CN100429511C - Electrochemical detection method and device of integrated in chip capillary electrophoresis - Google Patents
Electrochemical detection method and device of integrated in chip capillary electrophoresis Download PDFInfo
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- CN100429511C CN100429511C CNB2004100145990A CN200410014599A CN100429511C CN 100429511 C CN100429511 C CN 100429511C CN B2004100145990 A CNB2004100145990 A CN B2004100145990A CN 200410014599 A CN200410014599 A CN 200410014599A CN 100429511 C CN100429511 C CN 100429511C
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- 238000000835 electrochemical detection Methods 0.000 title claims abstract description 18
- 238000005251 capillar electrophoresis Methods 0.000 title abstract description 3
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- 238000001514 detection method Methods 0.000 claims abstract description 22
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 10
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- 238000001962 electrophoresis Methods 0.000 claims description 29
- 239000011263 electroactive material Substances 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
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- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 239000012146 running buffer Substances 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 5
- 125000006850 spacer group Chemical group 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 238000010422 painting Methods 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract 2
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 239000013307 optical fiber Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 12
- UCTWMZQNUQWSLP-UHFFFAOYSA-N adrenaline Chemical compound CNCC(O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 229960003638 dopamine Drugs 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
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- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention discloses a new electrochemical detection method established based on a new test principle in the process of capillary electrophoresis for a chip and a device. Firstly, a special-purpose high-voltage power supply of a chip capillary is utilized for monitoring and controlling whether a separation pipeline and a sample feeding pipeline are expedite or not; afterwards, high voltage is added to the separation pipeline to activate a working electrode; after the pipelines are expedite and the electrode is processed well, the working electrode is clamped on an optical fiber clamp matched with a three-dimensional regulator, and the front end of the working electrode under a stereoscopic microscope is arranged in a micro pipeline. The working electrode of ultra-micro circular disc carbon fiber is arranged at the inner part of the micro pipeline by the precise three-dimensional regulator, and high-efficiency separating detection to electro-inactive substances and electro-active substances is realized; the present invention breaks through the detection range of the existing electrochemistry test technique, and thus, the present invention not only can detect the electro-active substances, but also can detect the electro-inactive substances; the present invention carries out the high-efficiency separation and the high-sensitivity detection to inorganic and organic samples by correctly controlling the positions of electric potential and the working electrode in special regions.
Description
Technical field
The present invention is a kind of model electrochemical detection technique and isolated plant that is integrated in chip capillary cataphoresis, specifically, be in the process of integrated electrochemical technology and chip capillary cataphoresis isolation technics, by the position of accurate control electrochemical working electrode, sample is carried out high efficiency separation and high-sensitivity detection.
Background technology
One of research forward position focus of analysis science is exactly a micro-total analysis system at present.Traditional analytical instrument and means all need lot of manpower and material resources, and whole process automation degree is very low, and simultaneously the consumption of the reagent and the energy is bigger, and these have caused adverse effect in from now on development all for analysis science.Under this background, the research of micro-total analysis system is arisen at the historic moment.Micro-total analysis system can be integrated in the whole analysis process in laboratory such as sample preparation, sample filtering, sample separation and sample detection etc. and carry out on the little chip block, can realize the robotization and the microminiaturization of whole analysis process, enter into huge numbers of families and lay a good foundation for analytical instrument from now on becomes consumer product.
Focus is more in the research of present micro-total analysis system, and one of them important focus is exactly the high-sensitivity detection technology that is integrated in chip.The commercial detection method of success is the laser-Induced Fluorescence Detection method at present, and it can detect the material that can be excited to send fluorescence by laser at post, and sensitivity is high, and separation efficiency is also higher.But the usually necessary derivatization of the material that is detected uses the cost of laser higher simultaneously.So further commercialization has been difficult to realize.Comparatively speaking, electrochemical measuring technique is a kind of high sensitivity, is easy to microminiaturized detection technique.The principle research basis of electrochemical detection method is deep, and comparative maturity, instrument commercialized degree are than higher, and microminiaturized degree is also than higher, and it may become the detection method of being accepted by masses in future fully.
But three kinds of electrochemical detection methods of development respectively have relative merits at present.The ampere method can detect electroactive material, and sensitivity is higher relatively, but working electrode is contaminated easily; Conductance method can detect the material that influences solution conductivity, and versatility is better, but sensitivity is not high; Potential method can detect specific material, and selectivity ratios is higher, but range of application is narrower comparatively speaking.Another critical problem is the accurate location of working electrode, because the microminiaturization of pipeline, this has become a common problem.
Therefore, integrated novel low cost, high sensitivity, universal electrochemical detection method in chip are with micro-total analysis system commercialization early and move towards the only way which must be passed of huge numbers of families.
Summary of the invention
The present invention seeks to: use simple instrument and equipment, position by accurate control electrochemical working electrode, realize under the constant potential high-sensitivity detection to non-electroactive material, solve working electrode and pipeline opening alignment issues in the chip capillary cataphoresis Electrochemical Detection, keep high-sensitivity detection simultaneously electroactive material; A kind of convenience also is provided and monitors the method for electroosmotic flow effectively, the commercialization that helps micro-total analysis system is used.
Technical solution of the present invention is: be integrated in the model electrochemical detection method of chip capillary cataphoresis, micro-fluidic chip is fixed on the chip supporting platform, and electrochemical working electrode is fixed on the three-dimensional regulation device, then damping fluid is injected electrochemical investigating pond; Make the application of sample of described micro-fluidic chip and separating pipe all be full of damping fluid with vacuum pump; To separate high-field electrode, separate ground-electrode, application of sample high-field electrode, application of sample ground-electrode, galvanochemistry contrast electrode, galvanochemistry be placed on the detection position to electrode and fix; Each electrode is connected used galvanochemistry instrument and chip capillary cataphoresis with on the high-voltage power supply, at first utilize micro flow control chip capillary electrophoresis whether unimpeded with high-voltage power supply monitoring separating pipe and application of sample pipeline, on separating pipe, add the high pressure of long period then, simultaneously working electrode is activated; Wherein platinum electrode is used as separation high pressure, application of sample high pressure, separation ground connection and the application of sample ground-electrode of microchannel, after unobstructed and electrode is handled well at pipeline, with working electrode be clipped in the supporting fibre clip of three-dimensional regulation device on, under stereomicroscope, the front end of working electrode is placed on microchannel.Three-dimensional regulating mechanism by precision is placed on the inside of microchannel with ultra micro disk carbon fiber working electrode, has realized non-high efficiency separation electroactive and electroactive material is detected.Working electrode is placed on the interior approximately 30-100 micron of inside outlet of microchannel.Especially about 50 microns.
Whole device is made of the chip supporting platform of an integrated micro three-dimensional regulation device, comprises compositions such as micro-fluidic chip, chip capillary high-voltage power supply special, vacuum pump, ultrasonic cleaning instrument, infrared lamp, some platinum electrodes, stereomicroscope, microelectrode glass-pulling instrument simultaneously.Micro-fluidic chip is fixed on the chip supporting platform.With ready-made ultra micro disk working electrode be clipped in the supporting fibre clip of three-dimensional regulation device on, with the leakproof of vacuum silicone grease, note between working electrode and pipeline opening, maintaining a certain distance.After in detection cell, having added damping fluid, make damping fluid be full of pipeline with vacuum pump.At first utilize chip capillary high-voltage power supply special monitoring separating pipe and application of sample pipeline whether unimpeded, on separating pipe, add the high pressure of long period then, simultaneously working electrode is activated.After unobstructed and electrode is handled well at pipeline, under stereomicroscope, the front end of ultra micro disk working electrode is placed in the outlet of microchannel about 50 microns.
Wherein platinum electrode is used as separation high pressure, application of sample high pressure, separation ground connection and the application of sample ground-electrode of microchannel, and the ultra micro disk working electrode of use, is made as the carbon fiber about 8 microns generally at the 5-10 micron with diameter 5-20 micron.Also can adopt other diameter is that other of 5-20 micron is as gold electrode, platinum electrode, copper electrode etc.Process is as follows, draws on the instrument in glass microelectrode glass capillary is pulled into the tip, exposes about 1 mm length after microscopically penetrates its tip with individual carbon fibers, fix with glue, pouring into carbon dust in the back, is 500 microns copper wire jam-pack carbon dust with diameter, fixing endways with glue.The carbon fiber electrode of making is electroplated with cathode electrodip painting on electrochemical workstation, dried by the fire 20 minutes down at 170 degrees centigrade then.Cut the front end of carbon fiber electrode flat standby with clean scalpel at microscopically before using.
The optimal operating parameter of this technology is: separation voltage: 200V/cm～500V/cm; Working electrode detects current potential :+1V-1V (non-electroactive material) and 0V+2V (electroactive material); Running buffer PBS (phosphate) solution is used for electroactive material, and Tris solution is used for non-electroactive material.
Concrete effect of the present invention is as follows: use this device thoroughly to solve the alignment issues of working electrode and pipeline opening in the chip capillary cataphoresis Electrochemical Detection, guaranteed the reappearance of test result; Prior, when keeping efficiently dividing high detection, can use this device to detect to non-electroactive material such as sodion, potassium ion and lithium ion etc. to electroactive material such as dopamine and adrenaline; Also can use this device that the state of chip capillary is monitored in addition, for the application of chip capillary cataphoresis on producing provides condition; Chip and working electrode can separately be changed, and can further reduce cost and consume.
Description of drawings
Fig. 1 is the organigram of overlooking of chip capillary cataphoresis integrated electrochemical system.Among the figure: 1, have chip capillaceous; 2, constant potential galvanochemistry instrument; 3, the chip capillary cataphoresis high-voltage power supply; 4, computing machine; 5, chip pad; 6, the base of whole supporting platform; 7, separate high-field electrode; 8, separate ground-electrode; 9, the application of sample high-field electrode; 10, the application of sample ground-electrode; 11, electrochemical working electrode; 12, the galvanochemistry contrast electrode; 13, galvanochemistry is to electrode; 14, accurate three-dimensional regulation device; 15, have the spacer of clearance hole; 16, electrochemical investigating pond.
Fig. 2 is the side view of chip capillary cataphoresis integrated electrochemical system.Among the figure: 17, the cofferdam of electrochemical investigating pond; 15, have the spacer of clearance hole; 14, accurate three-dimensional regulation device; 6, the base of whole supporting platform; 5, chip pad; 1, have chip capillaceous; 18, the support between chip pad and the total base; 11, electrochemical working electrode.
Fig. 3 is the amplification organigram of electrochemical working electrode.Among the figure: 11-1, carbon or other can be made the fiber of electrode material; 11-2, connecting line (copper wire or other conductive material); 11-3, cathode electrodip painting; 11-4, carbon dust; 11-5, glass tube.
Fig. 4 is the schematic diagram of native system.Among the figure: 21, separate high-pressure side; 22, separate earth terminal; 11, electrochemical working electrode; 12, the galvanochemistry contrast electrode; 13, galvanochemistry is to electrode; 23, the back electromotive force of split tunnel; 24, the solution internal resistance between split tunnel and the ground-electrode; 25, split tunnel mesohigh end is to the solution internal resistance between the electrochemical working electrode; 26, the split tunnel electrochemical working electrode is to the solution resistance between the electrochemical investigating pond; 27, the contact of split tunnel and electrochemical investigating pond; 28, the Faradaic impedance on the electrochemical working electrode; 29, the charging capacitor electric capacity on the electrochemical working electrode; 30, the solution internal resistance of contrast electrode in the electrochemical investigating pond; 31, in the electrochemical investigating pond to the solution internal resistance of electrode.
Fig. 5 is the electrophoretogram of variable concentrations PBS sample introduction separation detection.
Fig. 6 is the graph of a relation of peak area and sample introduction PBS inverse concentration among Fig. 5.
Fig. 7 is the electrophoretogram of variable concentrations sodion and lithium ion sample introduction separation detection.
Fig. 8 is the electrophoretogram of variable concentrations dopamine and adrenaline sample introduction separation detection.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
The water that adopts in the experimentation is redistilled water, and the sample of separation detection is pure material.The mother liquor of lithium chloride, sodium chloride, potassium chloride, dopamine and adrenaline etc. all is mixed with the concentration of 10mM with redistilled water, be diluted to required concentration with the running buffer that separates before using.Separation detection lithium chloride, sodium chloride and potassium chloride phosphoric acid salt buffer also can be used the Tris damping fluid; Separation detection dopamine and adrenaline can be used phosphate buffer.
In chip capillary cataphoresis integrated electrochemical system shown in Figure 1, earlier chip (1) is cleaned oven dry before the experiment, be fixed on the chip supporting platform (5) with double faced adhesive tape then, electrochemical working electrode (11) is fixed on (14) on the three-dimensional regulation device, clearance hole on the spacer (15) fills up with the vacuum silicone grease, then damping fluid is injected electrochemical investigating pond (16); Make the application of sample of chip and separating pipe all be full of damping fluid with vacuum pump; To separate high-field electrode (7), separate ground-electrode (8), application of sample high-field electrode (9), application of sample ground-electrode (10), galvanochemistry contrast electrode (12), galvanochemistry be placed on suitable stationkeeping to electrode (13) etc.; Each electrode is connected on used galvanochemistry instrument (2) and the chip capillary cataphoresis usefulness high-voltage power supply (3).Galvanochemistry instrument (2) all links to each other with computing machine (4) with high-voltage power supply (3) with chip capillary cataphoresis.
This novel configuration can be carried out highly sensitive detection to electroactive and non-electroactive material under the galvanochemistry potentiostatic mode.In the described principle schematic of Fig. 4, after applying the separation high pressure, owing in the solution internal resistance (30) in the electrochemical investigating pond between the galvanochemistry contrast electrode, the electrochemical investigating pond solution internal resistance (31) between the electrode and the solution internal resistance (26) between electrochemical investigating pond and the separation ground-electrode are compared very for a short time with the internal resistance of solution in the microchannel, so can be thought potential drop between the contact (27) of electrochemical working electrode and split tunnel and electrochemical investigating pond at the potential drop that produces between electrochemical working electrode and the electrochemical investigating pond.When sample plug arrived electrochemical investigating pond by electrochemical working electrode when, the variation of solution resistance acted on potential drop on the working electrode charging capacitor (29) with generation.On the other hand, the material that has redox active in the sample will cause the variation of Faradaic impedance and oxidation-reduction potential on working electrode.
For non-electroactive sample, the variation of solution resistance causes the variation of dissolved oxygen DO reduction potential in the solution, and then causes the variation of electric current.Therefore, under certain conditions, the mensuration of non-electroactive material can be achieved by the variation of measuring the oxygen electric current.
We use phosphate buffer that above principle is verified.When running buffer is 10mM PBS, with the PBS solution sample introduction of 7mM, consider the relation between solution concentration and the resistance to 15mM, the variation of working electrode current potential can be write as:
where
c
0＝-b/a
C wherein
0Represent the concentration of running buffer and sample introduction solution respectively with c, A is the area of section of separating pipe, and on behalf of electrochemical working electrode, L stretch into the distance of pipeline, and Λ is the equivalent conductance of PBS.The electrophoretogram of gained is seen accompanying drawing 5, and the inverse mapping of the peak current that obtains and concentration is obtained accompanying drawing 6, meets oxygen dynamics volt-ampere curve.Clearly this mode also can be used for accurately measuring the electroosmotic flow in the chip capillary cataphoresis.
Next we utilize native system respectively non-electroactive material (lithium ion and sodion) and electroactive material (dopamine and adrenaline) to be carried out separation detection, and the electrophoretogram of experiment is seen Fig. 7 and Fig. 8.The peak height of lithium ion and sodion presents linear relationship from 200 μ M to 1000 μ M in concentration among Fig. 7, and dopamine and adrenergic peak height are linear at 50 μ M too among Fig. 8 in the concentration range of 200 μ M.These two experimental results have illustrated high sensitivity, high separating efficiency and the very strong versatility of new system.
Claims (7)
1. electrochemical detection method that is integrated in chip capillary cataphoresis, micro-fluidic chip is fixed on the chip supporting platform, and electrochemical working electrode is fixed on the three-dimensional regulation device, then damping fluid is injected electrochemical investigating pond; Make the application of sample of chip and separating pipe all be full of damping fluid with vacuum pump; To separate high-field electrode, separate ground-electrode, application of sample high-field electrode, application of sample ground-electrode, galvanochemistry contrast electrode, galvanochemistry be placed on the detection position to electrode and fix; Each electrode is connected used galvanochemistry instrument and chip capillary cataphoresis with on the high-voltage power supply, it is characterized in that at first utilizing chip capillary high-voltage power supply special monitoring separating pipe and application of sample pipeline whether unimpeded, on separating pipe, add the high pressure of long period then, simultaneously working electrode is activated; Wherein platinum electrode is used as separation high-field electrode, application of sample high-field electrode, separation ground-electrode and the application of sample ground-electrode of microchannel, after unobstructed and electrode is handled well at pipeline, with working electrode be clipped in the supporting fibre clip of three-dimensional regulation device on, three-dimensional regulating mechanism by precision under stereomicroscope is placed on the inside of microchannel with the front end of working electrode, realizes non-high efficiency separation electroactive and electroactive material is detected; Detecting operational factor when detecting non-electroactive material is: operating potential :-0.5 arrives+2V; Running buffer: conductivity and measured object have the aqueous solution than big-difference; Detecting operational factor when detecting electroactive material is: operating potential :-0.5 arrives+2V; Running buffer: aqueous solution.
2. the electrochemical detection method that is integrated in chip capillary cataphoresis according to claim 1 is characterized in that working electrode is placed on the interior 30-100 micron of inside outlet of microchannel.
3. the electrochemical detection method that is integrated in chip capillary cataphoresis according to claim 1, it is characterized in that a spacer is arranged between electrochemical investigating pond on the chip supporting platform and three-dimensional regulation device, have a clearance hole power supply chemical work electrode to pass on the spacer, the size in hole will guarantee that working electrode has certain scope of activities.
4. the electrochemical detection method that is integrated in chip capillary cataphoresis according to claim 1 is characterized in that the constant potential that carries out chip capillary cataphoresis by integrated electrochemical detection system detects.
5. the electrochemical detection method that is integrated in chip capillary cataphoresis according to claim 1 is characterized in that it is carbon fibre material, gold electrode, platinum electrode or the copper electrode of 5-20 micron that working electrode material adopts diameter.
6. the electrochemical detection method that is integrated in chip capillary cataphoresis according to claim 5, it is characterized in that working electrode is an individual carbon fibers disk working electrode, carbon fiber with diameter 5-10 micron, individual carbon fibers is exposed 1 mm length after wearing the glass capillary tip, fixes with glue, pours into carbon dust in the back, it with diameter 500 microns copper wire jam-pack carbon dust, fixing endways with glue, with the carbon fiber electrode of making, cathode electrodip painting is electroplated, oven dry.
7, the electrochemical detection method that is integrated in chip capillary cataphoresis according to claim 6 is characterized in that single piece of metal fiber disk working electrode, and adopting diameter is gold electrode, platinum electrode or the copper electrode of 5-20 micron.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100394172C (en) * | 2005-01-25 | 2008-06-11 | 中国科学院化学研究所 | Micro-capillary electropheresis apparatus |
| CN100367033C (en) * | 2005-04-21 | 2008-02-06 | 南京大学 | Microflow control chip integrated unit in integrated constant temperature system in high efficiency |
| CN102183669B (en) * | 2011-02-15 | 2013-07-17 | 中国科学院化学研究所 | Micro-fluidic chip for in-vivo on-line simultaneous detection of ascorbic acid and magnesium ion and preparation method thereof |
| CN102788831B (en) * | 2012-08-13 | 2014-07-30 | 中国科学院研究生院 | Microfluidic chip electrophoretic-electrochemical detecting device with adjustable pH after separation and use thereof |
| CN104048918B (en) * | 2014-06-04 | 2016-08-24 | 徐静 | A kind of capillary electrophoresis full-contact fluorescence detection cell |
| CN106093168B (en) * | 2016-06-14 | 2018-12-07 | 中国科学院合肥物质科学研究院 | Phosphate radical electrochemical sensor based on MEMS technology and its application in dynamic detection phosphate radical |
| CN107515210B (en) * | 2017-06-12 | 2020-04-14 | 南京大学 | Handheld high-flux matrix electrochemiluminescence chip analysis system |
| CN109758786B (en) * | 2018-12-29 | 2020-12-01 | 四川大学 | Micro-channel device for forming stable annular flow |
| JP7533245B2 (en) * | 2021-01-27 | 2024-08-14 | 株式会社島津製作所 | Microchip electrophoresis device |
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| US20020100714A1 (en) * | 2001-01-31 | 2002-08-01 | Sau Lan Tang Staats | Microfluidic devices |
| US20030000835A1 (en) * | 2001-06-28 | 2003-01-02 | Agilent Technologies, Inc. | Microfluidic system |
| CN1336543A (en) * | 2001-09-03 | 2002-02-20 | 武汉大学 | Capillary electrophoretic electrochemical detector with integrated chip and its making process |
| US20030094370A1 (en) * | 2001-11-22 | 2003-05-22 | Shimadzu Corporation | Chip type electrophoresis device |
| WO2003050035A2 (en) * | 2001-12-06 | 2003-06-19 | Nanostream, Inc. | Adhesiveless microfluidic device fabrication |
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|---|---|
| CN1563972A (en) | 2005-01-12 |
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