are loaded and fixed on a second XY moving platform of the aluminum alloy ion source bracket>Add sample->Sample introduction->Setting capillary electrophoresis separation voltage, electrospray voltage and mass spectrum detection parameter +.>Sample detection->Data processing->And (5) post-treating the capillary.
Compared with the prior art, the invention has the outstanding effects that:
the ink-jet sample injection-capillary electrophoresis-mass spectrum combined device can realize high-sensitivity detection of samples such as compounds, proteins, antibodies and the like.
The device provided by the invention is convenient to assemble, simple to operate, capable of realizing accurate sample injection and saving the sample consumption, and can be used for efficient separation and high-sensitivity detection of samples. Compared with the existing instrument and equipment, the device provided by the invention has the advantages of higher manufacturing cost, miniaturization and portability of the whole design, easiness in assembly and maintenance, less sample and reagent consumption and higher practical value and commercial value based on the inkjet printing sample injection and high-pressure driving sheath flow technology.
The inkjet sample injection-capillary electrophoresis-mass spectrometry device and the working method thereof are further described below with reference to the accompanying drawings and specific examples.
Drawings
FIG. 1 is a schematic diagram of the overall structure of an ink-jet sample injection-capillary electrophoresis-mass spectrometry device of the present invention;
FIG. 2 is a schematic diagram of a device for flushing a capillary tube;
FIG. 3 is a photograph of an ink-jet sample, a left image of a sample taken by a high-speed camera, and a right image of the sample taken by the high-speed camera;
FIG. 4 is a mass spectrum of the device of the invention for analyzing and detecting SigmaMAb;
fig. 5 is a graph of the exact molecular weight of SigmaMAb after deconvolution.
The device comprises a 1-ink-jet printing chip, a 2-liquid storage tank, a 3-first platinum wire electrode, a 4-first XY moving platform, a 5-XYZ moving platform, a 6-first capillary, a 7-T-shaped three-way joint, an 8-glass capillary, a 9-second platinum wire electrode, a 10-sheath liquid bottle, an 11-second capillary, a 12-second XY moving platform, a 13-aluminum alloy ion source bracket, a 14-mass spectrum sample injection port, a 15-first high-voltage direct current power supply, a 16-electrospray high-voltage direct current power supply, a 17-ink-jet printing port, an 18-capillary inlet end, a 19-capillary outlet end, a 20-transparent cover, a 21-miniature positive pressure pump, a 22-hose, a 23-centrifuge tube, a 24-centrifuge tube bracket and a 25-waste liquid bottle.
Detailed Description
The experimental methods used in the following examples are all conventional methods unless otherwise specified; materials, reagents and the like used, unless otherwise specified, are commercially available.
Example 1
As shown in FIG. 1, the ink-jet sample injection-capillary electrophoresis-mass spectrum combined device comprises an ink-jet sample injection unit, a capillary electrophoresis unit, a capillary mass spectrum connection unit and a high-voltage power supply unit. The ink-jet sample injection unit comprises an ink-jet printing chip 1 and a first XY moving platform 4; the capillary electrophoresis unit comprises an XYZ moving platform 5 and a liquid storage tank 2 which is fixed on the XYZ moving platform 5 and is used for containing buffer solution, a first platinum wire electrode 3 is inserted into the liquid storage tank 2, and a capillary inlet end 18 of a first capillary 6 penetrates out of the bottom of the liquid storage tank 2; the capillary mass spectrum connecting unit comprises a T-shaped tee joint 7 for connecting a first capillary tube 6 and a mass spectrum sample injection port 14, wherein a capillary outlet end 19 of the first capillary tube 6 penetrates from a first interface of the T-shaped tee joint 7, penetrates out of a second interface on the opposite side and then penetrates into a glass capillary tube 8, an outlet of the glass capillary tube 8 is opposite to the mass spectrum sample injection port 14, a third interface of the T-shaped tee joint 7 is connected with a sheath liquid bottle 10 through a second capillary tube 11, and the capillary mass spectrum connecting unit is integrally fixed on an aluminum alloy ion source bracket 13; the high voltage power supply unit comprises a first high voltage dc power supply 15 and an electrospray high voltage dc power supply 16 for separation.
Specifically:
the ink-jet printing unit comprises an ink-jet printing chip 1 and a first XY moving platform 4, wherein the ink-jet printing chip 1 is fixed on the upper surface of the first XY moving platform 4 through a bracket, and the ink-jet printing chip 1 can move along the X direction and the Y direction by controlling the first XY moving platform 4. Four channels are arranged in the ink-jet printing chip 1, each channel can store different samples, and the ceramic is pressed on the chip by changing the driving voltage, so that the sample injection amount of the samples in each channel is accurately controlled, and pL sample control is realized; the first XY moving stage 4 is for fixing and moving the inkjet printing chip 1 so as to be aligned with the capillary inlet end 18 of the first capillary 6.
The capillary electrophoresis unit comprises an XYZ moving platform 5, a bracket is fixed on the upper surface of the XYZ moving platform 5, a liquid storage tank 2 filled with buffer solution is fixed on the upper surface of the bracket, and the liquid storage tank 2 can move along the X direction, the Y direction and the Z direction by controlling the XYZ moving platform 5. The first platinum wire electrode 3 is inserted into the liquid storage tank 2, and the capillary inlet end 18 of the first capillary 6 passes out of the bottom of the liquid storage tank 2. When sample injection is needed, the liquid storage tank 2 is controlled to fall through the XYZ mobile platform 5, so that the inlet end 18 of the capillary tube is exposed from the liquid level of the liquid storage tank 2; when the buffer liquid needs to be switched, the liquid storage tank 2 is controlled to rise through the XYZ moving platform 5, so that the inlet end 18 of the capillary tube falls below the liquid level of the liquid storage tank 2. The liquid storage tank 2 is formed by 3D printing, and the ink-jet printing chip 1 is arranged above the liquid storage tank 2; the first capillary 6 is a capillary of length 70 cm and inner diameter 50 microns for sample separation.
The capillary mass spectrum connecting unit comprises a T-shaped tee joint 7 for connecting a first capillary tube 6 and a mass spectrum sample injection port 14, a capillary outlet end 19 of the first capillary tube 6 penetrates from a first interface of the T-shaped tee joint 7, penetrates out of a second interface on the opposite side and then penetrates into a glass capillary tube 8, an outlet of the glass capillary tube 8 is opposite to the mass spectrum sample injection port 14, a third interface of the T-shaped tee joint 7 is connected with a sheath liquid bottle 10 through a second capillary tube 11, and the T-shaped tee joint 7 and the sheath liquid bottle 10 are integrally fixed on an aluminum alloy ion source bracket 13. The glass capillary 8 is made of borosilicate glass, has an outer diameter of 1. 1 mm, an inner diameter of 0.75 mm, and a tip of 0.2-0.3 mm, and is used for electrospray ionization. The aluminum alloy ion source bracket 13 comprises an aluminum alloy bracket and a second XY moving platform 12 for fixing the T-shaped three-way joint 7, wherein the T-shaped three-way joint 7 is fixed on the upper surface of the second XY moving platform 12, and the lower surface of the second XY moving platform 12 is fixed on the aluminum alloy bracket. A digital microscope is also fixed on the aluminum alloy bracket and used for observing the tip of the glass capillary tube 8 and the mass spectrum sample inlet 14 in real time, and the distance between the tip and the mass spectrum sample inlet is 4mm. The sheath fluid bottle 10 is used for providing sheath fluid flow, and the second platinum wire electrode 9 is inserted into the sheath fluid bottle 10. The second capillary 11 has a length of 15 cm and an inner diameter of 50 μm.
The high voltage power supply unit comprises a first high voltage dc power supply 15 and an electrospray high voltage dc power supply 16 for separation. The first high-voltage direct current power supply 15 is used for being connected with the first platinum wire electrode 3 in the liquid storage tank 2 and providing separation voltage, and the separation voltage is 0-30 kV. The electrospray high-voltage direct current power supply 16 is used for being connected with the second platinum wire electrode 9 in the sheath liquid bottle 10, is not only used for providing driving of sheath liquid, but also provides electrospray voltage, and the voltage is 0-5kV.
The aluminum alloy ion source bracket 13 is also provided with a transparent cover 20, and the T-shaped three-way joint 7, the sheath liquid bottle 10 and the second XY moving platform 12 are all positioned in the transparent cover 20.
As shown in fig. 2, the apparatus further comprises a flushing device comprising a miniature positive pressure pump 21, the miniature positive pressure pump 21 being in communication with the centrifuge tube 23 through a stopper of the centrifuge tube 23 by a hose 22 (the hose 22 is not in contact with the liquid in the centrifuge tube 23), the centrifuge tube 23 being disposed on a centrifuge tube holder 24. When the first capillary tube 6 needs to be flushed, the inlet end of the first capillary tube 6 is inserted into the liquid in the centrifuge tube 23 through the plug of the centrifuge tube 23, and the other end is inserted into the waste liquid bottle 25. The number of centrifuge tubes 23 is 3, and 1M NaOH and H are respectively filled in the centrifuge tubes 2 O and buffer solution (the buffer solution has the same formula as the buffer solution in the liquid storage tank 2).
Example 2
The detection was performed on a 0.2. 0.2 mg/mL SigmaMAb sample using the inkjet sample-capillary electrophoresis-mass spectrometry device of example 1. The buffer was 30% acetic acid solution. The sheath fluid was a mixed solution of 20% acetic acid and 25% acetonitrile.
The working method comprises the following steps: first capillary pretreatmentThe first capillary, the glass capillary, the second capillary for sheath flow and the T-shaped three-way joint are loaded and fixed on a second XY moving platform of the aluminum alloy ion source bracket>Add sample->Sample introduction->Setting capillary electrophoresis separation voltage, electrospray voltage and mass spectrum detection parameter +.>Sample detectionData processing->And (5) post-treating the capillary.
The specific method comprises the following steps:
(1) Sample preparation: 1M NaOH, H 2 O, buffer solution, sheath fluid, sample, etc.
(2) Flushing the first capillary tube before sample injection: 1M NaOH is arranged in a centrifuge tube 23 of 5 mL, as shown in fig. 2, the centrifuge tube 23 is connected with a capillary inlet end 18 of a first capillary tube 6, the capillary inlet end 18 is immersed in liquid of the centrifuge tube 23, the centrifuge tube 23 is connected with a micro positive pressure pump 21 through a hose 22, the hose 22 is not contacted with the liquid of the centrifuge tube 23, and is used for providing flushing power and flushing for 5 min; in the same way, switch to being provided with H 2 And (3) flushing the centrifuge tube for 10 min, switching to flushing the pipeline in the centrifuge tube filled with the buffer solution for 10 min, and finally filling the buffer solution into the first capillary tube 6.
(3) The inlet end 18 of the washed capillary tube is fixed in the liquid storage tank 2, and the outlet end 19 of the capillary tube passes through the T-shaped three-way joint 7 and is fixed. The outlet end 19 of the capillary tube penetrates into the glass capillary tube 8, the third interface of the T-shaped tee joint 7 is connected with the second capillary tube 11, and the sheath liquid bottle 10 is pressurized to enable the sheath liquid to fill the capillary tube, the T-shaped tee joint and the glass capillary tube; the distance between the glass capillary 8 and the mass spectrum sample inlet 14 was observed by a digital microscope, and the distance between the two was 4mm.
(4) Loading a sample to the ink-jet printing chip 1, and controlling the driving voltage and the sample feeding amount through software.
(5) The relative positions of the liquid storage tank 2 and the first capillary 6 are adjusted through the XYZ moving platform 5 and the second XY moving platform 12, and the position of the ink-jet printing chip 1 is adjusted through the first XY moving platform 4, so that the ink-jet port of the ink-jet printing chip is aligned with the center of the inlet end 18 of the capillary, and the ink-jet printing chip is used for sample injection, and the minimum sample amount can be about 160 PL/drop, as shown in fig. 3.
(6) After sample injection, the position of the inlet end of the capillary is adjusted by controlling the second XY moving platform, so that the capillary is immersed in the liquid storage tank 2 filled with the buffer solution.
(7) Capillary separation voltage, electrospray voltage and mass spectrometry Q-TOF method parameters were set. The buffer solution in the liquid storage tank 2 enters the capillary under the action of high pressure, and simultaneously, the sample separation is carried out.
The capillary electrophoresis separation voltage was set at 30 kV and the electrospray voltage was 3 kV.
Mass spectrometry parameter setting:
| mass spectrum scan range | Capillary voltage | Fracture voltage | Dryer flow rate | Dryer temperature |
| 2000-5000 m/z | 0 V | 380 V | 3 L/min | 350 ℃ |
(8) And (3) data processing: data were collected and analyzed using Agilent MassHunter workstation software and deconvolved with MassHunter BioConfirm and then analyzed for processing, as shown in fig. 4-5.
(9) After the sample detection is finished, H is used for 2 O washes the first capillary for 10 min.
The experimental result shows that the ink-jet sample injection-capillary electrophoresis-mass spectrometry combined device can realize high-sensitivity detection of samples such as compounds, proteins, antibodies and the like.
The above examples are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. An inkjet sampling-capillary electrophoresis-mass spectrum combined device is characterized in that: the device comprises an inkjet sample injection unit, a capillary electrophoresis unit, a capillary mass spectrum connection unit and a high-voltage power supply unit;
the inkjet sampling unit comprises an inkjet printing chip and a first XY moving platform;
the capillary electrophoresis unit comprises an XYZ mobile platform and a liquid storage tank fixed on the XYZ mobile platform, wherein a first platinum wire electrode is inserted into the liquid storage tank, and the inlet end of the capillary of the first capillary penetrates out upwards from the bottom of the liquid storage tank;
the capillary mass spectrum connecting unit comprises a T-shaped tee joint used for connecting a first capillary and a mass spectrum sample injection port, wherein the capillary outlet end of the first capillary penetrates from a first interface of the T-shaped tee joint, penetrates out from a second interface on the opposite side and then penetrates into a glass capillary, the outlet of the glass capillary is opposite to the mass spectrum sample injection port, a third interface of the T-shaped tee joint is connected with a sheath liquid bottle through the second capillary, and the capillary mass spectrum connecting unit is integrally fixed on an aluminum alloy ion source bracket;
the high voltage power supply unit includes a first high voltage direct current power supply and an electrospray high voltage direct current power supply for separation.
2. The inkjet sampling-capillary electrophoresis-mass spectrometry device of claim 1, wherein: a plurality of channels are arranged in the ink-jet printing chip, and each channel is used for storing different samples; the tablet ceramic on the chip can be controlled by changing the driving voltage, so that the sample injection amount of the sample can be accurately controlled, and pL sample control can be realized; the first XY moving stage is configured to hold and move the inkjet printing chip in alignment with the capillary inlet end.
3. The inkjet sampling-capillary electrophoresis-mass spectrometry device of claim 1, wherein: a first platinum wire electrode is inserted into the liquid storage tank; the XYZ moving platform is used for fixing and moving the liquid storage pool.
4. The inkjet sampling-capillary electrophoresis-mass spectrometry device of claim 1, wherein: the first capillary is a capillary with the length of 70 cm and the inner diameter of 50 micrometers and is used for sample separation.
5. The inkjet sampling-capillary electrophoresis-mass spectrometry device of claim 1, wherein: the glass capillary is made of borosilicate glass, has an outer diameter of 1 mm, an inner diameter of 0.75 mm, and a tip of 0.2-0.3 mm, for electrospray ionization.
6. The inkjet sampling-capillary electrophoresis-mass spectrometry device of claim 1, wherein: the aluminum alloy ion source support comprises an aluminum alloy support and a second XY moving platform for fixing the T-shaped three-way joint, a digital microscope is fixed on the aluminum alloy support and used for observing the tip end of the glass capillary tube and the mass spectrum sample injection port in real time, and the distance between the tip end of the glass capillary tube and the mass spectrum sample injection port is 4mm.
7. The inkjet sampling-capillary electrophoresis-mass spectrometry device of claim 1, wherein: the sheath liquid bottle is used for providing sheath liquid flow, and a second platinum wire electrode is inserted into the sheath liquid bottle; the second capillary tube had a length of 15 cm and an inner diameter of 50 microns.
8. The inkjet sampling-capillary electrophoresis-mass spectrometry device of claim 1, wherein: the first high-voltage direct current power supply is used for being connected with a first platinum wire electrode in the liquid storage tank and providing separation voltage, and the separation voltage is 0-30 kV.
9. The inkjet sampling-capillary electrophoresis-mass spectrometry device of claim 1, wherein: the electrospray high-voltage direct current power supply is used for being connected with a second platinum wire electrode in the sheath liquid bottle and used for driving sheath liquid and simultaneously providing electrospray voltage of 0-5kV.
10. The method for operating the inkjet sample injection-capillary electrophoresis-mass spectrometry device according to any one of claims 1 to 9, characterized in that: first capillary pretreatmentThe first capillary, the glass capillary, the second capillary for sheath flow and the T-shaped three-way joint are loaded and fixed on a second XY moving platform of the aluminum alloy ion source bracket>Add sample->Sample introduction->Setting capillary electrophoresis separation voltage, electrospray voltage and mass spectrum detection parameter +.>Sample detection->Data processing->And (5) post-treating the capillary.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988007888A1 (en) * | 1987-04-06 | 1988-10-20 | Battelle Memorial Institute | Combined electrophoresis-electrospray interface and method |
| US5415841A (en) * | 1993-05-28 | 1995-05-16 | Governers Of The University Of Alberta | Continuous biochemical reactor for analysis of sub-picomole quantities of complex organic molecules |
| CA2243560A1 (en) * | 1996-01-23 | 1997-07-31 | Rapigene, Inc. | Methods and compositions for determining the sequence of nucleic acid molecules |
| FR2865145A1 (en) * | 2004-01-19 | 2005-07-22 | Commissariat Energie Atomique | Microfluid droplet dispenser, especially for cytometry, has main and secondary channels, physical property measuring device and pressure wave generator |
| WO2015121366A1 (en) * | 2014-02-13 | 2015-08-20 | Analis S.A. | Ce-ms interface |
| CN105092678A (en) * | 2015-08-03 | 2015-11-25 | 李绍平 | Capillary electrophoresis and eletro-chromatography insert part |
| CN106248777A (en) * | 2016-08-18 | 2016-12-21 | 东南大学 | A kind of normal pressure open type sampling system |
| CN108020592A (en) * | 2017-11-03 | 2018-05-11 | 中国科学院武汉物理与数学研究所 | The method of phosphatidyl choline and application in a kind of mass spectrometry quantitative analysis serum of Capillary Electrophoresis |
| CN109444247A (en) * | 2018-11-01 | 2019-03-08 | 宁波大学 | A kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device and method |
| CN110459459A (en) * | 2019-07-29 | 2019-11-15 | 中国科学院上海有机化学研究所 | A kind of ion induction electrospray ionisation method and apparatus |
| WO2021063968A1 (en) * | 2019-09-30 | 2021-04-08 | INSERM (Institut National de la Santé et de la Recherche Médicale) | Method and composition for diagnosing chronic obstructive pulmonary disease |
| CN213337441U (en) * | 2020-09-14 | 2021-06-01 | 中国科学院城市环境研究所 | Capillary electrophoresis device and capillary electrophoresis mass spectrometer |
-
2023
- 2023-11-20 CN CN202311543174.8A patent/CN117269287A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988007888A1 (en) * | 1987-04-06 | 1988-10-20 | Battelle Memorial Institute | Combined electrophoresis-electrospray interface and method |
| US5415841A (en) * | 1993-05-28 | 1995-05-16 | Governers Of The University Of Alberta | Continuous biochemical reactor for analysis of sub-picomole quantities of complex organic molecules |
| CA2243560A1 (en) * | 1996-01-23 | 1997-07-31 | Rapigene, Inc. | Methods and compositions for determining the sequence of nucleic acid molecules |
| FR2865145A1 (en) * | 2004-01-19 | 2005-07-22 | Commissariat Energie Atomique | Microfluid droplet dispenser, especially for cytometry, has main and secondary channels, physical property measuring device and pressure wave generator |
| WO2015121366A1 (en) * | 2014-02-13 | 2015-08-20 | Analis S.A. | Ce-ms interface |
| CN105092678A (en) * | 2015-08-03 | 2015-11-25 | 李绍平 | Capillary electrophoresis and eletro-chromatography insert part |
| CN106248777A (en) * | 2016-08-18 | 2016-12-21 | 东南大学 | A kind of normal pressure open type sampling system |
| CN108020592A (en) * | 2017-11-03 | 2018-05-11 | 中国科学院武汉物理与数学研究所 | The method of phosphatidyl choline and application in a kind of mass spectrometry quantitative analysis serum of Capillary Electrophoresis |
| CN109444247A (en) * | 2018-11-01 | 2019-03-08 | 宁波大学 | A kind of transient state capillary isotachophoresis-electron spray-mass spectrometry device and method |
| CN110459459A (en) * | 2019-07-29 | 2019-11-15 | 中国科学院上海有机化学研究所 | A kind of ion induction electrospray ionisation method and apparatus |
| WO2021063968A1 (en) * | 2019-09-30 | 2021-04-08 | INSERM (Institut National de la Santé et de la Recherche Médicale) | Method and composition for diagnosing chronic obstructive pulmonary disease |
| CN213337441U (en) * | 2020-09-14 | 2021-06-01 | 中国科学院城市环境研究所 | Capillary electrophoresis device and capillary electrophoresis mass spectrometer |
Non-Patent Citations (3)
| Title |
|---|
| FENGMING CHEN等: "Single-Cell Analysis Using Drop-on-Demand Inkjet Printing and Probe Electrospray Ionization Mass Spectrometry", 《ANALYTICAL CHEMISTRY》, vol. 88, no. 08, pages 4354 * |
| WEIFEI ZHANG等: "Inkjet printing based separation of mammalian cells by capillary electrophoresis", 《ANALYTICAL CHEMISTRY》, vol. 89, no. 17, pages 1 - 5 * |
| 廉哲等: "喷墨打印墨迹理化分析方法综述", 《刑事技术》, vol. 45, no. 05, pages 458 - 463 * |
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