CN101581709A - Off-column vertical chemiluminescence detection device for capillary electrochromatography - Google Patents
Off-column vertical chemiluminescence detection device for capillary electrochromatography Download PDFInfo
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- CN101581709A CN101581709A CNA2009101119479A CN200910111947A CN101581709A CN 101581709 A CN101581709 A CN 101581709A CN A2009101119479 A CNA2009101119479 A CN A2009101119479A CN 200910111947 A CN200910111947 A CN 200910111947A CN 101581709 A CN101581709 A CN 101581709A
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Abstract
The invention provides an off-column vertical chemiluminescence detection device for capillary electrochromatography. The detection device comprises a cell body, a spectrum detection window, a photomultiplier and the like. The detection device is characterized in that the capillary electrochromatography column and a chemiluminescence detection passage are arranged in a vertical position; the easily corroded part of the capillary electrochromatography column, which is exposed in a strongly alkali chemiluminescence reagent is extremely small; after leaving the column, the substance to be measured separated by the chromatographic column and the chemiluminescence reagent can quickly react and generate photoelectric response signals. The detection device has simple manufacture process, convenient usage and low cost, can effectively reduce the corrosion degree of the capillary electrochromatography, can eliminate the phenomenon that the alkali solution corrodes the chromatographic column packing material, and can prolong the service life of the separation column; the optical signals generated by the detection cell can be collected duly, the signal loss is small, the sensitivity is high, the stability and the repeatability are excellent, and the detection device can realize quick separation and high-sensitivity detection on the substances with chemiluminescence activity.
Description
Technical field
The present invention relates to be used for the design from column vertical chemiluminescence detection device of capillary electric chromatogram.
Background technology
Capillary electric chromatogram (CEC)-chemiluminescence (CL) coupling technique has had both CEC high selectivity and the highly sensitive characteristics of CL, be in the present microanalysis efficiently, method for separating and analyzing fast.(Lin, Z., Xie, Z., L ü, H., Lin, X., Wu, X., Chen, G, Anal.Chem., 2006,78,5322-5328.) CEC-CL coupling technique key is the detection interface that the two is connected, interface capability directly affects the separation efficiency of capillary column and the sensitivity of detection.
Existing CEC-CL interface mainly contains: detect interface (Lin, Z., Xie, Z., L ü, H., Lin, X., Wu, X., Chen, G., Anal.Chem., 2006,78,5322-5328 in the coaxial streaming of post with from the coaxial streaming of post; Lin, Z., Lin, J., Wu, X., Lin, X., Xie, Z., Electrophoresis, 2008,29,401-409).Wherein in the coaxial streaming of post, detecting device is positioned between high-voltage power supply, past column reaction reagent such as H
2O
2In alkaline medium, easily decompose the generation bubble and cause the electric current instability, and under electric field driven, alkaline reagent can enter capillary column by backward transfer, modify the filler reaction, cause pillar to damage with silica gel base in the post.In the coaxial streaming of post, ground-electrode moves to the capillary column front portion from the end of reaction capillary column, has avoided that reagent decomposes the generation bubble under electric field behind the post, but reagent is still under effect of electric field, may move and enter the separation capillary front end, cause the pillar filler to subside.What be worth drawing attention is, coaxial streaming interface generally adopts bushing type, exists big not enough: enter the bigger reaction tube of internal diameter when analyte flows out from separating column, when mixing with luminescence reagent, cause eddy current diffusion easily, cause the peak broadening and reduce post and imitate and detection sensitivity; Simultaneously, adopt coaxial streaming interface, the capillary electric chromatographic column long period of soaking is in the strong basicity luminescence system, capillary electric chromatographic column can't bear strong basicity (generally tolerating pH＜10), long period of soaking can cause the frangible fracture of chromatographic column, and alkali lye may move and enters the separation capillary post under electric field action, corrode filler in the post and make its leakage of subsiding, cause that the chromatographic column post is imitated, reappearance reduces and shorten serviceable life, and reaction kapillary and the sewer pipe of the leakage of filler after can making it stop up, and influences the chemiluminescence detection analysis.
At present, it is clear and definite not propose a kind of structure as yet, eddy current diffusion influence in the time of can having reduced the mixing of the coaxial streaming interface of capillary electric chromatogram solution, or avoid capillary electric chromatogram separating column long period of soaking alkali lye, the design of avoiding luminescence reagent to be subjected to the electric field action migration to enter the chemiluminescence detecting of capillary electric chromatographic column.
Summary of the invention
The objective of the invention is at the problems referred to above, design a kind of novel capillary electric chromatogram from column vertical chemiluminescence detection device.
Capillary electric chromatogram of the present invention comprises detection cell body, spectral detection window, photomultiplier etc. from column vertical chemiluminescence detection device.The chemical illuminating reagent passage and the capillary electric chromatographic column of described pick-up unit are in
Shape upright position, capillary chromatographic column expose in the corrosion-vulnerable part of strong basicity luminescence reagent minimum, can rapid reaction with chemical illuminating reagent behind the isolated one-tenth separating column to be measured of chromatographic column and produce the photoelectric response signal.The spectral detection window of described pick-up unit is vertical with the separation capillary post, and the photomultiplier (PMT) that directly is positioned over collection determinand light signal is preceding, and the signal that chemiluminescence reaction produces can in time be collected by PMT, reduces the loss of light signal; Described photomultiplier connects computer-controlled faint light detecting device; Described detection cell, luminescence reagent passage and photomultiplier all are arranged in the camera bellows.
Advantage of the present invention is:
1, the present invention at first adopts from post and detects, guaranteed that luminescence reagent is subjected to electric field action a little less than, reduce the possibility that migration of agents enters capillary column; Adopt the separating column design vertical with the post postcapillary, the trouble of having avoided separating column long period of soaking alkali lye and having produced, adopt the detection window design vertical simultaneously with the separation capillary post, eddy current diffusion influence when also having reduced coaxial streaming interface solution and mixing, contrast is from the coaxial streaming interface of post, and stream interface can significantly improve detection cell sensitivity, the minimizing district is with broadening, prolongs separating column serviceable life and enhanced system stability in novel merging from column vertical.
2, the present invention is a detected object with the luminescent substance Luminol and the ABEI of classics, and the detectability that records Luminol and ABEI is respectively 2.0 * 10
-9Mol/L and 5.0 * 10
-9Mol/L (S/N=3), it is better than the level of the capillary electric chromatogram of bibliographical information from the post chemiluminescence detection.In addition, utilize this invention to realize that successfully detectability is respectively 2 * 10 to the separation and the detection of derivatization phenoxy carboxylic acid class herbicide
-9Mol/L, 2 * 10
-9Mol/L, 3 * 10
-9Mol/L and 2 * 10
-8Mol/L, detection sensitivity is higher.
3, the present invention make simple, easy to use, expense is cheap, and detection sensitivity and separation efficiency height, system stability is good, can realize quick separation and high-sensitivity detection to the material with chemiluminescence activity.
Description of drawings
Fig. 1: capillary electric chromatogram is from the column vertical chemiluminescence detection device synoptic diagram,
Wherein: 1-detection cell body; 2-optical glass; The 3-detection window; 4-separation capillary post channel slot; 5-separation capillary post; The interface of 6-separation capillary post and stainless-steel tube channel slot; The interface of 7-stainless-steel tube channel slot and pond body; 8-post postcapillary channel slot; 9-waste liquid capillary channel groove; 10-post postcapillary; 11-photomultiplier (PMT); 12-waste liquid kapillary; The 13-ground-electrode.
Fig. 2: capillary electric chromatogram detects Lominol and ABEI, 1-Lominol from the coaxial streaming of post/vertical chemiluminescence; 2-ABEI
Fig. 3: capillary electric chromatogram detects derivatization phenoxy carboxylic acid class herbicide, 1:MCPP from column vertical chemiluminescence; 2:2-PPA; 3:2,3-CPPA; 4:2,4-D
Embodiment
Embodiment of the present invention 1 are described below in conjunction with the accompanying drawings: detection cell body of the present invention (1) bottom is with optical glass (2), and pond body (1) xsect length and width are identical with the optical glass length and width; Pond body (1) bottom centre position is provided with the diversion trench of a diameter 200～500 μ m, length 2～5mm, and as detection window (3), pond body (1) and optical glass (2) are fixed with epoxy resin bonding.
The position of center line of detection cell body (1) vertical detection window (3) is equipped with stainless steel pipes channel slot (4), be used for fixing separation capillary post (5), it stretches into the top in detection window (3) zone straight by channel slot (4), styletable is positioned at the position that just exceeds needle tubing, separation capillary post (5) and the interface (6) of stainless-steel tube channel slot (4) and the interface (7) of stainless-steel tube channel slot (4) and pond body (1) are all fixed with epoxy resin bonding; The upper and lower of detection window (3) has one stainless-steel tube channel slot (8,9) is housed respectively, and the center line of its center line and detection window (3) point-blank; Channel slot (8) is used for fixing post postcapillary (10), and interface is fixed with epoxy resin bonding, and channel slot (9) is used for fixing kapillary (12), and as the waste liquid delivery line, interface seals with epoxy resin.
Luminescence reagent is introduced by post postcapillary (10), post postcapillary (10) arrives the top of separation capillary post (5) by channel slot (8), and the luminescence reagent of measured matter that wash-out goes out from capillary column (5) and post postcapillary (10) introducing converges and produces luminous signal at detection window (3); It is preceding that pond body (1) directly is positioned over the photomultiplier (PMT) (11) of gathering the determinand light signal, ground-electrode (13) is fixed on the stainless-steel tube channel slot (4), form from the post pattern with separation capillary post (5) endpiece, the signal that reaction produces can in time be collected by PMT (11).
Utilizing pressurization capillary electric chromatogram from the column vertical chemiluminescence detection cell, is detected object with the luminescent substance Luminol and the ABEI of classics, investigates the performance of this interface, the results are shown in Figure 2.The detection of measuring Luminol and ABEI from the coaxial streaming interface of post is limited to 6.0 * 10
-8Mol/L and 8.0 * 10
-8Mol/L is limited to 2.0 * 10 from the detection of column vertical splice grafting mouth gained
-9Mol/L and 5.0 * 10
-9Mol/L, detection sensitivity obviously exceeds from the coaxial streaming interface of post, has realized lower concentration detectability.Experiment condition is: and polymerization integer column (100 μ m i.d. * 375 μ m o.d. * 30cm); Moving phase is acetonitrile/borate=10/90 (%v/vpH8.0; 10mmol/L); Flow velocity is 0.01mL/min; Luminescence reagent is K behind the post
3Fe (CN)
6=0.25mmol/L NaOH=1.0mol/L; The luminescence reagent flow velocity is 0.5mL/h behind the post; Separation voltage is 4kV; Chromatographic peak is (1) luminol 1 * 10
-6Mol/L, (2) ABEI 2 * 10
-6Mol/L.
Utilize pressurization capillary electric chromatogram vertical from post chemiluminescence detection pond, the phenoxy carboxylic acid class herbicide of separation detection derivatization, the results are shown in Figure 3:MCPP, 2-PPA, 2,3-CPPA and 2, the range of linearity of 4-D reaches 2-3 the order of magnitude, and detectability is respectively 2 * 10-9mol/L, 2 * 10-9mol/L, 3 * 10-9mol/L and 2 * 10-8mol/L.Experiment condition is: and polymerization integer column (100 μ m i.d. * 375 μ m o.d. * 30cm); Moving phase is acetonitrile/borate=25/75 (%v/v; PH6.8; 20mmol/L); Flow velocity is 0.01mL/min; Luminescence reagent is K3Fe (CN) 6=0.1mmol/L NaOH=1.8mol/L behind the post; The luminescence reagent flow velocity is 0.5mL/h behind the post; Separation voltage is 5kV; Chromatographic peak is (1) MCPP, (2) 2-PPA, and (3) 2,3-CPPA, (all 4.0 * 10-7mol/L) for (4) 2,4-D.
Claims (5)
1, a kind of capillary electric chromatogram comprises pond body, spectral detection window, photomultiplier etc. from column vertical chemiluminescence detection device; The chemical illuminating reagent passage and the capillary electric chromatographic column of described pick-up unit be in "
" the shape upright position, capillary chromatographic column exposes in the corrosion-vulnerable part of strong basicity luminescence reagent minimum, can rapid reaction with chemical illuminating reagent behind the isolated one-tenth separating column to be measured of chromatographic column and produce the photoelectric response signal; The spectral detection window of described pick-up unit is provided with photomultiplier; Described photomultiplier connects computer-controlled faint light detecting device; Described detection cell, luminescence reagent passage and photomultiplier all are arranged in the camera bellows.
2, according to claim 1 from column vertical chemiluminescence detection device, it is characterized in that: the diversion trench of width of pond body (1) bottom centre etching 200～500 μ m, length 2～5mm, closely cover optical glass (2), form detection window (3); The center line vertical with detection window (3) is provided with one stainless steel pipes channel slot (4) is housed, and is used for fixing separation capillary electric chromatographic column (5).
3, according to claim 1 from column vertical chemiluminescence detection device, it is characterized in that: channel slot (4) stretches into detection window (3) top straight, separation capillary post (5) styletable is positioned at and exceeds needle tubing 0.5～1.5mm position, interface (7) sealing and fixing of stainless-steel tube channel slot and pond body.
4, according to claim 1 from column vertical chemiluminescence detection device, it is characterized in that: detection window (3) upper and lower is provided with stainless-steel tube channel slot (8,9), the center line of passage (8,9) and detection window (3) straight line that exists together; Luminescence reagent is introduced by post postcapillary (10), and separation capillary post (5) is in vertical position with the chemical illuminating reagent passage; Described photomultiplier (PMT) (11) is a signal picker, in time gathers the signal that the luminescence reagent reaction produces.
5, according to claim 1 from column vertical chemiluminescence detection device, it is characterized in that: ground-electrode (13) is fixed on the stainless-steel tube channel slot (4), forms from the post pattern with separation capillary post (5) endpiece.
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| CN2009101119479A CN101581709B (en) | 2009-06-10 | 2009-06-10 | Off-column vertical chemiluminescence detection device for capillary electrochromatography |
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|---|---|---|---|
| CN2009101119479A CN101581709B (en) | 2009-06-10 | 2009-06-10 | Off-column vertical chemiluminescence detection device for capillary electrochromatography |
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| CN101581709B CN101581709B (en) | 2012-06-27 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102680621A (en) * | 2011-03-09 | 2012-09-19 | 北京康华源医药信息咨询有限公司 | Chemiluminescence detection technology and application thereof |
| CN102866195A (en) * | 2012-09-19 | 2013-01-09 | 西南大学 | Immobilized-enzyme-based end-column detection interface for capillary electrophoresis |
| CN110632233A (en) * | 2019-10-24 | 2019-12-31 | 上海裕达实业有限公司 | Constant temperature chromatographic device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0342154B1 (en) * | 1988-05-10 | 1992-01-02 | Alusuisse-Lonza Services Ag | Device for measuring the hydrogen concentration in aluminium melts |
| CN1156694C (en) * | 2001-10-26 | 2004-07-07 | 中国科学院长春应用化学研究所 | Electrochemically luminous test pool for end of electrophoretic capillary column |
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- 2009-06-10 CN CN2009101119479A patent/CN101581709B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102680621A (en) * | 2011-03-09 | 2012-09-19 | 北京康华源医药信息咨询有限公司 | Chemiluminescence detection technology and application thereof |
| CN102680621B (en) * | 2011-03-09 | 2016-08-24 | 常州博闻迪医药科技有限公司 | A kind of chemiluminescence detection technology and application thereof |
| CN102866195A (en) * | 2012-09-19 | 2013-01-09 | 西南大学 | Immobilized-enzyme-based end-column detection interface for capillary electrophoresis |
| CN102866195B (en) * | 2012-09-19 | 2014-05-14 | 西南大学 | Immobilized-enzyme-based end-column detection interface for capillary electrophoresis |
| CN110632233A (en) * | 2019-10-24 | 2019-12-31 | 上海裕达实业有限公司 | Constant temperature chromatographic device |
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