CN102866195A - Immobilized-enzyme-based end-column detection interface for capillary electrophoresis - Google Patents
Immobilized-enzyme-based end-column detection interface for capillary electrophoresis Download PDFInfo
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- CN102866195A CN102866195A CN2012103484106A CN201210348410A CN102866195A CN 102866195 A CN102866195 A CN 102866195A CN 2012103484106 A CN2012103484106 A CN 2012103484106A CN 201210348410 A CN201210348410 A CN 201210348410A CN 102866195 A CN102866195 A CN 102866195A
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Abstract
The invention provides an immobilized-enzyme-based end-column detection interface for capillary electrophoresis. The interface comprises a detection interface cover, a transparent window and a sealing gasket positioned between the detection interface cover and the transparent cover. A hollowed reaction channel is formed in the sealing gasket. A film covering immobilized enzymes on the reaction channel is arranged between the detection interface cover and the sealing gasket. The detection interface cover is provided with a reaction liquid inlet and a waste liquid outlet, which are communicated with the two ends of the reaction channel respectively. A capillary connector communicated with the reaction channel is also arranged on the detection interface, is used for the insertion of a capillary, and is positioned at the reaction liquid inlet of the reaction channel. According to the detection interface, the using amount of the enzymes can be remarkably reduced, the stability and activity of the enzymes can be improved, a dead volume in the reaction channel and a dilution effect can be effectively prevented, detection sensitivity can be improved, and the detection interface is ideal for the immobilized-enzyme-based end-column detection of the capillary electrophoresis, and can be used for the enzyme catalysis reaction-based end-column detection of the capillary electrophoresis.
Description
Technical field
The present invention relates to the capillary electrophoresis technique field, particularly detect interface behind a kind of capillary electrophoresis column based on immobilised enzymes.
Background technology
Capillary Electrophoresis is a kind of emerging isolation technics that grows up the eighties in 20th century, it has efficiently, fast, the advantage such as consumption is low, become in recent years one of most active research direction of analytical chemistry.From technical merit, Capillary Electrophoresis has developed into different clastotypes, thereby satisfies the optimal separation of heterogeneity sample in pipe.Kapillary clastotype commonly used has: capillary zone electrophoresis, capillary gel electrophoresis, Micellar Electrokinetic Chromatography, capillary electric chromatogram.Sample size capillaceous is highly suitable for the analysis of micro-biological sample receiving upgrading, but also the sensitivity that detects is had higher requirement simultaneously.Although laser-induced fluorescence (LIF), the detection techniques such as mass spectrum have satisfied the requirement that Capillary Electrophoresis detects, expensive instrument price and complicated trace routine have limited their range of application.The enzyme that will have unique high catalytic efficiency is applied to amplification detection signal raising sensitivity in the Capillary Electrophoresis, is more and more paid close attention to.
The application of enzymic catalytic reaction in Capillary Electrophoresis can be divided into three kinds of patterns: before the post, enzyme reaction behind post, post.In the post preferment reaction pattern, resolvase and immobilised enzymes are put into the sample tubule, and enzymic catalytic reaction occurs before sample enters kapillary, and kapillary is only as split tunnel.This method enzyme consumption is larger, especially adopts resolvase, and enzymic disposable uses and can not reclaim, and has caused the waste of reagent.In post enzyme reaction pattern, enzyme is filled in the kapillary, and enzyme reaction and detachment process are carried out in kapillary simultaneously.Since 1992, (the Bao J. such as Bao; Regnier F. E. J. Chromatogr. 1992,608,217) first resolvase is applied to Capillary Electrophoresis in post enzyme reaction system, has emerged in large numbers in 20 years in the past in a large number about the various reports of in Capillary Electrophoresis, using in the reaction of post resolvase.In addition, enzyme also can be fixed in the capillary column.For example, (the Tang Z. M. such as Tang; Kang, J. W. Anal. Chem. 2006,78,2514) adopt ionic bonding technology fix blood ACE at the medicine of capillary inlet end screening treatment hypertension and diabetes.(Wojcik, the R. such as Wojcik; Vannatta, M.; Dovichi, N. J. Anal. Chem. 2010,82,1564) alkaline phosphatase is fixed on the two-dimensional capillary electrophoresis of the first capillary tip designs, has simplified the processing of sample between bidimensional.But because capillary tube inner wall is very narrow and small, need to use complicated technique for fixing, and thisly often can not satisfy simultaneously the top condition of enzyme reaction and capillary electrophoresis separation in post enzyme reaction technology, the Joule heat that produces in the kapillary during electrophoresis has had a strong impact on the active and stable of enzyme.Unsettled enzyme reaction product (such as the active oxygen that uses in the chemiluminescence detection, the free radical that uses in the Electrochemical Detection) can not adopt above two kinds of patterns to analyze owing to easily decompose the forfeiture detection of active after its reaction.Simultaneously, the burden that the relevant coreagent of enzyme reaction and reaction product have increased capillary electrophoresis separation in these two kinds of patterns.In the enzyme reaction pattern, enzyme is written in the past column reaction pond behind the post, produces immediately detection signal at capillary outlet end and substrate reactions, has avoided the drawback because of unstable product and electrophoresis process generation.But this pattern is used resolvase more, because the separation and detection step is brought impurity into, enzyme solutions can not reclaim, and the use of a large amount of resolvases has caused inevitable reagent waste.
Detect application in Capillary Electrophoresis in order to further expand enzymatic, detect interface after having designed the capillary electrophoresis column based on immobilised enzymes.
Summary of the invention
Immobilised enzymes detects interface after the object of the present invention is to provide a kind of capillary electrophoresis column, has solved significantly to use resolvase to cause the enzyme reagent waste in the prior art poor, the active low problem of enzyme stability.
The objective of the invention is to be achieved through the following technical solutions:
Detect interface behind the capillary electrophoresis column based on immobilised enzymes, described detection interface comprises the detection access flap, transparent window film and the gasket seal between detection access flap and transparent window film, described gasket seal is provided with the reaction channel of hollow out, be provided with the film that covers the immobilised enzymes on described reaction channel between described detection access flap and the gasket seal, and detect access flap and be provided with reactant liquor entrance and the waste liquid outlet that communicates with the reaction channel two ends respectively, also be provided with on the described detection interface and communicate with described reaction channel and be used for inserting capillary interface capillaceous, described capillary interface is positioned at the reactant liquor inlet end of reaction channel.
This detection interface is applicable to detect behind the post, has improved Enzymic stability, reduces simultaneously enzyme in the consumption of flow detection system.This detection interface can be used for various capillary electrophoresis separation patterns, comprise capillary zone electrophoresis, capillary gel electrophoresis, Micellar Electrokinetic Chromatography, capillary electric chromatogram, detecting device coupling that simultaneously also can be relevant with various enzyme reactions is such as laser induced fluorescence detector, ultraviolet-visible absorption spectroscopy detecting device, electrochemical detector.
Preferably, the volume that holds of described reaction channel is 2.5 μ L ~ 10 μ L.
In order to improve the sensitivity of detection, described reaction channel is bar shaped, and two ends are circular arc, can effectively reduce liquid and accumulate.
Preferably, described reaction channel is that height is 0.01 ~ 0.05 cm, and length is 1.5 cm ~ 3.0 cm, and wide is 0.10 cm ~ 0.15 cm.
Preferably, described reactant liquor entrance is consistent with reaction channel length with distance between the waste liquid outlet, and the diameter of reactant liquor entrance and waste liquid outlet is 0.05 cm ~ 0.10 cm.
Preferably, the material of described detection access flap is teflon.
Preferably, described gasket seal (2) is resilient material.
Preferred, described resilient material is silica gel or rubber.
Preferably, described transparent window film is the clear, colorless organic glass.
Among the present invention, fixed enzyme membrane can use conventional enzyme immobilization technology, such as cross-linking method and combined techniques etc., water-soluble enzyme or water-fast enzyme is received on the natural or synthetic macromolecule carrier by chemical bond-linking, after chemical method is processed, be fixed in the reaction channel top.
Be preferably, the manufacturing process of fixed enzyme membrane is as follows: enzyme solutions is added drop-wise on the UltraBind film (length and width are consistent with sense channel) of aldehyde radical activation, aldehyde radical on amino on the enzyme and the UltraBind film forms reversible Schiff alkali, and then drip and to go back original reagent and make between enzyme and the UltraBind film and form firmly covalent bond, can use after then drying.
Beneficial effect of the present invention: (1) is of the present invention farthest to have reduced the consumption of enzyme in the flow detection system based on detecting interface behind the capillary electrophoresis column of immobilised enzymes, significantly strengthens Enzymic stability and activity, thus the Effective Raise detection sensitivity.(2) immobilised enzymes reaction channel volume is little behind the post of the present invention's design, and minimum adding volume is 2.5 μ L, exists without dilution effect and dead volume.Enzyme reaction just is detected immediately once generation, is applicable to the detection of unstable enzyme reaction product.Simultaneously, the enzyme reaction pattern has avoided before the post, in the post enzyme reaction Joule heat and separation component complexity on the impact of whole system behind the post.(3) immobilised enzymes detection interface arrangement can be used for the various clastotypes of Capillary Electrophoresis behind the capillary electrophoresis column of the present invention, comprise capillary zone electrophoresis, capillary gel electrophoresis, Micellar Electrokinetic Chromatography, capillary electric chromatogram, detecting device coupling that simultaneously also can be relevant with various enzyme reactions is such as laser induced fluorescence detector, ultraviolet-visible absorption spectroscopy detecting device, electrochemical detector.
Description of drawings
In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention is described in further detail below in conjunction with accompanying drawing, wherein:
Fig. 1 is the structural representation that immobilised enzymes detects interface behind the capillary electrophoresis column of the present invention (1: detect access flap, 2: gasket seal, 3: transparent window film, 4: the film of immobilised enzymes, 5: kapillary).
Fig. 2 be contain the capillary electric chromatogram chemical photic device figure that the present invention detects interface (6: detect interface, 7: the miniflow syringe pump, 8: platinum electrode, 9: damping fluid holds the pond, 10: waste liquid pool, 11: photomultiplier, 12: magazine).
Fig. 3 is the enzymatic chemiluminescence principle figure (HRP: horseradish peroxidase of detection interface capillary outlet end of the present invention; BPB: bromophenol blue, 1: detect access flap, 2: gasket seal, 3: transparent window film, 4: the film of immobilised enzymes, 5: kapillary).
Fig. 4 is that detection interface of the present invention applies to the working curve that detects glycocoll in the capillary electric chromatogram chemiluminescence.
Embodiment
In order to make the purpose, technical solutions and advantages of the present invention clearer, the below is described in detail the preferred embodiments of the present invention.
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.The experimental technique of unreceipted actual conditions in the preferred embodiment usually according to normal condition, or carries out according to the condition that manufacturer advises.
Detect interface behind the capillary electrophoresis column based on immobilised enzymes, as shown in Figure 1, comprise and detect access flap 1, transparent window film 3 and the gasket seal 2 between detection access flap and transparent window film, detecting access flap 1 uses teflon best, gasket seal 2 is provided with the reaction channel of hollow out, detect between access flap 1 and the gasket seal 2 and be provided with the film 4 that covers the immobilised enzymes on reaction channel, and detect access flap 1 and be provided with reactant liquor entrance and the waste liquid outlet that communicates with the reaction channel two ends respectively, also be provided with the capillary interface that communicates with described reaction channel and be used for inserting kapillary 5 on the interface detecting, capillary interface is positioned at the reactant liquor inlet end of reaction channel.
In order to improve the sensitivity of detection, avoid dilution effect and dead volume to exist, reaction channel is set to bar shaped, and the bar shaped two ends are circular arc, volume is preferably 2.5 μ L ~ 10 μ L, 4.5 μ L more preferably, and the reaction channel height is 0.01 cm ~ 0.05 cm, length is 1.5 cm ~ 3.0 cm, and wide is 0.10 cm ~ 0.15 cm.Further, the reactant liquor entrance that detects on the access flap 1 is consistent with the length of reaction channel with distance between the waste liquid outlet, and the diameter of reactant liquor entrance and waste liquid outlet is 0.05 cm ~ 0.10 cm, is preferably 0.08 cm.Gasket seal has the effect with the reaction tank sealing, selects the resilient material sealing effectiveness better, and the gasket seal that silica gel or rubber are made is best.Transparent window film is selected the material of light transmission, is preferably the organic glass of clear, colorless.In order to make the detection interface can cooperate existing instrument to use, can detect the size setting of interface and the size of existing Instrument Matching.Present embodiment will detect access flap 1 and be set to long 4.0 cm, and wide is 2.5 cm, and thickness is 0.8 cm; The length of transparent window film 3 is 4.0 cm, and wide is 2.5 cm, and thickness is 0.3 cm.
The capillary electric chromatogram chemical photic device, as shown in Figure 2, kapillary 5 is connected with the capillary interface that detects interface, take the capillary electric chromatographic column capillaceous of having modified nm of gold as example, to grow is 60 cm, internal diameter be capillary electric chromatographic column one end of 75 μ m with the poly-propionyl imines coating of burning 0.5 cm, insert and detect the interface reaction channel, the capillary electric chromatographic column other end is put into damping fluid and is held pond 9.Then will detect interface 6 and place photomultiplier 11 tops, and the face of transparent window film 3 is contacted with photomultiplier 11 detection faces, will detect interface 6 again and photomultiplier 11 all places airtight magazine 12, to avoid the interference of extraneous light.The reactant liquor entrance that detects interface 6 is connected with miniflow syringe pump 7; Waste liquid outlet is connected with waste liquid pool 10, damping fluid is held between pond 9 and the waste liquid pool 10 put into platinum electrode 8, connects with polyfluortetraethylene pipe in the whole system for the distribution of commodities, and internal diameter is preferably 0.08 cm.Form voltage by platinum electrode 8 at the two ends of capillary electric chromatographic column during electrophoresis, because the carried charge of different material is different, thereby reach the effect of separate substance.
The capillary electric chromatogram chemical photic device detects glycocoll:
Immobilised enzymes paper membrane preparation method is as follows: be that 5.0 mg/mL horseradish peroxidase solution are added drop-wise on the UltraBind film (2.7 cm * 0.20 cm) of aldehyde radical activation with 30 μ L concentration, room temperature is placed 2h under moistening environment, then drips 1.0 mg/mL NaCNBH
3Solution takes out behind reaction 40 min under the room temperature and dries.The enzyme paper film of making is close to teflon with double faced adhesive tape and is covered inboard center.Capillary electric chromatographic column is fixed in enzyme paper film below, and capillary outlet stretches into reaction channel 0.5 cm; Each several part tightly is fixed together by screw, forms a reaction channel that is about 4.5 μ L.
During detection, the operating voltage of photomultiplier is set to-800 V, the miniflow syringe pump imports in the reaction channel with the phosphate buffer (12 mM, pH 9.0) that the flow velocity of 20 μ L/min will contain 6.2 μ M bromophenol blues, as the coreagent of immobilised enzymes reaction.Contain the phosphate buffer (5.0 mM, pH 8.5) of 0.75 mM hydrogen peroxide as the kapillary dissociating buffer, contain damping fluid and hold pond 9, the electrophoresis driving force that the voltage difference by 12 KV produces enters in the kapillary.After the chemiluminescence signal baseline stability, segregation drive sample introduction 15 s by 20 cm differences in height finish capillary sample inlet.In the reaction channel porch, glycocoll flows out together reaction reaction with the phosphate buffer that contains hydrogen peroxide from capillary column, produce chemiluminescence signal under the catalysis of immobilized HRP, and it detects principle as shown in Figure 3.Light signal just can be captured by photomultiplier 11 immediately once emission, and is converted into electric signal.
Sample pretreatment: chemiluminescence can not occur in glycocoll itself, adopts the ethylenediamine catalysis method to use in the detection
N-(4-aminobutyl)-
NThe different luminol of-ethyl glycocoll of deriving makes chemiluminescence attribute group on the glycine molecule band.Concrete steps are: (1) is with 200 μ L, 0.50 mM's
N-(4-aminobutyl)-
NThe different luminol of-ethyl joins with 0.50 mM's of volume
N, NIn-two succinimidyl carbonate solution, mixed solution reacted 2 hours under room temperature after eddy current mixes.(2) sample of 100 μ L methyl alcohol dissolvings is joined in the solution that step (1) reaction obtains with the 0.15 M ethylenediamine methanol solution of 20 μ L, after eddy current mixes, under room temperature, reacted again 2 hours equally, get test sample.Then 10 times of test sample dilute with waters are pressed above-mentioned method gravity sample introduction afterwards.
Under above-mentioned experimental technique and condition, having measured concentration is the glycocoll standard solution of 0.5 μ M, 1 μ M, 10 μ M, 30 μ M, 50 μ M, 100 μ M and 200 μ M, and the result as shown in Figure 4.The result shows, glycine concentration is good linear relationship with the chemiluminescence peak height in 0.5 μ M ~ 200 μ M scopes, and the match equation of linear regression is:
I(a. u.)=66.15
C(μ M)+812.84 (
R 2 =0.9921),
IRepresent chemiluminescence intensity,
CRepresent the concentration of glycocoll, its detectability (S/N=3) is 0.12 μ M.Detect 50 μ M glycocoll continuous five times, the transit time of glycocoll is respectively 7.5% and 5.4% with the relative standard deviation that goes out peak intensity, has shown the repeatability that the method is good.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and not depart from the present invention that appended claims limits.
Claims (9)
1. detect interface behind the capillary electrophoresis column based on immobilised enzymes, it is characterized in that: described detection interface comprises detection access flap (1), transparent window film (3) and the gasket seal (2) between detection access flap and transparent window film, described gasket seal is provided with the reaction channel of hollow out, be provided with the film (4) that covers the immobilised enzymes on described reaction channel between described detection access flap (1) and the gasket seal (2), and detect access flap (1) and be provided with reactant liquor entrance and the waste liquid outlet that communicates with the reaction channel two ends respectively, also be provided with on the described detection interface and communicate with described reaction channel and be used for inserting capillary interface capillaceous, described capillary interface is positioned at the reactant liquor inlet end of reaction channel.
2. detect interface behind the described capillary electrophoresis column based on immobilised enzymes according to claim 1, it is characterized in that: the volume that described reaction channel holds is 2.5 μ L ~ 10 μ L.
3. detect interface behind the described capillary electrophoresis column based on immobilised enzymes according to claim 1, it is characterized in that: described reaction channel is that bar shaped and two ends are circular arc.
4. detect interface behind the described capillary electrophoresis column based on immobilised enzymes according to claim 3, it is characterized in that: described reaction channel is that height is 0.01 ~ 0.05 cm, and length is 1.5 cm ~ 3.0cm, and wide is 0.10 cm ~ 0.15 cm.
5. detect interface behind each described capillary electrophoresis column based on immobilised enzymes according to claim 1-4, it is characterized in that: the distance between described reactant liquor entrance and the waste liquid outlet and the equal in length of reaction channel, the diameter of described reactant liquor entrance and waste liquid outlet are 0.05 cm ~ 0.10 cm.
6. detect interface behind the described capillary electrophoresis column based on immobilised enzymes according to claim 1, it is characterized in that: the material of described detection access flap (1) is teflon.
7. detect interface behind the described capillary electrophoresis column based on immobilised enzymes according to claim 1, it is characterized in that: described gasket seal (2) is resilient material.
8. detect interface behind the described capillary electrophoresis column based on immobilised enzymes according to claim 7, it is characterized in that: described resilient material is silica gel or rubber.
9. detect interface behind the described capillary electrophoresis column based on immobilised enzymes according to claim 1, it is characterized in that: described transparent window film (3) is the clear, colorless organic glass.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0812350A1 (en) * | 1995-01-24 | 1997-12-17 | RIGHETTI, Pier Giorgio | An immobilized enzyme reactor |
| JP2000338085A (en) * | 1999-05-26 | 2000-12-08 | Shimadzu Corp | Method for detecting chemiluminescence and microchip electrophoretic apparatus using the method |
| CN1987432A (en) * | 2006-12-15 | 2007-06-27 | 武汉大学 | Capillary tube electrophoresis chemical luminous detector for monocell analysis |
| CN101581709A (en) * | 2009-06-10 | 2009-11-18 | 福州大学 | Off-column vertical chemiluminescence detection device for capillary electrochromatography |
| CN102243151A (en) * | 2010-09-20 | 2011-11-16 | 华东理工大学 | Zero dead volume capillary electrophoresis and laser induced fluorescence detection online derivatization device |
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2012
- 2012-09-19 CN CN201210348410.6A patent/CN102866195B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0812350A1 (en) * | 1995-01-24 | 1997-12-17 | RIGHETTI, Pier Giorgio | An immobilized enzyme reactor |
| JP2000338085A (en) * | 1999-05-26 | 2000-12-08 | Shimadzu Corp | Method for detecting chemiluminescence and microchip electrophoretic apparatus using the method |
| CN1987432A (en) * | 2006-12-15 | 2007-06-27 | 武汉大学 | Capillary tube electrophoresis chemical luminous detector for monocell analysis |
| CN101581709A (en) * | 2009-06-10 | 2009-11-18 | 福州大学 | Off-column vertical chemiluminescence detection device for capillary electrochromatography |
| CN102243151A (en) * | 2010-09-20 | 2011-11-16 | 华东理工大学 | Zero dead volume capillary electrophoresis and laser induced fluorescence detection online derivatization device |
Non-Patent Citations (2)
| Title |
|---|
| HAOYUE XIE 等: "《A novel enzyme-immobilized flow cell used as end-column chemiluminescent detection interface in open-tubular capillary electrochromatography》", 《THE ROYAL SOCIETY OF CHEMISTRY》 * |
| LIN WANG 等: "《Trivalent copper chelate-luminol chemiluminescence system for highly sensitive CE detection of dopamine in biological sample after clean-up using SPE》", 《ELECTROPHORESIS》 * |
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