CN1238714C - Electric sample introduction multiunit tube for capillary electrophoresis - Google Patents

Electric sample introduction multiunit tube for capillary electrophoresis Download PDF

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Publication number
CN1238714C
CN1238714C CN 200410018026 CN200410018026A CN1238714C CN 1238714 C CN1238714 C CN 1238714C CN 200410018026 CN200410018026 CN 200410018026 CN 200410018026 A CN200410018026 A CN 200410018026A CN 1238714 C CN1238714 C CN 1238714C
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China
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pipe
sample
electrode
electric
capillary electrophoresis
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CN 200410018026
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CN1570621A (en
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曹成喜
李杉
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Abstract

The present invention relates to an electric sample feeding composite pipe for capillary electrophoresis. A double-pipe type band diaphragm structure is adopted, wherein one pipe is designed to be a sample pipe, the other pipe is an electrode pipe, and the two pipes are respectively used for accommodating capillaries and platinum electrodes of electric sample feeding; meanwhile, the joint inner pipe wall between the sample pipe and the electrode pipe is provided with a porous diaphragm which is used for preventing the flowing of liquid between the sample pipe and the electrode pipe, and the porosity of the diaphragm can perform a favorable function of electric conduction; the connection of curved surface is formed between the bottom and the outer wall of the sample pipe, and in such a way, a dead corner of an electric field can be effectively eliminated. The present invention effectively solves the problem of the convection current of liquid caused by bubble generation on the surface of the electrodes and non-uniformity of heat during the traditional electric sample feeding (comprising field amplification sample feeding), and effectively avoids the dead corner of the electric field of electric sample feeding simultaneously.

Description

The electrokinetic injection complex pipe that is used for Capillary Electrophoresis
Technical field
The present invention relates to a kind of electrokinetic injection complex pipe that is used for Capillary Electrophoresis, the conventional pressure sample introduction of several samples, gravity sample introduction and the electrokinetic injection that can be widely used in Capillary Electrophoresis, especially large volume electrokinetic injection enrichment improves stability and the detection sensitivity of analyzing Capillary Electrophoresis.
Background technology
(capillary electrophoresis CE) is the high efficiency separation analytical technology to Capillary Electrophoresis, has been widely used in the separation and the analysis of multiple compounds such as gene, protein, medicine.Because internal diameter is little, conventional CE applied sample amount generally be controlled at column volume 5% in, last sample volume is between several-tens nl.Thormann (A.B.Wey, C.-X.Zhang and W.Thormann, J.Chromatogr.A 853:95-106, the large volume sample injection beneficiation technologies that adopts such as 1999), sampling volume can be brought up to hundreds of nl, even reach μ l level, but reach the above order of magnitude of 10 μ l far away.Successfully develop micropreparation CE through bigger kapillary in the Hjerten utilizations such as (J.-L.Liao, R.Zhang and S.Hjerten, J.Chromatogr.A 676:421-430,1994), but its sample introduction ability is still below 10 μ l levels.Therefore, CE is difficult to the micropreparation needs of truly protein, DNA and medicine etc.
Sample sample introduction enrichment (Y.He and H.K.Lee, Anal.Chem.71:995-1001,1999) is amplified in the field can significantly improve sampling volume.But the used sample hose of electrical field magnified injection (comprising conventional electrokinetic injection) is the single hose structure, and platinum electrode and kapillary coexist in the sample liquid in the sample hose during electrokinetic injection; Therefore, sample hose itself is again an electrode tube, and sample liquid itself is again an electrode solution.This design causes the electrolysis bubble of platinum electrode generation when electrical field magnified injection to cause the convection current of sample liquid.Simultaneously, when electrical field magnified injection, also exist sample liquid because of electric field due to irregular the irregular thermal convection that causes of temperature and sample hose because of designing the electric field dead angle due to improper.These all will lower the efficient of electrical field magnified injection enrichment and preparation greatly.Because the existence at convection current, thermal convection and electric field dead angle due to the bubble, conventional electrokinetic injection (comprising electrical field magnified injection) repeated relatively poor is unfavorable for the quantitative test of strictness.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of electrokinetic injection complex pipe that is used for Capillary Electrophoresis is provided, the electrolysis bubble that platinum electrode produces when eliminating the large volume electrokinetic injection causes the convection current of sample liquid, the irregular thermal convection that causes of temperature due to reduction sample liquid electric field is irregular, eliminate sample hose because of designing the electric field dead angle of improper generation, improve the volume of electrokinetic injection and the efficient of enrichment, improve the stable and repeated of electrokinetic injection (comprising electrical field magnified injection).
For achieving the above object, the present invention adopts following embodiment: the design of abandoning original single hose sample hose, then make the electrokinetic injection complex pipe of double hose band barrier film into, wherein a pipe is designed to sample hose, and another pipe is electrode tube, is used for admitting the kapillary and the platinum electrode of electrokinetic injection respectively.Simultaneously on inner tubal wall total between sample hose and the electrode tube porous septum is set, is used for preventing the liquid flow between sample hose and the electrode tube, the poriness of barrier film can play the favorable conductive effect again.Between the bottom of sample hose and outer wall,, can eliminate the electric field dead angle effectively like this for curved surface is connected.At last, complex pipe is equipped with a pipe lid.
Complex pipe of the present invention is combined by sample hose, electrode tube, barrier film, Guan Gai.Sample hose is designed to uprightly, by forming at the bottom of outer tube wall, inner tubal wall, barrier film and the pipe, for curved surface is connected (being used for eliminating the electric field dead angle), between the general 10-2000 μ of the sample liquid volume l that it holds, and corresponding sample liquid scale mark is arranged between the pipe end and the outer tube wall.Electrode tube is a rising structure, and by forming at the bottom of outer tube wall, inner tubal wall, barrier film and the pipe, the sample liquid volume that it holds generally designs between 200-2000 μ l, and corresponding sample liquid scale mark is arranged.Barrier film is fixed on inner tubal wall and pipe at the end, or on the top of inner tubal wall, its effect is that the conduction for liquid between sample hose and the electrode tube provides passage, resists liquid flow and convection current between two pipes simultaneously.Barrier film can with miillpore filter or dialysis membrane or ultrafiltration be touched or porous ceramics or gel are made.Complex pipe is equipped with a pipe lid, and pipe covers and can design capillary canal and platinum electrode duct, and kapillary and the current passage that provides of platinum electrode are provided for they, and the pipe lid can be made by materials such as plastics or rubber.Can make by transparent hydrophobic material at the bottom of inner tubal wall, outer tube wall and the pipe.Whole complex pipe profile can be designed to cylindrical or prismatic.
During use, fill with sample liquid and electrode solution respectively at sample hose and electrode tube, move up and down complex pipe or kapillary and platinum electrode, kapillary and platinum electrode just enter the sample liquid of sample hose and the electrode solution of electrode tube respectively.Open the high-voltage power supply of CE, just can carry out conventional electrokinetic injection or large volume sample injection enrichment.
The present invention has following advantage and effect:
The first, effectively eliminated the convection current of the sample liquid that the conventional electric sample introduction bubble that electrolysis produces when (comprising electrical field magnified injection) causes.When (comprising electrical field magnified injection), platinum electrode and kapillary coexist in the sample liquid at the conventional electric sample introduction.Because the existence of electrolysis can form bubble in platinum electrode surface, the rising of bubble inevitably produces the convection current of liquid.The present invention has avoided the influence of the convection current of bubble generation to sample liquid fully.
The second, effectively avoided the thermal convection that hot unevenness causes when (comprising electrical field magnified injection) of conventional electric sample introduction.In traditional electrokinetic injection, there is serious electric field heterogeneity.Because the electricity of solution is led to uniformly, so heat production is heteropical in the solution, thereby the temperature of solution also is heteropical along with the carrying out of electrokinetic injection.This inevitably produces thermal convection.The present invention has avoided the heterogeneity of electric field to a great extent.Though in sample liquid, capillary end place electric field density maximum, heat production are at most, temperature is the highest; But capillary end can design the peak at sample liquid, therefore can not cause tangible thermal convection.
Three, greatly eliminated the electric field dead angle.Have a lot of electric fields dead angle in traditional electrokinetic injection (comprising electrical field magnified injection), this can cause the decline of sample introduction efficiency and repeatability.The present invention adopts curved design at place, electric field dead angle, capillary end is contacted the surface of sample liquid, especially the design (inner tubal wall and outer tube wall are hydrophobic material, and capillary end is a water wetted material) at Fig. 1 can form arc curved surface automatically, can effectively eliminate the electric field dead angle like this.
Four, significantly improved the stable and repeated of electrokinetic injection.Convection current, thermal convection and electric field dead angle etc. that above-mentioned electrolysis bubble produces are to cause the instable main cause of electrokinetic injection.These electrokinetic injection stability adverse factors have been avoided in enforcement of the present invention effectively, therefore will improve the stable and repeated of electrokinetic injection.
The present invention has following application prospect:
The first, the electrokinetic injection that is used for the CE routine comprises the electrical field magnified injection enrichment.Up to the present, the pattern of conventional electrokinetic injection is still carried out electrokinetic injection for platinum electrode and kapillary insert sample liquid simultaneously, therefore has above-mentioned a series of problems of can't avoiding, as convection current and electric field dead angle.The present invention has effectively eliminated the multiple unfavorable factor of conventional electrokinetic injection when (comprising electrical field magnified injection), can obviously improve the stable and repeated of CE, improves the contribution of multiple enrichment method to CE sensitivity.
The second, be used to preparation property CE.Though the research report of a small amount of preparation CE is arranged, the report of rarely found in actual applications preparation CE.This applied sample amount that mainly is attributed to CE is few, generally has only below the 5 μ l even whole capillary is full of sample liquid.Utilize the present invention, in conjunction with the beneficiation technologies of other electrokinetic injections, CE provides condition for the micropreparation type.
The 3rd, by cover the pneumatic duct of design at pipe, realize and the compatibility of pressure sample introduction, can be used for conventional pressure and gravity sample introduction.
Description of drawings
Fig. 1 is the structural representation of barrier film low-laying type electrokinetic injection complex pipe embodiment of the present invention.
Among Fig. 1, the 1st, sample hose (part that the dotted line wire frame comprises), the 2nd, electrode tube (part that the dotted line wire frame comprises), 3 is barrier film, 4 are the pipe lid, and 5 is the sample hose outer tube wall, and 6 is the electrode tube outer tube wall, 7 are the pipe end, and 8 is the sample liquid scale, and 9 is the electrode solution scale, 10 for connecting curved surface, and 11 is inner tubal wall, and 12 is capillary canal, 13 is the platinum electrode duct, and 14 is sample liquid, and 15 is electrode solution, 16 is kapillary, and 17 is platinum electrode, and 18 is the height clamp.
Fig. 2 is the structural representation of barrier film top loaded type complex pipe embodiment of the present invention.
Among Fig. 2,3 is barrier film, and 4 are the pipe lid, 5 is the sample hose outer tube wall, and 6 is the electrode tube outer tube wall, and 7 are the pipe end, 8 is the sample liquid scale, and 9 is the electrode solution scale, and 10 for connecting curved surface, 11 is inner tubal wall, and 12 is capillary canal, and 13 is the platinum electrode duct, 14 is sample liquid, and 15 is electrode solution, and 16 is kapillary, 17 is platinum electrode, and 18 is the height clamp.
Fig. 3 is the structural representation of simple type complex pipe embodiment of the present invention.
Among Fig. 3,3 is barrier film, and 4 are the pipe lid, and 5 is the sample hose outer tube wall, and 6 is the electrode tube outer tube wall, 7 are the pipe end, and 8 is the sample liquid scale, and 9 is the electrode solution scale, and 10 for connecting curved surface, and 11 is inner tubal wall, 14 is sample liquid, and 15 is electrode solution, and 16 is kapillary, and 17 is platinum electrode, and 18 is the height clamp.
Embodiment
Below in conjunction with accompanying drawing technical scheme of the present invention is described further.
The electrokinetic injection composite pipe structure that is used for Capillary Electrophoresis of the present invention adopts double hose band membrane configuration as shown in Figure 1, comprises that mainly sample hose 1, electrode tube 2, barrier film 3 and pipe cover 4.Sample hose 1 is rising structure with electrode tube 2, is made up of outer tube wall, the pipe end 7 separately and inner tubal wall 11, the barrier film 3 that both have respectively.The conduction of liquid provides passage between the barrier film 3 that is provided with between sample hose 1 and the electrode tube 2 is for sample hose 1 and electrode tube 2.In the embodiment of barrier film low-laying type electrokinetic injection complex pipe shown in Figure 1, barrier film 3 is arranged on the bottom of inner tubal wall 11 and manages at the end 7.Having a pipe to cover 4 on complex pipe top covers on sample hose 1 and the electrode tube 2, pipe covers 4 tops height clamp 18 is set, pipe covers and has capillary canal 12 and platinum electrode duct 13 on 4, kapillary 16 inserts sample liquid 14 by height clamp 18 and capillary canal 12, and platinum electrode 17 inserts electrode solution 15 by height clamp 18 and platinum electrode duct 13.Sample hose outer tube wall 5 and pipe adopt at the end 7 and are connected curved surface 10 and connect, with elimination electric field dead angle.Sample liquid scale 8 is arranged on the sample hose outer tube wall 5, electrode solution scale 9 is arranged on the electrode tube outer tube wall 6.
Figure 2 shows that the structure of barrier film top loaded type electrokinetic injection complex pipe.Compared to Figure 1, barrier film 3 is arranged on the top of inner tubal wall 11.During use, kapillary 16 inserts the sample liquid 14 and the approaching pipe end 7.
The complex pipe of the barrier film low-laying type electrokinetic injection of Fig. 1, and the complex pipe of the barrier film top loaded type electrokinetic injection of Fig. 2 can be used for the CE of robotization electrokinetic injection, is suitable for the very high high performance capillary electrophoresis of automaticity (as the HPCE of Beckmann company and the HPCE of Agilent company).
Figure 3 shows that the structure of the simple and easy complex pipe that is suitable for the lower CE of automaticity.Compare with structure shown in Figure 1, it is not fixedly to cover on the complex pipe that pipe covers 4, pipe covers and does not also design capillary canal 12 and platinum electrode duct 13 on 4, can cover 4 by tube used for bottom pouring during use, and kapillary 16 and platinum electrode 17 are directly inserted sample hose 1 and electrode tube 2 to assigned address.

Claims (4)

1, a kind of electrokinetic injection complex pipe that is used for Capillary Electrophoresis, it is characterized in that adopting double hose band membrane configuration, comprise sample hose (1), electrode tube (2), barrier film (3) and pipe lid (4), in the inner tubal wall (11) that sample hose (1) and electrode tube (2) have barrier film (3) is set, for the conduction of liquid between sample hose (1) and the electrode tube (2) provides passage, pipe lid (4) covers on sample hose (1) and the electrode tube (2), have capillary canal (12) and platinum electrode duct (13) on the pipe lid (4), adopt between sample hose outer tube wall (5) and the pipe end (7) and is connected curved surface (10) and connects with elimination electric field dead angle, sample liquid scale (8) is arranged on the sample hose outer tube wall (5), electrode solution scale (9) is arranged on the electrode tube outer tube wall (6).
2, the electrokinetic injection complex pipe that is used for Capillary Electrophoresis as claimed in claim 1 is characterized in that described barrier film (3) is arranged between inner tubal wall (11) bottom and the pipe end (7).
3, the electrokinetic injection complex pipe that is used for Capillary Electrophoresis as claimed in claim 1 is characterized in that described barrier film (3) is arranged on inner tubal wall (11) top.
4, the electrokinetic injection complex pipe that is used for Capillary Electrophoresis as claimed in claim 1 is characterized in that described pipe lid (4) can take off.
CN 200410018026 2004-04-29 2004-04-29 Electric sample introduction multiunit tube for capillary electrophoresis Expired - Fee Related CN1238714C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200410018026 CN1238714C (en) 2004-04-29 2004-04-29 Electric sample introduction multiunit tube for capillary electrophoresis

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Application Number Priority Date Filing Date Title
CN 200410018026 CN1238714C (en) 2004-04-29 2004-04-29 Electric sample introduction multiunit tube for capillary electrophoresis

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CN1238714C true CN1238714C (en) 2006-01-25

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WO2017046783A1 (en) * 2015-09-20 2017-03-23 Dh Technologies Development Pte. Ltd. Small sample injection vial
CN114235910A (en) * 2021-12-21 2022-03-25 重庆文理学院 Elastomer pH meter

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