CN107115692B - A kind of inner wall modifies the open tubular capillary column and its application of carboxymethyl column [5] aromatic hydrocarbons - Google Patents
A kind of inner wall modifies the open tubular capillary column and its application of carboxymethyl column [5] aromatic hydrocarbons Download PDFInfo
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- CN107115692B CN107115692B CN201710318109.3A CN201710318109A CN107115692B CN 107115692 B CN107115692 B CN 107115692B CN 201710318109 A CN201710318109 A CN 201710318109A CN 107115692 B CN107115692 B CN 107115692B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/206—Packing or coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
- B01D15/3861—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36 using an external stimulus
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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Abstract
The present invention discloses a kind of carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open tubular column and its application.Carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open tubular column preparation method is as follows: capillary is passed through aminopropyl triethoxysilane solution after pretreatment, makes its surface amination；Carboxymethyl column [5] aromatic hydrocarbons is fixed on capillary tube inner wall by amidation process by column [5] arene solution for being passed through carboxyl substitution again.Carboxymethyl column [5] aromatic hydrocarbons is applied to chromatographic isolation field for the first time by the present invention, and preparation method is simple, low in cost, and securely, property is stablized for obtained coating bonding.Carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open tubular column prepared by the present invention has preferable separating effect to aromatic series benzene homologues and chiral separation.
Description
Technical field
The invention belongs to technical field of chromatography, and in particular to a kind of inner wall modification carboxymethyl column [5] aromatic hydrocarbons capillary electricity color
Compose open tubular column and its preparation method and application.
Background technique
Capillary electric chromatogram is a kind of fast and efficiently micro separation technique, it combines the high selection of high performance liquid chromatography
The high efficiency of property and Capillary Electrophoresis.According to existence form of the stationary phase in column, capillary electric chromatogram is divided into capillary filling
Column, capillary monolithic column and capillary open tubular column.Wherein, capillary open tubular column has preparation method simple, is not likely to produce bubble,
The features such as electroosmotic flow speed is big is suitable for efficient, quickly separation analysis.But capillary open tubular column is compared to low, column capacity is small
The shortcomings that also constrain the development of capillary open tubular column.Therefore, novel capillary stationary phase is developed, preparation is compared to big, column capacity
High capillary open tubular column is the key that push capillary electric chromatogram development.
Column aromatic hydrocarbons be it is a kind of be formed by connecting by methylene in phenyl ring contraposition by hydroquinone or Hydroquinone ether it is novel
Macrocyclic host molecule, compared with traditional host molecule, column aromatic hydrocarbons has following characteristics: the rigid structure of high degree of symmetry, phenolic hydroxyl group
It is easy to be functionalized, and good dissolubility in organic solvent.The appearance of this kind of Novel macrocyclic host molecule of column aromatic hydrocarbons by
Extensive concern has been applied to the fields such as material, biology, extraction and detection.Carboxymethyl column [5] aromatic hydrocarbons is a kind of column [5] aromatic hydrocarbons
Carboxymethyl column [5] aromatic hydrocarbons is fixed to capillary tube inner wall, used by derivative using its unique host and guest's volume property and architectural characteristic
It is separated in electrochromatography, there is not been reported both at home and abroad.
Summary of the invention
To overcome problems of the prior art, the present invention provides a kind of inner wall modification carboxymethyl column [5] aromatic hydrocarbons capillary
Pipe electrochromatography open tubular column, preparation method is simple to operation, and the bonding of gained coating securely, stablize by property.
Specific technical solution is as follows:
A kind of inner wall modification carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open tubular column, is prepared by the following method to obtain:
1) pretreatment of capillary: capillary first uses 1M NaOH solution to rinse 2h, then successively uses H2O, 0.1M HCl is molten
Liquid, H2O rinses 10min, is dried with nitrogen；
2) the aminopropyl triethoxysilane aqueous solution that dose volume score is 10%, is passed into the resulting hair of step 1)
In tubule, continues 5min and be placed at 95 DEG C with Teflon duct occlusion capillary both ends and reacted 30min；
3) step 2) is repeated, then 30min is rinsed with methanol, washes away residual solution, obtain the amidized capillary of inner wall；
4) it is 2mg/mL carboxymethyl column [5] aromatic hydrocarbons N, N- dimethyl methyl that concentration is passed through into the capillary that step 3) is modified
Capillary both ends Teflon pipe is connected cyclization, is placed at 70 DEG C and reacts 2h by amide solution 5min；Then it is rinsed with methanol
30min；
5) step 4) is repeated to get the capillary electric chromatogram open tubular column modified to inner wall by carboxymethyl column [5] aromatic hydrocarbons.
The structural formula of carboxymethyl column [5] aromatic hydrocarbons is lower formula (I):
Preferably, the capillary is quartz capillary.
Preferably, the step 4) carries out primary.
Preferably, the step 4) carries out five times.
Above-mentioned open tubular capillary column is in the separation analysis of the capillary electric chromatogram of aromatic series benzene homologues and chiral separation
Application.
The present invention is passed through aminopropyl triethoxysilane solution into pretreated capillary, modifies in capillary tube inner wall
Aminoterminal, then it is passed through carboxymethyl column [5] aromatic hydrocarbons n,N-Dimethylformamide solution, it is anti-by the amidation between amino and carboxyl
It answers, carboxymethyl column [5] aromatic hydrocarbons is fixed on capillary tube inner wall.
Operating procedure schematic diagram of the invention is as shown in Figure 1.
The present invention has the following advantages and effects:
(1) macrocyclic host molecular columns arene derivatives are applied to chromatographic isolation field, present invention preparation for the first time by the present invention
Method is simple to operation, and the bonding of gained coating securely, stablize by property.
(2) carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open tubular column prepared by the present invention is to aromatic series benzene homologues and dansyl
Changing amino acid has preferable separating effect.
Detailed description of the invention
Fig. 1 is fixed carboxymethyl column [5] aromatic hydrocarbons of the present invention in the operating procedure schematic diagram of capillary tube inner wall.
Fig. 2 is that the electrochromatography of 3 kinds of aromatic series benzene homologues of the present invention separates figure；Wherein, peak 1 is toluene, and peak 2 is ethylbenzene, peak 3
For propyl benzene.
Fig. 3 is that the electrochromatography of 3 kinds of chiral separations of the present invention separates figure；Wherein, peak 1 is dansylated threonine, and peak 2 is
Dansylated leucine, peak 3 are dansylated valine.
Specific embodiment
By following detailed description combination attached drawing it will be further appreciated that the features and advantages of the invention.Provided implementation
Example is only the explanation to the method for the present invention, remaining content without limiting the invention in any way announcement.[embodiment 1]
The quartz capillary (50 μm of i.d. × 375 μm o.d.) of long 33cm is first rinsed into 2h with 1M NaOH solution, then
Successively use H2O, 0.1M HCl solution, H2O successively rinses 10min, is then dried up with nitrogen stream.At room temperature with syringe by ammonia third
Ethyl triethoxy silicane alkane aqueous solution (10%, v/v) is passed through in pretreated capillary, continues 5min, then by capillary two
End connects cyclization with Teflon pipe, is placed in 95 DEG C of baking ovens and reacts 30min, this step is repeated once.Then it is rinsed with methanol
30min obtains the capillary that inner wall has modified amino.At room temperature, with syringe by carboxymethyl column [5] aromatic hydrocarbons N, N- dimethyl
Formamide solution is passed through in the capillary column of inner wall modification amino, is continually fed into 5min, and capillary both ends Teflon pipe is connected
It is connected into ring, is placed in 70 DEG C of water-baths and reacts 2h, then rinses 30min with methanol, this step is repeated once, and it is uniform to obtain inner wall
The capillary electric chromatogram open tubular column of coated with multiple layer carboxymethyl column [5] aromatic hydrocarbons.
[embodiment 2]
The quartz capillary (50 μm of i.d. × 375 μm o.d.) of long 33cm is first rinsed into 2h with 1M NaOH solution, then
Successively use H2O, 0.1M HCl solution, H2O successively rinses 10min, is then dried up with nitrogen stream.At room temperature with syringe by ammonia third
Ethyl triethoxy silicane alkane aqueous solution (10%, v/v) is passed through in pretreated capillary, continues 5min, then by capillary two
End connects cyclization with Teflon pipe, is placed in 95 DEG C of baking ovens and reacts 30min, this step is repeated once.Then it is rinsed with methanol
30min obtains the capillary that inner wall has modified amino.At room temperature, with syringe by carboxymethyl column [5] aromatic hydrocarbons N, N- dimethyl
Formamide solution is passed through in the capillary column of inner wall modification amino, is continually fed into 5min, and capillary both ends Teflon pipe is connected
It is connected into ring, is placed in 70 DEG C of water-baths and reacts 2h, then rinses 30min with methanol, this step is repeated four times, and it is uniform to obtain inner wall
The capillary electric chromatogram open tubular column of coated with multiple layer carboxymethyl column [5] aromatic hydrocarbons.
Performance test
Capillary column prepared by embodiment 1 is used for the capillary electricity of 3 kinds of toluene, ethylbenzene, propyl benzene aromatic series benzene homologues
Chromatographic isolation, separation detection operating procedure are as follows:
1. buffer: 10mM Na2HPO4Solution is adjusted to 8 with phosphoric acid pH, then with disposable water phase syringe filters mistake
Filter, 4 DEG C save for use.
2. sample preparation: configuration concentration is 3mg/mL toluene, ethylbenzene, propyl benzene methanol solution, isometric to mix, 4 DEG C of refrigerations
For use.
3. separation detection: 33cm carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open tubular column of preparation burns detection at 8.5cm
Window is fitted into getting stuck, and realizes separation detection using Agilent CE 7100.Sample volume is 10mbar × 5s, and Detection wavelength is
214nm, voltage 10kV.
As a result as shown in Fig. 2, coated with multiple layer carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open pipe prepared by embodiment 1
Column can realize the baseline separation to 3 kinds of aromatic series benzene homologues.
Capillary column prepared by embodiment 1 is used for dansylated valine, dansylated threonine, dansylated leucine 3
The capillary electric chromatogram separation of kind chiral separation, separation detection operating procedure are as follows:
1. buffer: 10mM Na2HPO4Solution is adjusted to 7 with phosphoric acid pH, then with disposable water phase syringe filters mistake
Filter, 4 DEG C save for use.
2. sample preparation: configuration concentration is the dansylated valine of 2mg/mL, dansylated threonine, dansylated leucine methanol
Solution, isometric to mix, 4 DEG C of refrigerations are stand-by.
3. separation detection: 33cm carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open tubular column of preparation burns detection at 8.5cm
Window is fitted into getting stuck, and realizes separation detection using Agilent CE 7100.Sample volume is 8mbar × 5s, and Detection wavelength is
214nm, voltage 15kV.
As a result as shown in figure 3, coated with multiple layer carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open pipe prepared by embodiment 1
Column can realize the baseline separation to 3 kinds of chiral separations.
Embodiments of the present invention are explained in detail above in conjunction with attached drawing, but the present invention is than being not limited to above-mentioned reality
Apply mode.It is all according to equivalent changes and modifications within the scope of the patent application of the present invention, should all belong to coverage area of the invention.
Claims (5)
1. a kind of inner wall modifies carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open tubular column, which is characterized in that make by the following method
It is standby to obtain:
1) pretreatment of capillary: capillary first uses 1 M NaOH solution to rinse 2 h, then successively uses H2O, 0.1 M HCl is molten
Liquid, H2O rinses each 10 min, is dried with nitrogen；
2) the aminopropyl triethoxysilane aqueous solution that dose volume score is 10%, is passed into the resulting capillary of step 1)
In, continue 5 min, with Teflon duct occlusion capillary both ends, is placed at 95 DEG C and reacts 30 min；
3) step 2 is repeated, then 30 min is rinsed with methanol, washes away residual solution, obtain the amidized capillary of inner wall；
4) N of carboxymethyl column [5] aromatic hydrocarbons that concentration is 2 mg/mL, N- dimethyl are passed through into the capillary that step 3) is modified
Capillary both ends Teflon pipe is connected cyclization, is placed at 70 DEG C and reacts 2 h by 5 min of formamide solution；Then methanol is used
Rinse 30min；
5) step 4) is repeated to get the capillary electric chromatogram open tubular column modified to inner wall by carboxymethyl column [5] aromatic hydrocarbons.
2. inner wall according to claim 1 modifies carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open tubular column, feature exists
In the capillary is quartz capillary.
3. inner wall according to claim 1 modifies carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open tubular column, feature exists
In the step 4) carries out primary.
4. inner wall according to claim 1 modifies carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open tubular column, feature exists
In the step 4) carries out five times.
5. inner wall modification carboxymethyl column [5] aromatic hydrocarbons capillary electric chromatogram open tubular column as described in claim 1-4 any one exists
Application in the separation analysis of the capillary electric chromatogram of aromatic series benzene homologues and chiral separation.
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| CN113181890B (en) * | 2021-04-28 | 2022-09-16 | 中国科学院兰州化学物理研究所 | Preparation and application of amino functionalized chiral column [5] arene chromatographic stationary phase |
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| CN103127915A (en) * | 2013-03-12 | 2013-06-05 | 武汉大学 | Polytetrafluoroethylene microextraction column and preparation method thereof |
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| CN103127915A (en) * | 2013-03-12 | 2013-06-05 | 武汉大学 | Polytetrafluoroethylene microextraction column and preparation method thereof |
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| 柱芳烃合成及应用研究进展;卜婷婷等;《化工进展》;20150930;第34卷(第9期);全文 |
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