CN114504843B - Preparation method of capillary open-tube chromatographic column based on metal organic framework material - Google Patents
Preparation method of capillary open-tube chromatographic column based on metal organic framework material Download PDFInfo
- Publication number
- CN114504843B CN114504843B CN202111598127.4A CN202111598127A CN114504843B CN 114504843 B CN114504843 B CN 114504843B CN 202111598127 A CN202111598127 A CN 202111598127A CN 114504843 B CN114504843 B CN 114504843B
- Authority
- CN
- China
- Prior art keywords
- capillary
- tube
- framework material
- organic framework
- chromatographic column
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a capillary open-tube chromatographic column based on a metal organic framework material, which comprises the following steps: dissolving an organic ligand and an inorganic metal ion reagent in a solvent, uniformly mixing the mixture by ultrasonic to form a uniform and clear solution, injecting the solution into a carboxyl modified capillary column, sealing two ends of the capillary, carrying out a heat treatment bonding reaction, taking out the capillary after the reaction is finished, cutting off sealing parts at two ends, and flushing the sealing parts with methanol to obtain the capillary open-tube chromatographic column based on the metal organic framework material. The invention adopts an in-situ polymerization method to prepare the capillary tube open-tube chromatographic column based on the metal organic framework material, and has the advantages of high mechanical strength, difficult breakage, difficult bubble retention and the like because the metal organic framework material is directly bonded on the inner wall of the capillary tube.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis and analysis, and particularly relates to a preparation method of a capillary open-tube chromatographic column based on a metal organic framework material.
Background
Chirality is a natural property of compound molecules, and most of them are chiral from biomolecules such as amino acids, polysaccharides, proteins, and the like constituting living organisms to drugs for human use. Enantiomers of chiral compounds often have similar physicochemical structures, but often exhibit different activities in the fields of pharmacy, biology, etc. Therefore, the establishment of an efficient chiral separation analysis method has important research significance. Capillary electrochromatography is a novel efficient and rapid separation technique. The method is developed by neutralizing the advantages of high efficiency of capillary electrophoresis and high selectivity of high performance liquid chromatography, and has the advantages of high analysis speed, high column efficiency, low consumption of samples and solvents, and the like. The core of capillary electrochromatography is capillary electrochromatography column. Therefore, the preparation of the electrochromatography column with high column efficiency and good separation effect is the key point of research.
Capillary electrochromatography can be divided into three categories, depending on the form of the stationary phase present in the capillary: packed column electrochromatography, monolithic column electrochromatography and open tubular column electrochromatography. The preparation method of the open tubular column is simple, and the Joule heating effect, the bubble effect and the like can be eliminated simultaneously only by coating a layer of stationary phase on the inner wall of the capillary tube, so that the application field of capillary electrochromatography is further expanded. But due to its smaller size the column capacity is lower.
Since open column electrochromatography has the greatest drawbacks of being relatively small and low in column capacity, the key to preparing open columns is to increase the fixed surface area. The metal organic framework material is a microporous material formed by self-assembling metal ions and organic ligands through coordination bonds, and has the advantages of multiple structures, large specific surface area, regular pore channel structure, adjustable pore size, good solvent stability and the like. Due to the advantages, the metal organic framework material is introduced into the open-tube column electrochromatography, so that the mode of effectively increasing the surface area of the immobilized phase and the action sites of small molecules is adopted, and the chiral compound separation method has wide application prospect in the chiral compound separation field.
Disclosure of Invention
The invention aims to provide a preparation method of a capillary open-tube chromatographic column based on a metal organic framework material, which can be used for separating chiral compounds and solves the technical problems of low separation degree and low separation efficiency of chiral compounds separated by a capillary electrophoresis method in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a method for preparing a capillary open-tube chromatographic column based on a metal organic framework material, which comprises the following steps:
dissolving an organic ligand and an inorganic metal ion reagent with a molar ratio of 1 (1-6) in a solvent, uniformly mixing the mixture by ultrasonic to form a uniform and clear solution, injecting the solution into a carboxyl modified capillary column for 1-5 hours, sealing two ends of the capillary, performing a heat treatment bonding reaction, taking out the capillary after the reaction is finished, cutting off sealing parts at the two ends, and flushing the sealing parts with methanol for 0.5-1.5 hours to obtain the capillary open-tube chromatographic column based on the metal organic framework material.
The inorganic metal ion reagent is ZnCl 2 。
The solvent is methanol-water solution, and the volume ratio of methanol to water is 2:1.
The temperature of the heat treatment bonding reaction is 65-75 ℃ (preferably 70 ℃) and the time is 1-24 hours.
The preparation method of the organic ligand comprises the following steps:
quinine was dissolved in 10% strength H 2 SO 4 Wherein, the concentration of quinine is 0.1-1 g/mL (preferably 0.29 g/mL), a potassium permanganate aqueous solution with the concentration of 1-10% (preferably 5.1%) is added, the molar ratio of quinine to potassium permanganate is 1 (1.5-4), the reaction is carried out for 1-24 h under the condition of the temperature of 0 ℃, and the organic ligand is obtained through reflux, rotary evaporation to remove the solvent and recrystallization.
The solvent for the recrystallization of the organic ligand is as follows: ethanol water solution with volume ratio of 2:1.
The reflux temperature is 70-80 ℃ (preferably 70 ℃) for 0.8-2 hours (preferably 1 hour).
The preparation method of the carboxyl modified capillary column comprises the following steps:
pumping a methanol aqueous solution of 3-aminopropyl triethoxysilane with the concentration of 45-55% into the pretreated quartz capillary tube for 5-30 min, sealing the quartz capillary tube with rubber, and reacting for 1-24 h under the water bath condition with the temperature of 45-60 ℃ to finish amino modification;
pumping glutaraldehyde solution with the concentration of 1-3% and the pH of 11 into the column for 1-3 h, pumping potassium permanganate aqueous solution with the concentration of 0.05-0.15 mol/L into the column for 1-3 h, and flushing with ultrapure water for 1-3 h to finish carboxyl modification, thus obtaining the carboxyl modified capillary column.
The glutaraldehyde solution is prepared by adjusting the pH value through hydrochloric acid-water solution with the concentration of 1mol/L and sodium hydroxide-water solution with the concentration of 1 mol/L.
The method for treating the pretreated quartz capillary comprises the following steps:
the quartz capillary (75 mu m i.d. multiplied by 365 mu m o.d.) is sequentially washed for 0.5 to 1.5 hours by using sodium hydroxide aqueous solution with the concentration of 0.5 to 2mol/L, washed for 5 to 30 minutes by using ultrapure water, washed for 5 to 60 minutes by using hydrochloric acid solution with the concentration of 0.5 to 2mol/L, washed for 5 to 30 minutes by using ultrapure water, finally washed for 5 to 60 minutes by using methanol, dried by using nitrogen gas after being dried for 0.5 to 1.5 hours at the temperature of 95 to 105 ℃ to obtain the pretreated quartz capillary.
By adopting the technical scheme, the invention has the following advantages and beneficial effects:
the invention adopts an in-situ polymerization method to prepare the capillary tube open-tube chromatographic column based on the metal organic framework material, and has the advantages of high mechanical strength, difficult breakage, difficult bubble retention and the like because the metal organic framework material is directly bonded on the inner wall of the capillary tube. The stationary phase is directly used as a separation material, so that the capacity of the column is greatly increased, and the separation efficiency is effectively improved. The hydrophilicity and hydrophobicity of the capillary open-tube chromatographic column provided by the invention can be provided by the stationary phase, so that the separation of chiral compounds is facilitated. In the preparation process of the stationary phase, the adopted materials are low in price, the preparation conditions are easy to control, and the repeatability is good. The capillary open-tube chromatographic column material has good compatibility with biological samples, is particularly suitable for separation analysis of biological small molecular samples, and has wide application prospect in chiral compound separation and metabonomics research.
The invention realizes the separation of chiral dansyl amino acid enantiomer and chiral medicine with high efficiency and high separation degree.
Drawings
FIG. 1 is a schematic diagram showing the overall morphology of the capillary open-tube column prepared in example 1, as observed on a scanning electron microscope scale of 1 micron.
FIG. 2 is a schematic diagram showing a separation spectrum of chiral compounds in a capillary open-tube chromatographic column prepared in example 1, wherein in the left hand figure, 1 is dansyl chloride, 2 is L-dansyl phenylalanine, and 3 is D-dansyl phenylalanine; in the right figure, 1 is dansyl chloride, 4 is L-dansyl alanine, and 5 is D-dansyl alanine.
FIG. 3 is a schematic diagram showing the separation profile of chiral compounds in a capillary open-tube chromatographic column prepared in example 1, wherein in the left hand figure, 1 is dansyl chloride, 6 is L-dansyl serine, and 7 is D-dansyl serine; in the right figure, 1 is dansyl chloride, 8 is L-dansyl asparagine, and 9 is D-dansyl asparagine.
FIG. 4 is a schematic diagram showing a separation spectrum of chiral compounds in a capillary open-tube chromatographic column prepared in example 1, wherein in the left hand figure, 1 is dansyl chloride, 10 is L-dansyl threonine, and 11 is D-dansyl threonine; in the right figure, 1 is dansyl chloride, 12 is L-dansyl tyrosine, and 13 is D-dansyl tyrosine.
FIG. 5 is a schematic diagram showing the separation profile of chiral compounds in a capillary open-tube chromatographic column prepared in example 1, wherein in the left hand figure, 14 is thiourea, 15 is S-chlorphenamine and 16 is R-chlorphenamine; in the right figure, 14 is thiourea, 17 is S-ibuprofen, 18 is R-ibuprofen, and thiourea is a neutral marker.
FIG. 6 is a schematic representation of the separation profile of unmodified empty column versus dansyl-phenylalanine. Wherein 1 is dansyl chloride and 2 is dansyl phenylalanine.
Fig. 7 is a schematic view of the overall morphology of the metal-organic framework material of example 1 observed under a scanning electron microscope.
Fig. 8 is a schematic diagram of the results detected by the fourier transform infrared spectrometer of the metal organic framework material described in example 1.
Fig. 9 is a schematic diagram of nitrogen adsorption and desorption curves and pore size analysis of the capillary open-tube chromatographic column and unmodified hollow column based on the metal organic framework material prepared in example 1. The left figure is a capillary open tube column based on a metal organic framework material, and the right figure is an unmodified empty tube column.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
A preparation method of a capillary open-tube chromatographic column based on a metal organic framework material comprises the following steps:
first, pretreatment of a capillary:
2m feldspar capillaries (75 μm i.d.×365 μm o.d.) were rinsed sequentially with 1mol/L sodium hydroxide-water solution for 1h, with ultrapure water for 15min, with 1mol/L hydrochloric acid-water solution for 0.5h, with ultrapure water for 15min, finally with methanol for 0.5h, and then with nitrogen for blow-drying, and the quartz capillaries were placed in an oven and dried at 100℃for 1h.
Second, modification of functional groups
Pumping 50% methanol aqueous solution (volume ratio of APTES to methanol is 1:1) of 3-aminopropyl triethoxysilane (APTES) into the quartz capillary tube pretreated in the first step for 15min, sealing the quartz capillary tube with rubber, and reacting for 12h in a water bath at 55 ℃ to finish amino modification.
Adjusting the pH value of 2% glutaraldehyde-water solution to 11 through 1mol/L hydrochloric acid-water solution and 1mol/L sodium hydroxide-water solution, pumping into the column for 2h, pumping into 0.1mol/L potassium permanganate-water solution for 2h, and washing with ultrapure water for 1h to finish carboxyl modification, thereby obtaining a carboxyl modified capillary column;
third step, preparation of organic ligand
8g quinine was dissolved in 27.2mL H at a concentration of 10% 2 SO 4 In the method, 10.23g of potassium permanganate is dissolved in 200mL of ultrapure water to prepare a potassium permanganate solution, the molar ratio of quinine to potassium permanganate is 1:2.6, the potassium permanganate solution is added into the sulfuric acid solution to react for 12 hours at the temperature of 0 ℃, the solution is condensed and refluxed for 1 hour at the temperature of 70 ℃, the solvent is removed by rotary evaporation, and 4.2g of organic ligand is prepared by recrystallization with an ethanol water solution with the volume ratio of 2:1.
Fourth step, preparation of open-tube chromatographic column
5mg of the organic ligand prepared in the third step and 5mg of ZnCl are reacted 2 (organic ligand and ZnCl) 2 Is 1:2.5) in 1.5mL of methanol-water solution (volume ratio of methanol to water is 2: 1) Uniformly mixing for 1min by ultrasonic to form uniform and clear solution, injecting into a carboxyl modified capillary column prepared in the second step for 2h, sealing two ends of the capillary column, placing into a constant-temperature water bath kettle, performing in-situ reaction for 24h at the temperature of 70 ℃, taking out the capillary column after the reaction is finished, cutting off sealing parts at two ends, connecting to a nitrogen device, flushing with methanol for 1h, and obtaining the capillary open-tube chromatographic column based on the metal organic framework material, which is recorded as { (HQA) (ZnCl) 2 )(2.5H 2 O)} n And (5) a column.
Characterization of the capillary open tube column prepared in example 1 by scanning electron microscopy, FIG. 1 is a schematic diagram showing the overall morphology of the capillary open tube column prepared in example 1 observed under a scanning electron microscope (75 μm inner diameter) 1 μm scale, showing that the inner surface of the capillary column has obvious protrusions, indicating success in purifying { (HQA) (ZnCl) 2 )(2.5H 2 O)} n Bonded to the capillary inner surface.
The prepared capillary open-tube chromatographic column was mounted on a capillary electrophoresis apparatus (CE, beijing Hua Yangli Min apparatus CL1030, china) for capillary electrochromatography separation, and D/L-phenylalanine was successfully separated. Separation conditions: methanol/10 mM phosphate (ph=7) =10/90, sample injection time: 5s, separation temperature: room temperature.
The obtained chromatograms are shown in fig. 2 to 5. FIG. 2 is a schematic diagram of the separation spectrum of chiral compounds in the capillary open-tube column prepared in example 1. In the left graph, 1 is dansyl chloride, 2 is L-dansyl phenylalanine, and 3 is D-dansyl phenylalanine; in the right figure, 1 is dansyl chloride, 4 is L-dansyl alanine, and 5 is D-dansyl alanine.
FIG. 3 is a schematic diagram showing the separation profile of chiral compounds in a capillary open-tube chromatographic column prepared in example 1, wherein in the left hand figure, 1 is dansyl chloride, 6 is L-dansyl serine, and 7 is D-dansyl serine; in the right figure, 1 is dansyl chloride, 8 is L-dansyl asparagine, and 9 is D-dansyl asparagine.
FIG. 4 is a schematic diagram showing a separation spectrum of chiral compounds in a capillary open-tube chromatographic column prepared in example 1, wherein in the left hand figure, 1 is dansyl chloride, 10 is L-dansyl threonine, and 11 is D-dansyl threonine; in the right figure, 1 is dansyl chloride, 12 is L-dansyl tyrosine, and 13 is D-dansyl tyrosine.
FIG. 5 is a schematic diagram showing the separation profile of chiral compounds in a capillary open-tube chromatographic column prepared in example 1, wherein in the left hand figure, 14 is thiourea, 15 is S-chlorphenamine and 16 is R-chlorphenamine; in the right graph, 14 is thiourea, 17 is S-ibuprofen, 18 is R-ibuprofen, and thiourea is a neutral marker
The peak time of all the dansyl chlorides in fig. 2 to 5 is basically consistent, which indicates that the capillary column prepared in example 1 has better stability.
FIG. 6 is a schematic representation of the separation profile of unmodified empty column versus dansyl-phenylalanine. Wherein 1 is dansyl chloride and 2 is dansyl-phenylalanine. The blank column of FIG. 6 was then combined with the { (HQA) (ZnCl) column of FIG. 1 2 )(2.5H 2 O)} n Comparison of the columns to D/L-dansyl phenylalanine can be seen with { (HQA) (ZnCl 2 )(2.5H 2 O)} n The column can realize the separation of enantiomers.
Fig. 7 is a schematic view of the overall morphology of the metal-organic framework material of example 1 observed under a scanning electron microscope.
Fig. 8 is a schematic diagram of the results detected by the fourier transform infrared spectrometer of the metal organic framework material described in example 1.
Table 1 shows the separation of chiral amino acids and chiral drugs from the open capillary column and the empty column prepared in example 1, wherein t 1 And t 2 Retention time of two monomers after separation of chiral compound, R s The degree of separation between the monomers after separation of the chiral compound is defined as α, and the selectivity factor. As can be seen from the table, the unmodified empty column has no resolution of both the dansyl amino acid and the chiral drug, but { (HQA) (ZnCl) 2 )(2.5H 2 O)} n The column was then able to effect enantiomer separation, indicating { (HQA) (ZnCl) 2 )(2.5H 2 O)} n The modified capillary column has good separation efficiency and separation capacity for chiral compounds, and the theoretical plate number is 35000.
TABLE 1 resolution data for chiral compounds
Table 2 shows the reproducibility data of the column:
the repeatability test method comprises the following steps: the repeatability of the chromatographic column was determined using dansyl phenylalanine as sample, separation conditions: methanol/10 mM phosphate (ph=7) =1/9, sample injection time: 5s, separation voltage: 15kV, separation temperature: room temperature. The data in the table indicate that { (HQA) (ZnCl) was prepared 2 )(2.5H 2 O)} n The column has better repeatability.
TABLE 2
| Dansyl-phenylalanine | t 1 (RSD％) | t 2 (RSD％) | ɑ(RSD％) | R s (RSD％) |
| Batch room (n=5) | 1.700 | 2.000 | 1.400 | 4.400 |
| Daytime (n=5) | 1.600 | 2.300 | 1.700 | 4.700 |
| Inter-column (n=3) | 3.400 | 4.000 | 1.600 | 7.600 |
The test method of the nitrogen adsorption and desorption curve comprises the following steps: introducing adsorbate gas (N) into the sample tube at low temperature (liquid nitrogen bath) 2 ) Directly measuring adsorption partial pressure by controlling the balance pressure in the sample tube, and obtaining the adsorption quantity of the partial pressure point by a gas state equation; gradually adding the adsorbate gas to increase the adsorption equilibrium pressure to obtain an adsorption isotherm; and gradually pumping out the adsorbate gas to reduce the adsorption equilibrium pressure, so as to obtain a desorption isotherm.
Fig. 9 is a schematic diagram of nitrogen adsorption and desorption curves and pore size analysis of the capillary open-tube chromatographic column and unmodified hollow column based on the metal organic framework material prepared in example 1. The left drawing shows a capillary open-tube chromatographic column based on a metal organic framework material, the right drawing shows an unmodified hollow column, and the specific surface area of the invention is 78.801m 2 Per gram, is far greater than the specific surface area 33.809m of the hollow tubular column 2 /g。
Example 2
A preparation method of a capillary open-tube chromatographic column based on a metal organic framework material comprises the following steps:
first, pretreatment of a capillary:
2m feldspar capillaries (75 μm i.d.×365 μm o.d.) were rinsed with 1.5mol/L sodium hydroxide-water solution in sequence for 0.5h, with ultrapure water for 15min, with 1.5mol/L hydrochloric acid-water solution for 0.25h, with ultrapure water for 15min, finally with methanol for 0.5h, and then dried with nitrogen, and the quartz capillaries were dried in an oven at 100℃for 1h.
In the preparation method of the organic ligand in the third step, the molar ratio of quinine to potassium permanganate is 1:1.5, and other method steps are the same as in example 1.
The electroosmotic flow measuring method comprises the following steps: measuring electroosmotic flow of a chromatographic column and an empty column by taking thiourea as a neutral marker, and separating under the conditions: methanol/10 mM phosphate (ph=7) =1/9, sample injection time: 5s, separation voltage: 17.5kV, separation temperature: room temperature.
Table 3 shows electroosmotic flow data of the column and empty column obtained in example 2, which indicates successful synthesis of { (HQA) (ZnCl) 2 )(2.5H 2 O)} n And (5) a column.
TABLE 3 Table 3
| {(HQA)(ZnCl 2 )(2.5H 2 O)} n Column | Hollow pipe column | |
| pH | μ(10 -4 cm 2 V -1 s -1 ) | μ(10 -4 cm 2 V -1 s -1 ) |
| 5 | 1.510156256 | 1.854359084 |
| 6 | 2.496450829 | 2.772044433 |
| 7 | 3.155845538 | 3.964273774 |
| 8 | 4.443873344 | 5.302362426 |
| 9 | 4.956585092 | 5.609396753 |
Example 3
A preparation method of a capillary open-tube chromatographic column based on a metal organic framework material comprises the following steps:
first, pretreatment of a capillary:
2m quartz capillary (75 μm i.d.×365 μm o.d.) was rinsed with 2mol/L sodium hydroxide-water solution for 0.5h, with ultrapure water for 15min, with 2mol/L hydrochloric acid-water solution for 0.25h, with ultrapure water for 15min, with methanol for 0.5h, and then dried with nitrogen, and the quartz capillary was dried in an oven at 100deg.C for 1h.
In the preparation method of the organic ligand in the third step, the molar ratio of quinine to potassium permanganate is 1:1.5, and other method steps are the same as in example 1.
The electroosmotic flow measuring method comprises the following steps: measuring electroosmotic flow of a chromatographic column and an empty column by taking thiourea as a neutral marker, and separating under the conditions: methanol/10 mM phosphate (ph=7) =1/9, sample injection time: 5s, separation voltage: 17.5kV, separation temperature: room temperature.
Table 4 shows examples3 electroosmotic flow of the resulting column and empty column, data in the table indicate successful synthesis { (HQA) (ZnCl) 2 )(2.5H 2 O)} n And (5) a column.
TABLE 4 Table 4
| {(HQA)(ZnCl 2 )(2.5H 2 O)} n Column | Hollow pipe column | |
| pH | μ(10 -4 cm 2 V -1 s -1 ) | μ(10 -4 cm 2 V -1 s -1 ) |
| 5 | 1.572398533 | 1.852968098 |
| 6 | 2.250786419 | 2.697870957 |
| 7 | 3.334217102 | 4.183299061 |
| 8 | 4.623749359 | 5.276877106 |
| 9 | 4.955342217 | 5.911428287 |
Compared with the prior publications, the capillary tube has the advantages of high separation degree of chiral compounds, multiple separation types and good separation effect.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (4)
1. The preparation method of the capillary open-tube chromatographic column based on the metal organic framework material is characterized by comprising the following steps of: dissolving an organic ligand and an inorganic metal ion reagent in a molar ratio of 1:2.5 in a solvent, uniformly mixing the mixture by ultrasonic to form a uniform and clear solution, injecting the solution into a carboxyl modified capillary column for 1-5 hours, sealing two ends of the capillary, performing a heat treatment bonding reaction, taking out the capillary after the reaction is finished, cutting off sealing parts at the two ends of the capillary, and flushing the sealing parts with methanol for 0.5-1.5 hours to obtain the capillary open-tube chromatographic column based on the metal organic framework material;
the inorganic metal ion reagent is ZnCl 2 ；
The solvent is methanol-water solution, and the volume ratio of methanol to water is 2:1;
the temperature of the heat treatment bonding reaction is 65-75 ℃ and the time is 1-24 h;
the preparation method of the organic ligand comprises the following steps:
quinine was dissolved in 10% strength H 2 SO 4 Wherein, the concentration of quinine is 0.1-1 g/mL, 1-10% potassium permanganate aqueous solution is added, the mol ratio of quinine to potassium permanganate is 1 (1.5-4), the reaction is carried out for 1-24 h under the condition of 0 ℃, the reflux is carried out, the solvent is removed by rotary evaporation, and the organic ligand is obtained by recrystallization;
the preparation method of the carboxyl modified capillary column comprises the following steps:
pumping a methanol aqueous solution of 3-aminopropyl triethoxysilane with the concentration of 45-55% into the pretreated quartz capillary tube for 5-30 min, sealing the quartz capillary tube with rubber, and reacting for 1-24 h under the water bath condition with the temperature of 45-60 ℃ to finish amino modification;
pumping glutaraldehyde solution with the concentration of 1-3% and the pH value of 11 into the quartz capillary for 1-3 hours, pumping potassium permanganate aqueous solution with the concentration of 0.05-0.15 mol/L into the quartz capillary for 1-3 hours, and flushing the quartz capillary for 1-3 hours with ultrapure water to finish carboxyl modification, thus obtaining a carboxyl modified capillary column;
the method for treating the pretreated quartz capillary comprises the following steps:
washing the quartz capillary tube with 0.5-2 mol/L sodium hydroxide aqueous solution for 0.5-1.5 h, washing with ultrapure water for 5-30 min, washing with 0.5-2 mol/L hydrochloric acid solution for 5-60 min, washing with ultrapure water for 5-30 min, washing with methanol for 5-60 min, drying with nitrogen for 0.5-1.5 h at 95-105 ℃ to obtain the pretreated quartz capillary tube.
2. The method for preparing a capillary open tube chromatographic column based on metal organic framework material according to claim 1, wherein the solvent for recrystallization of the organic ligand is: ethanol water solution with volume ratio of 2:1.
3. The method for preparing a capillary open-tube chromatographic column based on a metal organic framework material according to claim 1, wherein the reflux temperature is 70-80 ℃ for 0.8-2 h.
4. The method for preparing a capillary open-tube chromatographic column based on metal organic framework material according to claim 1, wherein the glutaraldehyde solution is pH-adjusted by 1mol/L hydrochloric acid-water solution and 1mol/L sodium hydroxide-water solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111598127.4A CN114504843B (en) | 2021-12-24 | 2021-12-24 | Preparation method of capillary open-tube chromatographic column based on metal organic framework material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111598127.4A CN114504843B (en) | 2021-12-24 | 2021-12-24 | Preparation method of capillary open-tube chromatographic column based on metal organic framework material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114504843A CN114504843A (en) | 2022-05-17 |
| CN114504843B true CN114504843B (en) | 2023-05-02 |
Family
ID=81548161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111598127.4A Active CN114504843B (en) | 2021-12-24 | 2021-12-24 | Preparation method of capillary open-tube chromatographic column based on metal organic framework material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114504843B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005507863A (en) * | 2001-07-31 | 2005-03-24 | ブランデイス ユニヴァーシティー | Kinetic resolution of chiral 2- and 3-substituted carboxylic acids. |
| CN103331151A (en) * | 2013-07-04 | 2013-10-02 | 山东师范大学 | Non-interpenetrating chiral MOF stationary phase, its preparation method and application in enantiomer separation in HPLC |
| CN107649105A (en) * | 2017-09-19 | 2018-02-02 | 福州大学 | A kind of quinine immobilization ionic liquid multi-mode capillary integral post and preparation method thereof |
| CN111825849A (en) * | 2020-06-05 | 2020-10-27 | 上海大学 | Metal-organic framework compound containing carbamido and preparation method thereof |
| BG113194A (en) * | 2020-07-22 | 2020-11-16 | Виктор АТАНАСОВ | Metal-organic zinc complexes with ligand chloroquine, hydroxychloroquine and other quinine derivatives, use and method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6616825B1 (en) * | 2000-08-23 | 2003-09-09 | The Regents Of The University Of California | Electrochromatographic device for use in enantioselective separation, and enantioselective separation medium for use therein |
| CN101890305B (en) * | 2010-04-01 | 2013-04-17 | 大连理工大学 | Method for preparing metallic organic frame films |
| CN102220626B (en) * | 2011-05-25 | 2013-05-15 | 大连理工大学 | Method for preparing nano zeolitic metal-organic frameworks crystal through dynamic crystallization |
| US9078922B2 (en) * | 2011-10-13 | 2015-07-14 | The Regents Of The University Of California | Metal-organic frameworks with exceptionally large pore aperatures |
| AU2013296146B2 (en) * | 2012-07-26 | 2018-04-12 | Commonwealth Scientific And Industrial Research Organisation | Gas separation processes |
| CN103623795B (en) * | 2013-12-06 | 2015-06-10 | 武汉大学 | Preparation method for open tubular capillary based on metal-organic framework material |
| JP6764778B2 (en) * | 2016-12-20 | 2020-10-07 | 花王株式会社 | Chiral amino acid separation method |
| CN109569026B (en) * | 2018-01-11 | 2021-12-03 | 南开大学 | Preparation of chromatographic stationary phase with porous frame material as matrix for chiral separation |
| CN111068631B (en) * | 2018-10-22 | 2021-05-25 | 中国科学院大连化学物理研究所 | Preparation and application of cinchona alkaloid functionalized chiral hybrid monolithic stationary phase |
| CN111001187B (en) * | 2019-12-13 | 2021-02-19 | 武汉大学 | Preparation method of novel cyclodextrin metal organic framework material chiral capillary electrochromatography open tubular column |
| CN111704536A (en) * | 2020-06-15 | 2020-09-25 | 上海大学 | Natural product Loureirin B analogue, preparation method and application thereof |
-
2021
- 2021-12-24 CN CN202111598127.4A patent/CN114504843B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005507863A (en) * | 2001-07-31 | 2005-03-24 | ブランデイス ユニヴァーシティー | Kinetic resolution of chiral 2- and 3-substituted carboxylic acids. |
| CN103331151A (en) * | 2013-07-04 | 2013-10-02 | 山东师范大学 | Non-interpenetrating chiral MOF stationary phase, its preparation method and application in enantiomer separation in HPLC |
| CN107649105A (en) * | 2017-09-19 | 2018-02-02 | 福州大学 | A kind of quinine immobilization ionic liquid multi-mode capillary integral post and preparation method thereof |
| CN111825849A (en) * | 2020-06-05 | 2020-10-27 | 上海大学 | Metal-organic framework compound containing carbamido and preparation method thereof |
| BG113194A (en) * | 2020-07-22 | 2020-11-16 | Виктор АТАНАСОВ | Metal-organic zinc complexes with ligand chloroquine, hydroxychloroquine and other quinine derivatives, use and method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黎艳,刘虎威.毛细管电色谱手性分离进展.色谱.2000,第18卷(第03期),212-215页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114504843A (en) | 2022-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ansari et al. | Recent progress, challenges and trends in trace determination of drug analysis using molecularly imprinted solid-phase microextraction technology | |
| Fanali | Enantiomers separation by capillary electrochromatography | |
| Wang et al. | A room temperature ionic liquid (RTIL)‐mediated, non‐hydrolytic sol–gel methodology to prepare molecularly imprinted, silica‐based hybrid monoliths for chiral separation | |
| Zheng et al. | Recent developments and applications of molecularly imprinted monolithic column for HPLC and CEC | |
| CN101590394B (en) | Preparation method and use of molecular imprinting-absorbing extraction stirring rod | |
| Ding et al. | A metal organic framework-functionalized monolithic column for enantioseparation of six basic chiral drugs by capillary electrochromatography | |
| CN111307968B (en) | Flower ball-shaped covalent organic framework material and preparation and application thereof | |
| CN112316929A (en) | Covalent organic framework material, solid-phase microextraction probe, and preparation method and application thereof | |
| Hu et al. | Boronate-affinity hollow molecularly imprinted polymers for the selective extraction of nucleosides | |
| CN109589937A (en) | A kind of preparation method and applications of the solid-phase micro-extraction fibre of self assembling multilayer porphyrin organic frame compound | |
| Yuan et al. | Enantiomeric separation by capillary electrochromatography on a sulfated poly β-cyclodextrin modified silica-based monolith | |
| Ma et al. | Gold nanoparticles-functionalized monolithic column for enantioseparation of eight basic chiral drugs by capillary electrochromatography | |
| CN110479222B (en) | Preparation method of Zr (IV) -2-amino terephthalic acid complex hybrid polymer monolithic column and application thereof in solid phase micro-extraction | |
| CN109655569B (en) | SPME-GC detection method for amphetamine substances in urine | |
| Ding et al. | New approach for chiral separation: from polysaccharide-based materials to chirality-responsive polymers | |
| CN103599755B (en) | Phenolethanolamine A molecular engram film and preparation method thereof and application | |
| CN114504843B (en) | Preparation method of capillary open-tube chromatographic column based on metal organic framework material | |
| CN109158086B (en) | Method for ultrasensitively analyzing trace polybrominated diphenyl ethers in water | |
| CN1215329C (en) | Calixarene bonded silica gel immobile phase preparing process | |
| CN102169109A (en) | Method for preparing estrogen substitution template molecular imprinting solid phase micro extraction head | |
| CN112295552B (en) | Hierarchical pore UiO-66 solid-phase micro-extraction fiber prepared by in-situ etching method and application thereof | |
| CN110485165B (en) | Preparation and application of functionalized polyhedral oligomeric silsesquioxane modified polymer composite coating with specific enrichment function | |
| CN109771988B (en) | Diethyl phthalate solid-phase micro-extraction method based on molecular imprinting technology | |
| CN103990298B (en) | A kind of preparation method of surface and hydrophilic outer macropore organic-inorganic hybridization monolithic column | |
| CN113774447B (en) | Porphyrin-based covalent organic framework solid-phase microextraction coating prepared by one-step electrodeposition and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |