CN1304841C - Capillary liquid phase chromatographic column and its preparing method - Google Patents
Capillary liquid phase chromatographic column and its preparing method Download PDFInfo
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- CN1304841C CN1304841C CNB2004100779604A CN200410077960A CN1304841C CN 1304841 C CN1304841 C CN 1304841C CN B2004100779604 A CNB2004100779604 A CN B2004100779604A CN 200410077960 A CN200410077960 A CN 200410077960A CN 1304841 C CN1304841 C CN 1304841C
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Abstract
The present invention relates to a capillary liquid chromatographic column and a preparing method thereof. The capillary liquid chromatographic column comprises a whole elastic quartz capillary which dose not need adhesive joint, and the middle part of the capillary is provided with a sieve plate formed by the in-situ polymerization of organic polymers. A column body at one side of the sieve plate is filled with a stationary phase filled by a high-pressure homogenization filling method, and a detection window formed by burning out 2 to 3mm of a polyimide coating layer on the surface of the capillary is arranged on an eduction tube at the other side of the sieve plate. The chromatographic column of the present invention is prepared by the whole capillary without adhesive joint, and therefore, the reduction of column efficiency caused by the retention of a liquid flow in a dead zone is avoided. The present invention is simple in the preparing method, and is especially suitable for the separation analysis of biological, medicinal, environmental, etc. samples with small sample quantity and samples difficult to be separated by conventional liquid phase chromatography.
Description
Technical field
The present invention relates to a kind of liquid-phase chromatographic column and preparation method thereof, particularly about a kind of capillary liquid chromatographic column and preparation method thereof.
Background technology
Capillary liquid chromatography (μ-HPLC) be a kind of efficiently, method for separating and analyzing fast, (HPLC) compares with conventional liquid chromatography, has the over-all resolution efficiency height, stationary phase, moving phase and sample consumption are few, environmental pollution is little, easily, have broad application prospects, so become one of important research direction of chromatographic field in biochemical analysis, medicine and other fields with advantages such as detecting device on-line coupling such as secondary chromatographic system and mass spectrums.In recent years, μ-HPLC complements one another with two-dimensional gel electrophoresis as the efficient separation method of protein mixture, is bringing into play very important effect in protein science research.The preparation method of capillary chromatographic column is one of difficult point of μ-HPLC always, and the preparation of sieve plate is again a key wherein.
Different with conventional liquid-phase chromatographic column, because the column volume of capillary liquid chromatographic column is little, the influence that the dead volume coupled columns that exists in the chromatographic system is imitated is very big, therefore, the design of post tail and fairlead junction is very crucial, as designs and improperly will cause sample diffusion, and post is imitated and reduced.The post tail of the capillary liquid chromatographic column that uses design at present mainly contains three kinds of patterns, first kind: sieve plate 3 adopts porous Teflon (as shown in Figure 1), with internal diameter less than the quartzy capillary fairlead 4 of capillary column 1 near porous sieve plate 3, with epoxy resin 6 capillary column 1 and quartzy capillary fairlead 4 are coupled together.Prepare detection window 5 in the appropriate location of fairlead 4, detect on the post.There is the dead band inevitably in such connected mode, and sample diffusion owing to be detained, cause post to imitate and reduces to the dead band.Second kind: the mode of preparation sieve plate is similar to the sieve plate of electrochromatography, method by the sintering chromatograph packing material prepares sieve plate, but, the technology of this preparation sieve plate is difficult for grasping, the aperture of sieve plate is difficult to the control homogeneous, and this class sieve plate is the same with preceding a kind of sieve plate, often can only be in the preparation of styletable mouth, and the fairlead of band detection window needs to connect in addition.The third: sieve plate adopts porous Teflon or porous stainless steel, leads to by zero dead volume stainless steel two to connect cylinder, sieve plate and fairlead, but the two logical difficult processing of zero dead volume.
Summary of the invention
At the problems referred to above, the purpose of this invention is to provide a kind of capillary liquid chromatographic column and preparation method thereof.
For achieving the above object, the present invention takes following technical scheme: a kind of capillary liquid chromatographic column, it comprises that one whole need not bonding, and inwall is γ-pretreated elastic quartz capillary tube of methacrylic acid oxygen propyl trimethoxy silicane of 30% through the bifunctional reagent, described middle part capillaceous is provided with a sieve plate that is formed by the organic polymer in-situ polymerization, be filled with the stationary phase that adopts the high-pressure homogenization completion method to fill in the cylinder of described sieve plate one side, on the fairlead of described sieve plate opposite side, be provided with described capillary surface polyimide coating is burnt the detection window that 2～3mm forms.
The stationary phase of filling in the described kapillary is the positive liquid chromatography stuffing, or the reversed-phase liquid chromatography filler, or ion-exchange packing, or a kind of in the size exclusion chromatograph filler.
Described internal diameter capillaceous is 0.05～0.53mm.
A kind of method for preparing above-mentioned capillary liquid chromatographic column, it may further comprise the steps:
(1) selecting an internal diameter is the elastic quartz capillary tube of 0.05～0.53mm, adopts the bifunctional reagent that described capillary tube inner wall is carried out pre-service, and described bifunctional reagent is γ-methacrylic acid oxygen propyl trimethoxy silicane of 30%;
(2) adopt the organic polymer in-situ polymerization in described kapillary, to form the sieve plate of chromatographic column;
(3) adopt the high-pressure homogenization completion method that liquid chromatography stuffing is packed in the kapillary cylinder of described sieve plate one side, be fixed phase;
(4) polyimide coating of described kapillary outer wall is burnt 2～3mm, on the kapillary of described sieve plate opposite side, form detection window.
The preparation method of described sieve plate is as follows:
(1) adopt the bifunctional reagent that described kapillary is carried out pre-service;
(2) monomer mixture is mixed with pore-foaming agent 2: 2 by volume～3;
(3) add initiating agent again, ultrasonic mixing, and feeding nitrogen is removed the air in the described reaction mixture;
(4) reaction mixture that obtains in the step (3) is fed the pretreated kapillary of step (1) and form one section long fluid column of 2～3mm, and be located in the kapillary position of preparation sieve plate, two ends at described fluid column are full of with air respectively, and seal described two ends capillaceous with silica gel, in 40～80 ℃ of water-baths, reacted 18～24 hours, finish polyreaction, form the sieve plate of porous.
It is as follows to adopt the bifunctional reagent that described kapillary is carried out pretreated step:
(1) 0.1M NaOH, water, acetone are passed through kapillary successively;
(2) feed nitrogen, dry up kapillary;
(3) bifunctional reagent is full of in the kapillary after step (2) is handled, seals 12 hours;
(4) clean kapillary, nitrogen dries up.
The preparation method of described sieve plate is as follows:
(1) adopt the bifunctional reagent that described kapillary is carried out pre-service;
(2) monomer mixture is mixed with pore-foaming agent 2: 2 by volume～3;
(3) add initiating agent again, ultrasonic mixing, and feeding nitrogen is removed the air in the described reaction mixture;
(4) reaction mixture that obtains in the step (3) is fed the pretreated kapillary of step (1) and form one section long fluid column of 2～3mm, and be located in the kapillary position of preparation sieve plate, two ends at described fluid column are full of with air respectively, and seal described two ends capillaceous with silica gel, in 40～80 ℃ of water-baths, reacted 18～24 hours, finish polyreaction, form the sieve plate of porous.
Described monomer mixture is butyl methacrylate and methacrylate ethyl ester, and its mass ratio is 0.8～2: 1.
Described pore-foaming agent is a propyl alcohol, and butylene glycol and water, its mass ratio are 4～6: 3～5: 1.
Described initiating agent is an azoisobutyronitrile, and its addition is 0.5～1% of a described monomeric compound quality.
The present invention is owing to take above design, it has the following advantages: 1, the present invention adopt one need not be bonding whole elastic quartz capillary tube preparative liquid chromatography post, both comprised the cylinder of filling stationary phase, comprise sieve plate again, fairlead and detection window, particularly fairlead and cylinder are one, do not need other connection, avoided the formation in dead band, dead volume reduces, thereby has improved the post effect.2, the present invention adopts the sieve plate of organic polymer in-situ polymerization preparation, and it is the aperture homogeneous not only, and can be in any position preparation of cylinder.3, therefore the present invention owing to introduce the bifunctional reagent capillary tube inner wall is handled, can guarantee that sieve plate can bear high pressure and can slippage from kapillary in preparation sieve plate process.4, the present invention adopts conventional homogenate legal system to be equipped with stationary phase, compares with electronic filling with dry method, has higher post and imitates, technical also grasp easily.5, detection window of the present invention is to form by the polyimide coating of elastic quartz capillary tube outer wall being burnt 2～3mm, and therefore preparation easily.The preparation method of capillary liquid chromatographic column of the present invention is simple, is specially adapted to samples such as the few biology of sample size, medicine, environment and the compartment analysis of the sample that is difficult to separate with conventional liquid chromatography.
Description of drawings
Fig. 1 is the gluing capillary liquid chromatographic column synoptic diagram that connects in the prior art
Fig. 2 is a capillary liquid chromatographic column structural representation of the present invention
Fig. 3 a～3d is with the process in the bulk polymerization potpourri introducing kapillary when preparing sieve plate
Fig. 4 is 7 kinds of spectrograms that sample separates on capillary liquid chromatographic column of the present invention
Fig. 5 is 3 kinds of spectrograms that sample separates on capillary liquid chromatographic column of the present invention
Embodiment
As shown in Figure 2, capillary liquid chromatographic column of the present invention comprises cylinder 1, stationary phase (filler) 2, and sieve plate 3, fairlead 4, detection window 5, they all are present in one whole and need not in the bonding elastic quartz capillary tube.
Sieve plate preparation method of the present invention may further comprise the steps:
1, at first gets one whole elastic quartz capillary tube, adopt bifunctional reagent γ-methacrylic acid oxygen propyl trimethoxy silicane to handle the quartz capillary inwall.This bifunctional reagent's one end contains alkoxy grp, with silicon hydroxyl reaction capillaceous; The other end contains two keys, participates in polyreaction when monomer polymerization.
2, with monomer mixture butyl methacrylate and methacrylate ethyl ester (mass ratio 0.8～2: 1), and pore-foaming agent n-propanol, butylene glycol and water (mass ratio 4～6: 3～5: 1), 2: 2 by volume～3 mix in container.
3, add azoisobutyronitrile as initiating agent, initiated polymerization, the addition of initiating agent is 0.5～1% of an above-mentioned monomer mixture quality.
4, ultrasonic mixing feeds nitrogen the air of reaction mixture is removed;
5, polyblend is pressed into (shown in Fig. 3 a) in the kapillary, forming a bit of fluid column 12 (shown in Fig. 3 b) in the kapillary, afterwards air is pressed into (shown in Fig. 3 c) in the kapillary, drive fluid column 12 moves forward needs the preparation sieve plate until fluid column arrival position (shown in Fig. 3 d), seal the two ends of column capillary tube post rapidly with silicon rubber, be placed in 40～80 ℃ of water-baths and heated 18～24 hours, finish polyreaction, form the sieve plate 3 (as shown in Figure 2) of porous.
(6) with methyl alcohol or acetonitrile equal solvent flushing kapillary, remove residual organism such as pore-foaming agent.
Stationary phase of the present invention adopts high-pressure homogenization dress post method to load filler, concrete grammar is: at first according to the different in kind of filler, with appropriate solvent filler is prepared into homogenate, ultrasonic mixing, pack in the homogenate jar, (under 15～30MPa) homogenate is pressed in the capillary column 1 at certain pressure with high-pressure pump; After filler is loaded into designated length, termination of pumping, step-down.
The following scheme of the employing of the preparation of detection window 5 of the present invention: on the sieve plate 3 opposite side kapillary outer walls of filling in filler, the polyimide coating of capillary surface is burnt 2～3mm, and clean, as detection window 5 with ethanol.
The preparation of embodiment one, capillary liquid chromatographic column of the present invention
1, the pre-service of capillary column: getting internal diameter is 0.32mm, length is the elastic quartz capillary tube of 60cm, utilize the negative pressure of vacuum pump that the 0.1M sodium hydroxide solution was passed through kapillary 2 hours, water flushing kapillary is 7 up to pH, to pass through kapillary for the acetone of 50 times of kapillary volumes, dry up 2 minutes with nitrogen, get γ-methacrylic acid oxygen propyl trimethoxy silicane acetone soln of 30% and be full of capillary column, two ends were with silicone rubber seal 12 hours, use acetone rinsing, nitrogen dries up stand-by.
2, the preparation of in-situ polymerization sieve plate: butyl methacrylate, methacrylate ethyl ester are pressed mass ratio mix the formation monomer mixture at 1.3: 1, again with pore-foaming agent potpourri n-propanol, 1,4-butylene glycol and water mix formation pore-foaming agent potpourri with mass ratio at 5: 4: 1, monomer mixture and pore-foaming agent potpourri are mixed with volume ratio at 2: 3, add the azoisobutyronitrile that quality is a polymerization reaction monomer quality 1% again, ultrasonic mixing feeds nitrogen 2 minutes to remove the oxygen in the potpourri in potpourri.Shown in Fig. 3 a～d, with an air injector tube 7 (interior no liquid), insert the brown glass bottle 9 of band teflon threaded cap 8, pressure gas in bottle 9, make bulk polymerization potpourri 10 be pressed into kapillary 11 (handling), form 2mm polymkeric substance fluid column 12 with the bifunctional reagent.Upwards carry kapillary 11 then, make it break away from bulk polymerization potpourri 10 solution, use air injector tube 7 to bottle 9 compressed airs again, so that being incorporated into, polymkeric substance fluid column 12 needs to prepare the sieve plate place in the kapillary 11, with kapillary 11 two ends silicone rubber seals, be placed on heating taking-up after 20 hours in 60 ℃ of water-baths, use the washed with methanol capillary column.
3, the filling of stationary phase: the 0.2g 5 μ mC18 (octadecyl silane) that take a morsel are mixed with homogenate with the 1ml methenyl choloride, ultrasonic mixing, pack in the homogenate jar, be forced into 20Mpa, filler packed in the capillary column into stationary phase 2 long 20cm (as shown in Figure 2);
4, the preparation of detection window: the polyimide coating of fairlead 4 outer walls of sieve plate 3 opposite sides is burnt 2～3mm form detection window 5.
5, standard specimen test result: the methanol solution 200nl that gets thiocarbamide, benzene, toluene, naphthalene, biphenyl, phenanthrene, anthracene, moving phase is methanol (75/25), flow velocity is 3 μ l/min, under the 254nm wavelength, the capillary liquid chromatographic column for preparing according to the conventional method utilization separates, and its result as shown in Figure 4.The post of each chromatographic peak is imitated and is followed successively by every meter of 4.1,4.4,5.1,6.2,7.3,9.3 ten thousand column plate among the figure.
Embodiment two:
During the preparation sieve plate, monomer mixture butyl methacrylate, methacrylate ethyl ester are pressed mass ratio mix at 1.51: 1, remaining reagent dosage is with embodiment one.Sieve plate length is 3mm, and internal diameter is 0.32mm, long capillary tube 50cm, the long 15cm of stationary phase, fill 5 μ m C18 other with embodiment one.
The standard specimen test result: get the methanol solution of thiocarbamide, toluene and naphthalene, under the 254nm wavelength, utilize the capillary high performance liquid chromatography post for preparing to separate, its result as shown in Figure 5.Moving phase is methanol (50/50), and flow velocity is 4 μ l/min.The post of each chromatographic peak is imitated and is followed successively by every meter of 2.4,8.3,9.7 ten thousand column plate among the figure.
Claims (9)
1, a kind of capillary liquid chromatographic column, it comprises one whole, and to need not bonding and inwall be γ-pretreated elastic quartz capillary tube of methacrylic acid oxygen propyl trimethoxy silicane of 30% through the bifunctional reagent, described middle part capillaceous is provided with a sieve plate that is formed by the organic polymer in-situ polymerization, be filled with the stationary phase that adopts the high-pressure homogenization completion method to fill in the cylinder of described sieve plate one side, on the fairlead of described sieve plate opposite side, be provided with described capillary surface polyimide coating is burnt the detection window that 2～3mm forms.
2, capillary liquid chromatographic column as claimed in claim 1 is characterized in that: the stationary phase of filling in the described kapillary is the positive liquid chromatography stuffing, or the reversed-phase liquid chromatography filler, or ion-exchange packing, or a kind of in the size exclusion chromatograph filler.
3, capillary liquid chromatographic column as claimed in claim 1 or 2 is characterized in that: described internal diameter capillaceous is 0.05～0.53mm.
4, a kind of method for preparing claim 1 or 2 or 3 described capillary liquid chromatographic columns, it may further comprise the steps:
(1) selecting an internal diameter is the elastic quartz capillary tube of 0.05～0.53mm, adopts the bifunctional reagent that described capillary tube inner wall is carried out pre-service, and described bifunctional reagent is γ-methacrylic acid oxygen propyl trimethoxy silicane of 30%;
(2) adopt the organic polymer in-situ polymerization in described kapillary, to form the sieve plate of chromatographic column;
(3) adopt the high-pressure homogenization completion method that liquid chromatography stuffing is packed in the kapillary cylinder of described sieve plate one side, be fixed phase;
(4) polyimide coating of described kapillary outer wall is burnt 2～3mm, on the kapillary of described sieve plate opposite side, form detection window.
5, the preparation method of capillary liquid chromatographic column as claimed in claim 4 is characterized in that: it is as follows to adopt the bifunctional reagent that described kapillary is carried out pretreated step:
(1) 0.1M NaOH, water, acetone are passed through kapillary successively;
(2) feed nitrogen, dry up kapillary;
(3) bifunctional reagent is full of in the kapillary after step (2) is handled, seals 12 hours;
(4) clean kapillary, nitrogen dries up.
6, the preparation method of capillary liquid chromatographic column as claimed in claim 4 is characterized in that: the preparation method of described sieve plate is as follows:
(1) monomer mixture is mixed with pore-foaming agent 2: 2 by volume～3;
(2) add initiating agent again, ultrasonic mixing, and feeding nitrogen is removed the air in the described reaction mixture;
(3) reaction mixture that obtains in the step (2) is fed the pretreated described kapillary of step (1) and form one section long fluid column of 2～3mm, and be located in the kapillary position of preparation sieve plate, two ends at described fluid column are full of with air respectively, and seal described two ends capillaceous with silica gel, in 40～80 ℃ of water-baths, reacted 18～24 hours, finish polyreaction, form the sieve plate of porous.
7, the preparation method of capillary liquid chromatographic column as claimed in claim 6 is characterized in that: described monomer mixture is butyl methacrylate and methacrylate ethyl ester, and its mass ratio is 0.8～2: 1.
8, the preparation method of capillary liquid chromatographic column as claimed in claim 6 is characterized in that: described pore-foaming agent is a propyl alcohol, and butylene glycol and water, its mass ratio are 4～6: 3～5: 1.
9, the preparation method of capillary liquid chromatographic column as claimed in claim 6 is characterized in that: described initiating agent is an azoisobutyronitrile, and its addition is 0.5～1% of a described monomeric compound quality.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101105482B (en) * | 2007-07-27 | 2010-07-21 | 福州大学 | Usage method for electrochromatography capillary column production device |
| CN102513073B (en) * | 2011-12-12 | 2013-07-24 | 厦门大学 | Method for manufacturing capillary solid phase extraction microcolumn |
| CN102590402A (en) * | 2012-03-28 | 2012-07-18 | 厦门大学 | Preparing method of capillary tube chromatographic columns |
| CN108079980A (en) * | 2016-11-21 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of chromatographic column and preparation and application with hydrophobicity brush-type polymer coating |
| CN110494746A (en) * | 2017-03-03 | 2019-11-22 | 布莱阿姆青年大学 | Multi-modal, multi-detector liquid chromatographic system |
| AU2019223350A1 (en) * | 2018-02-26 | 2020-09-17 | Brigham Young University | Integrated column and detector in a module for liquid chromatography |
| CN111855877B (en) * | 2019-04-30 | 2024-05-24 | 中国科学院上海微系统与信息技术研究所 | MEMS-based multi-stationary-phase miniature packed column structure and preparation method thereof |
| CN115078602B (en) * | 2022-05-30 | 2024-05-28 | 郑州大学第一附属医院 | Capillary high-pressure liquid chromatographic column and ultrasonic preparation method and application thereof |
| CN115356425A (en) * | 2022-07-27 | 2022-11-18 | 上海奥浦迈生物科技股份有限公司 | NanoHPLC-Titer system applied to culture medium supernatant albumin quantification |
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| EP0414324A1 (en) * | 1989-08-25 | 1991-02-27 | Koninklijke Philips Electronics N.V. | Method of manufacturing a separation column and a separation column |
| CN1499201A (en) * | 2002-11-08 | 2004-05-26 | 中国科学院大连化学物理研究所 | Method for connecting capillary columns with zero dead volume and dedicated device |
| US6758966B2 (en) * | 2000-01-04 | 2004-07-06 | Waters Investments Limited | Capillary columns employing monodispersed particles |
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2004
- 2004-09-21 CN CNB2004100779604A patent/CN1304841C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB856873A (en) * | 1956-02-10 | 1960-12-21 | Evans Electroselenium Ltd | Improvements in or relating to apparatus for counting small particles |
| GB1074504A (en) * | 1963-10-08 | 1967-07-05 | Ceskoslovenska Akademie Ved | A column for greatly accelerated caromatographic processes |
| JPS6110769A (en) * | 1984-06-26 | 1986-01-18 | Yuji Takayama | Capillary column having detachable metal capillary tube portion |
| EP0414324A1 (en) * | 1989-08-25 | 1991-02-27 | Koninklijke Philips Electronics N.V. | Method of manufacturing a separation column and a separation column |
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