CN116159543A - Preparation method and application of capillary electrochromatography open tubular column based on chiral covalent organic framework material - Google Patents
Preparation method and application of capillary electrochromatography open tubular column based on chiral covalent organic framework material Download PDFInfo
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- 238000002045 capillary electrochromatography Methods 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 56
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- 238000000926 separation method Methods 0.000 claims abstract description 27
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- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 19
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- -1 2- (4-hydroxyphenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine Chemical compound 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 9
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 238000005576 amination reaction Methods 0.000 claims abstract description 6
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- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 14
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- HNDVDQJCIGZPNO-RXMQYKEDSA-N D-histidine Chemical compound OC(=O)[C@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-RXMQYKEDSA-N 0.000 claims description 7
- 229930195721 D-histidine Natural products 0.000 claims description 7
- KDXKERNSBIXSRK-RXMQYKEDSA-N D-lysine Chemical compound NCCCC[C@@H](N)C(O)=O KDXKERNSBIXSRK-RXMQYKEDSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 150000001413 amino acids Chemical class 0.000 claims description 5
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- 239000011259 mixed solution Substances 0.000 claims description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
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- 238000005516 engineering process Methods 0.000 claims description 2
- 230000005526 G1 to G0 transition Effects 0.000 abstract description 12
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 abstract description 9
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- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
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- 239000004471 Glycine Substances 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical group N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01D15/3833—Chiral chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/29—Chiral phases
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- Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
A preparation method and application of a capillary electrochromatography open tubular column based on chiral covalent organic framework materials relate to the preparation method and application of the capillary electrochromatography open tubular column. The method aims to solve the technical problems of small capacity and unsatisfactory separation effect of the existing capillary electrochromatography open tubular column. The method comprises the following steps: firstly, amination treatment is carried out on the inner wall of a capillary column, then 2- (4-hydroxyphenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 1,3, 5-trialdehyde phloroglucinol are grown into a covalent organic framework material in situ in the capillary column, and finally beta-cyclodextrin is introduced onto the covalent organic framework material through a post-modification method, so that a chiral covalent organic framework material stationary phase is formed. The capillary electrochromatography open tubular column based on chiral covalent organic framework material prepared by the invention can realize good separation effect on amino acid enantiomers. Can be used in the field of organic separation.
Description
Technical Field
The invention relates to a preparation method and application of a capillary electrochromatography open tubular column.
Background
Chirality is an important element related to life and science, such as protein, amino acid, sugar and other substances, and some medicines, pesticides and the like, have chirality. Enantiomers always exhibit different optical and chemical properties due to their strong steric directionality. Except glycine, all naturally occurring amino acids exist in both isomeric forms of the L-and D-configuration. Only L-amino acids are essential components of organisms and play a very important role in life activities, whereas D-amino acids may exhibit toxicity or metabolic abnormalities [ Sensors and Actuators B Chemical (2020,319,128265) ]. Therefore, selective chiral recognition of amino acids is of great research value, particularly in clinical diagnostics and therapy. With the increasing demand for the identification of optically pure compounds, efforts have been made to develop efficient, economical, convenient chiral separation assays.
Capillary electrochromatography is an aggregate having the advantages of both capillary electrophoresis and high performance liquid chromatography. As a powerful electric micro-separation method, the method has the characteristics of high separation efficiency, small sample consumption, high separation selectivity, short analysis time and the like, and is widely applied to various analysis fields such as medicines, biology, environment and the like. In the chiral resolution process, the chiral stationary phase has a key effect on resolution of chiral compounds.
The Chinese patent with application number 201711422563.X discloses a preparation method of chiral bonding capillary electrochromatography open tubular column and application thereof, which designs a derivative with isocyanic acid group by utilizing the special structure and molecular characteristics of beta-cyclodextrin, and bonds the derivative with the inner wall of an aminated capillary tube to prepare the chiral bonding capillary electrochromatography open tubular column. But the open string has small column capacity and unsatisfactory separation effect.
Disclosure of Invention
The invention aims to solve the technical problems of small capacity and unsatisfactory separation effect of the existing capillary electrochromatography open tubular column, and provides a preparation method and application of the capillary electrochromatography open tubular column based on chiral covalent organic framework materials. The open tubular column takes a novel chiral covalent organic framework material with larger specific surface area and multiple action sites as a capillary electrochromatography open tubular column stationary phase, and has simple preparation method and good chiral separation performance.
The preparation method of the capillary electrochromatography open tubular column based on the chiral covalent organic framework material comprises the following steps:
1. sequentially flushing the capillary column with HCl solution, water and NaOH solution, sealing and placing the two ends of the capillary column for a period of time, flushing with water to neutrality, flushing with methanol, and drying with nitrogen;
2. the volume ratio is (60-50): injecting the mixed solution of the 3-aminopropyl triethoxysilane and the methanol in the step (40-50) into the capillary column treated in the step one, sealing two ends of the capillary column at 40-50 ℃ for reaction for 16-24 hours, amination the inner wall of the capillary, flushing with the methanol after the reaction is finished, and blowing nitrogen to dry;
3. the ratio of the 2- (4-hydroxyphenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and the 1,3, 5-trialdehyde phloroglucinol is (1-3) according to the mass: 1 into an organic solvent I, and then adding the organic solvent I into the organic solvent I according to the mass ratio of 2- (4-hydroxyphenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine to the acid catalyst of 1: (0.05-0.1), adding an acid catalyst into the organic solvent I, uniformly mixing by ultrasonic, filling into the capillary column treated in the second step, reacting for 24-72 h by using a water bath at 75-90 ℃, flushing by methanol after the reaction is finished, and drying by nitrogen;
4. according to the ratio of the mono-6-O-p-toluenesulfonyl-beta-cyclodextrin to the 2- (4-hydroxyphenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine in the step three, which is 1 to 3:1, adding the mono-6-O-p-toluenesulfonyl-beta-cyclodextrin into an organic solvent II, adding a certain amount of Azobisisobutyronitrile (AIBN), uniformly mixing by ultrasound, pouring into a capillary column treated in the step three, reacting for 12 to 24 hours by using a water bath at 60 to 80 ℃, flushing by using methanol after the reaction is finished, and drying by using nitrogen to obtain the capillary electrochromatography open tubular column based on chiral covalent organic framework materials.
Further, in the first step, the two ends of the capillary column are placed in a sealing way for 10-16 hours.
Further, the organic solvent I in the third step is one or a combination of any two of acetonitrile, N-dimethylformamide, ethyl acetate, N-butanol, o-dichlorobenzene and acetone.
Further, the acid catalyst in the third step is glacial acetic acid, dilute hydrochloric acid or trifluoroacetic acid.
Further, the organic solvent II in the fourth step is N, N-dimethylformamide, methanol, ethanol, acetone or dimethyl sulfoxide.
Further, the ratio of the mass of Azobisisobutyronitrile (AIBN) to the volume of the N, N-dimethylformamide solvent in the fourth step is (0.5 to 1) mg:1mL.
The application of the capillary electrochromatography open tubular column based on the chiral covalent organic framework material is that the capillary electrochromatography open tubular column based on the chiral covalent organic framework material is utilized to split amino acid enantiomers by adopting a capillary electrochromatography technology.
The method for splitting the amino acid enantiomer by utilizing the capillary electrochromatography open tubular column based on chiral covalent organic framework materials comprises the following steps:
and (3) operating the capillary electrochromatography open tubular column based on chiral covalent organic framework materials under electrochromatography operation conditions of different buffer solutions with pH value of=5, separation voltage of 12kV, separation temperature of 20 ℃, sample injection pressure of 50mbar and sample injection time of 2s to complete chiral resolution of D/L-histidine and D/L-lysine.
The capillary electrochromatography open tubular column based on the chiral covalent organic framework material is characterized in that firstly, the inner wall of the capillary column is subjected to amination treatment, then 2- (4-hydroxyphenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 1,3, 5-trialdehyde phloroglucinol are grown into the covalent organic framework material in situ in the capillary column, finally, beta-cyclodextrin is introduced onto the covalent organic framework material through a post-modification method to form a chiral covalent organic framework material stationary phase, and the prepared capillary electrochromatography open tubular column taking the chiral covalent organic framework material as the stationary phase shows good separation effect in the splitting of amino acid enantiomers.
The capillary electrochromatography open tubular column based on the chiral covalent organic framework material has the following beneficial effects:
(1) The capillary electrochromatography open tubular column is a covalent organic framework material stationary phase with hydroxyl, and simultaneously, chiral monomer beta-cyclodextrin is skillfully introduced into a covalent organic framework structure, so that the chiral covalent organic framework material stationary phase is successfully synthesized, and the range of the capillary electrochromatography chiral stationary phase is expanded;
(2) In the capillary electrochromatography open tubular column, the covalent organic framework material has larger specific surface area, and the problem of small capacity of the capillary electrochromatography open tubular column is solved by taking the chiral covalent organic framework material as a capillary electrochromatography stationary phase;
(3) The beta-cyclodextrin, imidazole ring, benzene ring and other groups are introduced into the capillary column to form a stationary phase with multiple mechanisms and modes, so that the chiral resolution capability is improved.
Drawings
FIG. 1 is a schematic diagram of a preparation flow of a chiral covalent organic framework material capillary electrochromatography open tubular column of the present invention;
FIG. 2 is an infrared spectrum of a chiral covalent organic framework material capillary electrochromatography open tubular stationary phase of example 1;
FIG. 3 is a diagram of the electrochromatography separation of D/L-histidine and D/L-lysine with a chiral covalent organic framework material capillary electrochromatography column of example 1.
Detailed Description
The invention is further described below with reference to examples and figures.
Example 1: the preparation method of the capillary electrochromatography open tubular column based on the chiral covalent organic framework material comprises the following steps:
1. washing the capillary column with 1mol/L HCl solution, water and 1mol/L NaOH solution for 30min respectively, wherein the inner diameter of the capillary column is 75 μm, the outer diameter is 365 μm, and the length is 40cm, sealing the two ends of the capillary column, washing with water bath at 40deg.C for 10h, washing with water to neutrality, washing with methanol, and blow-drying with nitrogen;
2. injecting a mixed solution of 3-aminopropyl triethoxysilane and methanol with the volume ratio of 50:50 into the capillary column treated in the first step, sealing two ends of the capillary column, placing the capillary column in a water bath at 40 ℃ for reaction for 24 hours, amination the inner wall of the capillary tube, flushing the methanol after the reaction is finished, and drying by nitrogen;
3. adding 0.015mmoL of 2- (4-hydroxyphenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 0.015mmoL of 1,3, 5-trialdehyde phloroglucinol into 4mL of N, N-dimethylformamide solvent, adding 0.001mmoL of glacial acetic acid, uniformly mixing by ultrasound, pouring into the capillary column treated in the second step, reacting for 48H in a water bath at 80 ℃, flushing with methanol after the reaction is finished, and drying by nitrogen;
4. adding 0.015mmoL of mono-6-O-p-toluenesulfonyl-beta-cyclodextrin into 2mL of N, N-dimethylformamide solvent, adding 0.0015g of AIBN, uniformly mixing by ultrasonic, pouring into the capillary column treated in the step three, reacting for 14h in a water bath at 70 ℃, flushing methanol after the reaction is finished, blowing nitrogen to dry, and obtaining the capillary electrochromatography open tubular column based on chiral covalent organic framework material. The specific preparation flow is shown in figure 1.
Adopting quartz glass plate to simulate the inner wall of capillary column, and adopting the steps of first, second, third and fourth to treat quartz glass plateScraping the solid on the glass plate, performing infrared spectrum characterization, wherein the infrared spectrums of the solid obtained after the third and fourth treatment are sequentially shown as curves b and c in fig. 2, the infrared spectrum of the mono-6-O-p-toluenesulfonyl-beta-cyclodextrin is shown as a curve a, and the curve a in fig. 2 shows that the infrared spectrum of the solid is 2930cm -1 And 1365cm -1 Respectively ascribed to the-CH on the skeleton of the mono-6-O-p-toluenesulfonyl-beta-cyclodextrin 2 And a characteristic absorption peak of s=o. 1655cm in Curve b -1 And 1331cm -1 The characteristic absorption peaks respectively ascribed to c=c and C-N in the covalent organic framework material. The characteristic peaks of both the beta-cyclodextrin and the covalent organic framework material are retained in the chiral covalent organic framework stationary phase material (curve c), and the characteristic peak of s=o in the mono-6-O-p-toluenesulfonyl-beta-cyclodextrin disappears. The results show that the covalent organic framework was successfully synthesized within the capillary column and that the chiral monomer β -cyclodextrin was successfully incorporated onto this covalent organic framework.
Chiral resolution performance tests were performed using the chiral covalent organic framework material based capillary electrochromatography open tubular column prepared in example 1:
the chiral separation of D/L-histidine and D/L-lysine was performed by using the capillary electrochromatography open tubular column based on chiral covalent organic framework material prepared in example 1 under electrochromatography operation conditions of 20mmol/L of ammonium acetate buffer solution with pH=5, separation voltage of 12kV, separation temperature of 20 ℃, sample injection pressure of 50mbar and sample injection time of 2 s. FIG. 3 is a graph of the electrochromatography separation of D/L-histidine and D/L-lysine at a wavelength of 200nm ultraviolet detection, and it can be seen from FIG. 3 that baseline separation is achieved for both amino acid enantiomers, which proves that the capillary electrochromatography open tubular column based on chiral covalent organic framework material prepared in example 1 has very strong chiral resolution capability.
Example 2: the preparation method of the capillary electrochromatography open tubular column based on the chiral covalent organic framework material comprises the following steps:
1. washing the capillary column with 1mol/L HCl solution, water and 1mol/L NaOH solution for 30min respectively, wherein the inner diameter of the capillary column is 75 μm, the outer diameter is 365 μm, the length is 40cm, sealing the two ends of the capillary column, washing with water at 40deg.C for 10h, washing with water to neutrality, washing with methanol, and blow-drying with nitrogen;
2. injecting a mixed solution of 3-aminopropyl triethoxysilane and methanol with the volume ratio of 60:40 into the capillary column treated in the first step, sealing two ends of the capillary column, performing water bath reaction at 45 ℃ for 24 hours to aminate the inner wall of the capillary, flushing the methanol after the reaction is finished, and drying with nitrogen;
3. adding 0.020mmoL 2- (4-hydroxyphenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 0.010mmoL 1,3, 5-trialdehyde phloroglucinol into 4mL acetonitrile solvent, adding 0.0015mmoL glacial acetic acid, uniformly mixing by ultrasound, filling into the capillary column treated in the second step, reacting for 48H in a water bath at 90 ℃, flushing with methanol after the reaction is finished, and drying by nitrogen.
4. Adding 0.04mmoL of mono-6-O-p-toluenesulfonyl-beta-cyclodextrin into 2mL of dimethyl sulfoxide solvent, adding 0.0015g of AIBN, uniformly mixing by ultrasonic, pouring into the capillary column treated in the step three, carrying out water bath reaction at 80 ℃ for 12h, flushing with methanol after the reaction is finished, and drying by nitrogen to obtain the capillary electrochromatography open tubular column based on chiral covalent organic framework materials.
And (3) simulating the inner wall of the capillary column by adopting a quartz glass plate, sequentially adopting the first step, the second step, the third step and the fourth step to treat the quartz glass plate, scraping solids on the glass plate, and performing infrared spectrum characterization. The results show that, similar to example 1, the covalent organic framework was successfully synthesized in the capillary column and the chiral monomer β -cyclodextrin was successfully incorporated into this covalent organic framework.
The chiral resolution performance test using the capillary electrochromatography open tubular column based on chiral covalent organic framework material prepared in example 2 was as follows: the chiral covalent organic framework material-based capillary electrochromatography column prepared in example 2 was used for chiral resolution application of D/L-histidine and D/L-lysine under electrochromatography operation conditions of 20mmol/L of ammonium acetate buffer solution with pH=5, separation voltage of 12kV, separation temperature of 20 ℃, sample injection pressure of 50mbar and sample injection time of 2 s. The baseline separation of the two amino acid enantiomers is realized, and the capillary electrochromatography open tubular column based on the chiral covalent organic framework material prepared by the embodiment has strong chiral resolution capability.
Example 3: the preparation method of the capillary electrochromatography open tubular column based on the chiral covalent organic framework material comprises the following steps:
1. sequentially flushing the capillary columns with 1mol/L HCl solution, water and 1mol/L NaOH solution for 30min, wherein the inner diameter of the capillary column is 75 μm, the outer diameter of the capillary column is 365 μm, the length of the capillary column is 40cm, sealing the two ends of the capillary column, flushing with water to neutrality at 40 ℃ in water bath for 12h, flushing with methanol, and drying with nitrogen;
2. injecting a mixed solution of 3-aminopropyl triethoxysilane and methanol with the volume ratio of 55:45 into the capillary column treated in the first step, sealing two ends of the capillary column in a water bath at 50 ℃ for reaction for 18 hours, amination the inner wall of the capillary, flushing the methanol after the reaction is finished, and drying with nitrogen;
3. adding 0.030oL 2- (4-hydroxyphenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and 0.010mmoL 1,3, 5-trialdehyde phloroglucinol into a mixed solvent of 2mL acetone and 2mL n-butanol, adding 0.0022mmoL glacial acetic acid, carrying out ultrasonic mixing, pouring into the capillary column treated in the step two, carrying out water bath reaction at 75 ℃ for 72H, washing with methanol after the reaction is finished, and drying with nitrogen.
4. Adding 0.05mmoL of mono-6-O-p-toluenesulfonyl-beta-cyclodextrin into 2mL of acetone solvent, adding 0.0016g of AIBN, uniformly mixing by ultrasonic, pouring into the capillary column treated in the step three, carrying out water bath reaction at 65 ℃ for 18h, flushing with methanol after the reaction is finished, and drying by nitrogen to obtain the capillary electrochromatography open tubular column based on chiral covalent organic framework materials.
And (3) simulating the inner wall of the capillary column by adopting a quartz glass plate, sequentially adopting the first step, the second step, the third step and the fourth step to treat the quartz glass plate, scraping solids on the glass plate, and performing infrared spectrum characterization. The results show that, similar to example 1, the covalent organic framework was successfully synthesized in the capillary column and the chiral monomer β -cyclodextrin was successfully incorporated into this covalent organic framework.
The chiral resolution performance test was performed by using the capillary electrochromatography open tubular column based on chiral covalent organic framework material prepared in this example 3, and the specific steps are as follows: the chiral covalent organic framework material-based capillary electrochromatography column prepared in the embodiment 3 is utilized to carry out chiral resolution application on D/L-histidine and D/L-lysine under electrochromatography operation conditions of 20mmol/L of ammonium acetate buffer solution with pH=5, separation voltage of 12kV, separation temperature of 20 ℃, sample injection pressure of 50mbar and sample injection time of 2 s. The baseline separation of the two amino acid enantiomers is realized, and the chiral covalent organic framework capillary electrochromatography open tubular column prepared by the embodiment has strong chiral resolution capability.
The above embodiment is only a preferred embodiment of the present invention, but it is not intended to limit the present invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, all the technical schemes obtained by adopting the equivalent substitution or equivalent transformation are within the protection scope of the invention.
Claims (7)
1. A preparation method of a capillary electrochromatography open tubular column based on chiral covalent organic framework materials is characterized by comprising the following steps:
1. sequentially flushing the capillary column with HCl solution, water and NaOH solution, sealing and placing the two ends of the capillary column for a period of time, flushing with water to neutrality, flushing with methanol, and drying with nitrogen;
2. the volume ratio is (60-50): injecting the mixed solution of the 3-aminopropyl triethoxysilane and the methanol in the step (40-50) into the capillary column treated in the step one, sealing two ends of the capillary column at 40-50 ℃ for reaction for 16-24 hours, amination the inner wall of the capillary, flushing with the methanol after the reaction is finished, and blowing nitrogen to dry;
3. the ratio of the 2- (4-hydroxyphenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine and the 1,3, 5-trialdehyde phloroglucinol is (1-3) according to the mass: 1 into an organic solvent I, and then adding the organic solvent I into the organic solvent I according to the mass ratio of 2- (4-hydroxyphenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine to the acid catalyst of 1: (0.05-0.1), adding an acid catalyst into the organic solvent I, uniformly mixing by ultrasonic, filling into the capillary column treated in the second step, reacting for 24-72 h by using a water bath at 75-90 ℃, flushing by methanol after the reaction is finished, and drying by nitrogen;
4. according to the ratio of the mono-6-O-p-toluenesulfonyl-beta-cyclodextrin to the 2- (4-hydroxyphenyl) -1H-phenanthro [9,10-d ] imidazole-5, 10-diamine in the step three, which is 1 to 3, according to the mass ratio of 1, adding the mono-6-O-p-toluenesulfonyl-beta-cyclodextrin into an organic solvent II, adding a certain amount of azodiisobutyronitrile, uniformly mixing by ultrasound, pouring into a capillary column treated in the step three, reacting for 12 to 24 hours by using a water bath at 60 to 80 ℃, flushing by using methanol after the reaction is finished, and drying by using nitrogen to obtain the capillary electrochromatography open tubular column based on chiral covalent organic framework materials.
2. The preparation method of the capillary electrochromatography open tubular column based on the chiral covalent organic framework material, which is disclosed in claim 1, is characterized in that the organic solvent I in the step three is one or the combination of any two of acetonitrile, N-dimethylformamide, ethyl acetate, N-butanol, o-dichlorobenzene and acetone.
3. The method for preparing a capillary electrochromatography open tubular column based on chiral covalent organic framework materials according to claim 1 or 2, wherein the acid catalyst in the third step is glacial acetic acid, diluted hydrochloric acid or trifluoroacetic acid.
4. The method for preparing a capillary electrochromatography open tubular column based on chiral covalent organic framework materials according to claim 1 or 2, wherein the organic solvent II in the fourth step is N, N-dimethylformamide, methanol, ethanol, acetone or dimethyl sulfoxide.
5. The method for preparing a capillary electrochromatography open tubular column based on chiral covalent organic framework material according to claim 1 or 2, wherein the ratio of the mass of azodiisobutyronitrile to the volume of the N, N-dimethylformamide solvent in the fourth step is (0.5-1) mg:1mL.
6. The application of the capillary electrochromatography open tubular column based on the chiral covalent organic framework material prepared by the method of claim 1, which is characterized in that the application is to split amino acid enantiomers by utilizing the capillary electrochromatography open tubular column based on the chiral covalent organic framework material by adopting a capillary electrochromatography technology.
7. The use of a capillary electrochromatography open tubular column based on chiral covalent organic framework material according to claim 6, characterized in that the step of splitting the amino acid enantiomer by means of a capillary electrochromatography open tubular column based on chiral covalent organic framework material is as follows:
and (3) operating the capillary electrochromatography open tubular column based on chiral covalent organic framework materials under electrochromatography operation conditions of different buffer solutions with pH value of=5, separation voltage of 12kV, separation temperature of 20 ℃, sample injection pressure of 50mbar and sample injection time of 2s to complete chiral resolution of D/L-histidine and D/L-lysine.
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| CN108181414A (en) * | 2017-12-25 | 2018-06-19 | 齐齐哈尔大学 | The preparation method and applications of chiral linkage capillary electric chromatogram open tubular column |
| US20210023528A1 (en) * | 2018-01-11 | 2021-01-28 | Nankai University | Preparation of chromatographic stationary phase having porous framework material as matrix for chiral separation |
| CN115518415A (en) * | 2022-10-08 | 2022-12-27 | 沈阳化工大学 | Capillary electrochromatography method for separating pantoprazole racemate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108181414A (en) * | 2017-12-25 | 2018-06-19 | 齐齐哈尔大学 | The preparation method and applications of chiral linkage capillary electric chromatogram open tubular column |
| US20210023528A1 (en) * | 2018-01-11 | 2021-01-28 | Nankai University | Preparation of chromatographic stationary phase having porous framework material as matrix for chiral separation |
| CN115518415A (en) * | 2022-10-08 | 2022-12-27 | 沈阳化工大学 | Capillary electrochromatography method for separating pantoprazole racemate |
Non-Patent Citations (1)
| Title |
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| LIDI GAO ET AL.: "A covalent organic framework for chiral capillary electrochromatography using a cyclodextrin mobile phase additive", 《CHIRALITY》, vol. 34, 31 December 2022 (2022-12-31), pages 537 - 549 * |
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