CN103331151A - Non-interpenetrating chiral MOF stationary phase, its preparation method and application in enantiomer separation in HPLC - Google Patents
Non-interpenetrating chiral MOF stationary phase, its preparation method and application in enantiomer separation in HPLC Download PDFInfo
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Abstract
The invention relates to a non-interpenetrating chiral MOF (metal organic framework) stationary phase, its preparation method and application in enantiomer separation in HPLC (high-performance liquid chromatography). The stationary phase is a non-interpenetrating chiral three-dimensional porous framework complex with a structural formula as {[ZnL].H2O}n. An asymmetric structural unit {[ZnL].H2O} of the complex is composed of a Zn<2+>, an L ligand and a guest water molecule. The L ligand is -NH- containing chiral pyridine carboxylic acid, its chemical composition is [(N-(4-pyridylmethyl)-L-leucine.HBr)], and its molecular formula is C12H19BrN2O2. Chiral amino acid and 4-pyridylaldehyde are selected as raw materials to synthesize the-NH- containing pyridine carboxylic acid chiral ligand by a one-step process. The ligand and zinc acetate are adopted as raw materials to undergo room temperature diffusion so as to obtain the MOF stationary phase. The material provided in the invention has uniform chiral helical channel, uniform aperture and orifice, and can be used for separation of chiral drugs and other enantiomers. The separation is selectively dependent on the size of a separated enantiomer molecular size, but is not dependent on the functional group of the separated enantiomer. Thus, the non-interpenetrating chiral MOF stationary phase has the characteristics of traditional zeolite molecular sieve separation.
Description
Technical field
The present invention relates to fixedly phase and preparation method thereof and splitting the application of enantiomer of a kind of optical homochiral metal organic frame thing (MOF), belong to technical fields such as metallo-organic compound, material are synthetic, analytical chemistry.
Background technology
Enantiomter refers in kind and mirror image (mirror images) relation each other, but two stereoisomers that can not be overlapping fully are called for short enantiomer, have another name called optical isomeric compound or mirror image isomer.Corresponding molecule is called chiral molecules, and corresponding compound is called chipal compounds.
Enantiomer has significant performance difference in biologically active, pharmacology and toxicology, enantiomer as chiral drug, usually show different physiologically actives, wherein a kind of have a response characteristic that stimulates or suppress certain function, and another kind of do not have or more weak or have opposite response characteristic, or body is had side effects even toxicity.According to statistics, in the new drug of whole world listing, medicine with chirality activity accounts for 60%, in the listed 2050 kinds of medicines of U.S.'s pharmaceutical drug substance noun dictionary, contain more than one chiral centre in nearly half drug molecule, nearly more than 400 kinds of medicines are taken with racemic modification or diastereo-isomerism form.In the 500 kinds of situation of selling well medicines in the whole world in 2002, chiral drug reaches 289 kinds, accounts for 59% of whole drug ratios.World's chiral drug total sales volume had reached 2,500 hundred million dollars in 2010.Given this, various countries pharmaceutical control and administration department is defined in when declaring the new drug with chirality, need report pharmacology, toxicology, the pharmacokinetics data of each enantiomer simultaneously, in addition, the fractionation of enantiomer also is one of clinical medical difficult problem always, fields such as pharmacology, chemistry, biotechnology, chemical industry also increase day by day to the single enantiomer demand, and therefore, the fractionation of enantiomer and enantiomer analysis on Content thereof are one of important tasks in this field.
The chromatogram Split Method is the most commonly used in chiral resolution or the enantiomer disassemble technique, development method the most fast, comprises gas chromatography, liquid chromatography, thin-layer chromatography chromatography etc.Wherein, as high performance liquid chromatography (HPLC) method of chromatographic stationary phase, have characteristics such as, separating effect height applied widely to sample with chiral stationary phase.Nearly two during the last ten years, the HPLC chiral resolution has obtained rapidly development, and the chiral stationary phase of numerous types (CSPs) is as brush type, polymer-type, polysaccharide derivates type, ligand exchange type, big lopps and protein-based etc., be synthesized in succession, and be applied to separate dissimilar chipal compounds.But for certain type chiral column, only a kind of or several chipal compounds are had the chiral resolution ability, still not as anti-phase C18 post, numerous sample separation is had universality widely.In addition, have pore structure and the size of higher specific surface area, homogeneous, the selective dependence of fractionation is the aperture and the fixing preparation mutually of the chirality zeolite molecular sieve that splits molecular dimension of phase fixedly, is still keeping and is challenging.
Chirality MOF is the novel porous class sorbing material of a class, it is the advanced subject of current chemical research, chirality MOF has the pore structure of higher specific surface area, homogeneous, can carry out controlled synthesizing by selecting suitable metal or part, or by the modification of hole dimension and hole wall being carried out the modification of framework, therefore, this framework thing raw material that are a kind of potentialization of chromatogram chiral separation.
Summary of the invention
The purpose of this invention is to provide a kind of fixedly phase and preparation method thereof and in HPLC, split the application of enantiomer of IPN chirality MOF of not having, should fix the 3D porous framework that have homochiral mutually and not have IPN, fractionation to chiral drug and other enantiomer depends on the size that is split the enantiomer molecule, and does not rely on the functional group that is split enantiomer.
The technical scheme that the present invention takes is:
A kind of no IPN chirality MOF is phase fixedly, and it is that structural formula is { [ZnL] H
2The three-dimensional porous frame complex of non-IPN chirality of O}n; An its asymmetric construction unit { [ZnL] H
2O} is by a Zn
2+, a L part and an object hydrone form; The L part is to contain-the chiral pyridyl carboxylic acid of NH-, and its chemical composition is [(N-(4-picolyl)-L-leucine HBr)], and molecular formula is C
12H
19BrN
2O
2The three-dimensional porous frame complex of described non-IPN chirality has the chiral helical passage of homogeneous, and this chiral helical passage has
Aperture and aperture, if consider van der Waals radius, have
Duct and aperture, is occupied by object water in the helical duct.
Described no IPN chirality MOF is phase fixedly, and its molecular formula is C
12H
19N
2O
3ZnBr, wherein the mass fraction of C is that the mass fraction of 37.48%, H is that the mass fraction of 4.98%, N is 7.28%.
A kind of do not have a fixedly preparation method of phase of IPN chirality MOF, comprises that step is as follows:
(1) Xiang Shuizhong adds the mixed liquor of L-leucine, sodium carbonate, 4-aldehyde radical pyridine and methyl alcohol successively, stirs 1-3h under the room temperature; The ice bath cooling slowly adds sodium borohydride aqueous solution again, continues to stir 0.5-1.5h; Being acidified to pH with hydrobromic acid is 3-6, continues to stir 1-3h; Then, decompression distillation is to solid-state; With methanol extraction repeatedly, filter, filtrate is revolved steaming, make chiral ligand l – HL;
(2) in secondary ion water, add step (1) synthetic chiral ligand l-HL, zinc acetate, be placed in the small beaker, and small beaker put into the large beaker that fills methyl alcohol, sealing, at room temperature spread 2-3d, with in the small beaker the mixed liquor of crystallization filter, and the crystal that leaches with the methanol aqueous solution washing respectively repeatedly, makes chirality MOF{[ZnL] H
2O}n.
Fixedly among the preparation method of phase, the mass ratio of the described water of step (1), L-leucine, sodium carbonate, 4-aldehyde radical pyridine, sodium borohydride aqueous solution is 30-50:1.0-3.0:0.5-1.5:1.0-3.0:5-15 to above-mentioned no IPN chirality MOF; 4-aldehyde radical pyridine concentration is 0.2g/mL in the mixed liquor of 4-aldehyde radical pyridine and methyl alcohol; The mass concentration of sodium borohydride aqueous solution is 7%-15%.
Described chiral ligand l-HL, its chemical composition is [(N-(4-picolyl)-L-leucine HBr)], molecular formula is C
12H
19BrN
2O
2, wherein the mass fraction of C is 47.54%; The mass fraction 6.32% of H; The mass fraction 9.24% of N.
Among the above-mentioned preparation method, the mass ratio of the described secondary ion water of step (2), chiral ligand l-HL, zinc acetate is 8-10:0.3-0.5:0.15-0.35.The volume ratio of described methanol aqueous solution methyl alcohol and water is 0.5-1.5:1.
{ [ZnL] H that makes
2O}n, its lattice exists with P61 chirality space group, is the 3D porous framework of non-IPN; Its asymmetric construction unit contains a Zn
2+, a L part, a Br-and an object water; Its 1D chiral helical passage is occupied by object water, has
Aperture and aperture, if consider van der Waals radius, have
Duct and aperture; Its
Symbol is 8
3Its heat endurance reaches 270 ℃; This homochiral MOF is water insoluble, ethanol, methyl alcohol, oxolane, dimethyl formamide and dimethyl sulfoxide (DMSO).
The fixing application that in HPLC, splits drug enantiomer or other enantiomer as chromatographic stationary mutually of above-mentioned no IPN chirality MOF.Described enantiomer, the minimum power size of its molecule less than
What split selectively depends on by the size of fractionation enantiomer molecule.
Application process is: with chirality MOF{[ZnL] H
2O}n activates at 35-60 ℃ of vacuum drying 18-24h, joins in the methyl alcohol suspension of making [ZnL] n then, and the pressure of this suspension with 5000psi is pressed in the stainless steel chromatogram post; Mixture with cyclohexane and isopropyl alcohol is the phase that flows, and will treat that the branch sample crosses post.
The concentration of the suspension of described [ZnL] n is 1g/mL.
The volume ratio of described cyclohexane and isopropyl alcohol is 100:1-10.
Described its internal diameter of stainless steel chromatogram post is 4.6mm, length 100-200mm.
More than preparation is raw materials used all can buy from chemical reagents corporation.
Compared with prior art, the present invention does not have fixedly phase of IPN chirality MOF, and its outstanding feature is:
(1) selecting chiral amino acid and 4-pyridine carboxaldehyde for use is raw material, and a step process has synthesized the picolinic acid chiral ligand of a kind of containing-NH-, is raw material with this part and zinc acetate, and the room temperature diffusion has made the homochiral MOF that a kind of 3D of having does not have IPN.Raw material is cheap and easy to get, and synthesis technique is simple, and mild condition is easy to operate.
(2) described homochiral MOF has chiral helical passage, the homogeneous of homogeneous
Aperture and aperture (consider to have van der Waals radius
Duct and aperture), this is for splitting medicine as the chiral stationary phase of HPLC and other enantiomer is laid a good foundation.
(3) the HPLC chiral stationary phase of this homochiral MOF preparation, be used for the fractionation of chiral drug and other enantiomer, it splits and selectively depends on the size that is split the enantiomer molecule, and does not rely on the functional group that is split enantiomer, has the feature that traditional zeolite molecular sieve separates.
Description of drawings
Fig. 1 is the crystal structure figure of embodiment 8 chirality MOF; Wherein a is the perspective view of chiral helical passage, and b is the axial perspective view of c, and c is the accumulation graph of chirality MOF;
Fig. 2 schemes for the XRD of the MOF crystal that the present invention makes;
Fig. 3 is the HPLC figure that embodiment 12 chirality MOF chromatographic stationary split brufen mutually;
Fig. 4 is the HPLC figure that embodiment 13 chirality MOF chromatographic stationary split phenylpropanol mutually;
Fig. 5 is the HPLC figure that embodiment 14 chirality MOF chromatographic stationary split phenyl ethylamine mutually.
The specific embodiment
In order to make those skilled in the art person better understand the present invention program, the present invention is described in further detail below in conjunction with drawings and Examples.
Embodiment 1
Add the mixed liquor of L-leucine 1.0g, sodium carbonate 0.5g, 4-aldehyde radical pyridine 1.0g and methyl alcohol 5mL in the water of 30mL successively, stir 1h under the room temperature; The ice bath cooling slowly adds sodium borohydride aqueous solution 5g again, continues to stir 0.5h; Being acidified to pH with hydrobromic acid is 3, continues to stir 1h; Then, decompression distillation is to solid-state; Use the methanol extraction 3 times of 10mL respectively, filter, filtrate is revolved steaming, make chiral ligand l-HL; Described sodium borohydride aqueous solution, the mass fraction of sodium borohydride are 7%.
In the secondary ion water of 10mL, add synthetic chiral ligand l-HL0.4g, zinc acetate 0.25g, be placed in the small beaker, and small beaker is put into the large beaker that fills 50mL methyl alcohol, sealing, at room temperature spread 2.5d, with in the small beaker the mixed liquor of crystallization filter, and wash the crystal that leaches repeatedly with the methanol aqueous solution of 7.5mL respectively, make chirality MOF{[ZnL] H
2O}n; Described methanol aqueous solution, the volume ratio of methyl alcohol and water are 1.0:1.
Add the mixed liquor of L-leucine 1.5g, sodium carbonate 1.0g, 4-aldehyde radical pyridine 2.0g and methyl alcohol 10mL in the water of 40mL successively, stir 2h under the room temperature; The ice bath cooling slowly adds sodium borohydride aqueous solution 10g again, continues to stir 1h; Being acidified to pH with hydrobromic acid is 4.5, continues to stir 2h; Then, decompression distillation is to solid-state; Use the methanol extraction 3 times of 20mL respectively, filter, filtrate is revolved steaming, make chiral ligand l-HL; Described sodium borohydride aqueous solution, the mass fraction of sodium borohydride are 11%.
In the secondary ion water of 10mL, add synthetic chiral ligand l-HL0.4g, zinc acetate 0.25g, be placed in the small beaker, and small beaker is put into the large beaker that fills 50mL methyl alcohol, sealing, at room temperature spread 2.5d, with in the small beaker the mixed liquor of crystallization filter, and wash the crystal that leaches repeatedly with the methanol aqueous solution of 7.5mL respectively, make chirality MOF{[ZnL] H
2O}n; Described methanol aqueous solution, the volume ratio of methyl alcohol and water are 1.0:1.
Embodiment 3
Add the mixed liquor of L-leucine 3.0g, sodium carbonate 1.5g, 4-aldehyde radical pyridine 3.0g and methyl alcohol 15mL in the water of 50mL successively, stir 3h under the room temperature; The ice bath cooling slowly adds sodium borohydride aqueous solution 15g again, continues to stir 1.5h; Being acidified to pH with hydrobromic acid is 6, continues to stir 3h; Then, decompression distillation is to solid-state; Use the methanol extraction 3 times of 30mL respectively, filter, filtrate is revolved steaming, make chiral ligand l-HL; Described sodium borohydride aqueous solution, the mass fraction of sodium borohydride are 15%.
In the secondary ion water of 10mL, add synthetic chiral ligand l-HL0.4g, zinc acetate 0.25g, be placed in the small beaker, and small beaker is put into the large beaker that fills 50mL methyl alcohol, sealing, at room temperature spread 2.5d, with in the small beaker the mixed liquor of crystallization filter, and wash the crystal that leaches repeatedly with the methanol aqueous solution of 7.5mL respectively, make chirality MOF{[ZnL] H
2O}n; Described methanol aqueous solution, the volume ratio of methyl alcohol and water are 1.0:1.
The preparation of chiral ligand l-HL is with embodiment 1;
In the secondary ion water of 10mL, add synthetic chiral ligand l-HL0.3g, zinc acetate 0.15g, be placed in the small beaker, and small beaker is put into the large beaker that fills 40mL methyl alcohol, sealing, at room temperature spread 2d, with in the small beaker the mixed liquor of crystallization filter, and wash the crystal that leaches repeatedly with the methanol aqueous solution of 5mL respectively, make chirality MOF{[ZnL] H
2O}n; Described methanol aqueous solution, the volume ratio of methyl alcohol and water are 0.5:1.
Embodiment 5
The preparation of chiral ligand l-HL is with embodiment 2;
In the secondary ion water of 10mL, add synthetic chiral ligand l-HL0.3g, zinc acetate 0.15g, be placed in the small beaker, and small beaker is put into the large beaker that fills 40mL methyl alcohol, sealing, at room temperature spread 2d, with in the small beaker the mixed liquor of crystallization filter, and wash the crystal that leaches repeatedly with the methanol aqueous solution of 5mL respectively, make chirality MOF{[ZnL] H
2O}n; Described methanol aqueous solution, the volume ratio of methyl alcohol and water are 0.5:1.
The preparation of chiral ligand l-HL is with embodiment 3;
In the secondary ion water of 10mL, add synthetic chiral ligand l-HL 0.3g, zinc acetate 0.15g, be placed in the small beaker, and small beaker is put into the large beaker that fills 40mL methyl alcohol, sealing, at room temperature spread 2d, with in the small beaker the mixed liquor of crystallization filter, and wash the crystal that leaches repeatedly with the methanol aqueous solution of 5mL respectively, make chirality MOF{[ZnL] H
2O}n; Described methanol aqueous solution, the volume ratio of methyl alcohol and water are 0.5:1.
Embodiment 7
The preparation of chiral ligand l-HL is with embodiment 1;
In the secondary ion water of 10mL, add synthetic chiral ligand l-HL0.5g, zinc acetate 0.35g, be placed in the small beaker, and small beaker is put into the large beaker that fills 60mL methyl alcohol, sealing, at room temperature spread 3d, with in the small beaker the mixed liquor of crystallization filter, and wash the crystal that leaches repeatedly with the methanol aqueous solution of 10mL respectively, make chirality MOF{[ZnL] H
2O}n; Described methanol aqueous solution, the volume ratio of methyl alcohol and water are 1.5:1.
The preparation of chiral ligand l-HL is with embodiment 2;
In the secondary ion water of 10mL, add synthetic chiral ligand l-HL 0.5g, zinc acetate 0.35g, be placed in the small beaker, and small beaker is put into the large beaker that fills 60mL methyl alcohol, sealing, at room temperature spread 3d, with in the small beaker the mixed liquor of crystallization filter, and wash the crystal that leaches repeatedly with the methanol aqueous solution of 10mL respectively, make chirality MOF{[ZnL] H
2O}n; Described methanol aqueous solution, the volume ratio of methyl alcohol and water are 1.5:1.
Embodiment 9
The preparation of chiral ligand l-HL is with embodiment 3;
In the secondary ion water of 10mL, add synthetic chiral ligand l-HL 0.5g, zinc acetate 0.35g, be placed in the small beaker, and small beaker is put into the large beaker that fills 60mL methyl alcohol, sealing, at room temperature spread 3d, with in the small beaker the mixed liquor of crystallization filter, and wash the crystal that leaches repeatedly with the methanol aqueous solution of 10mL respectively, make chirality MOF{[ZnL] H
2O}n; Described methanol aqueous solution, the volume ratio of methyl alcohol and water are 1.5:1.
Performance test
With the chiral ligand l-HL that embodiment 1 or embodiment 2 or embodiment 3 make, recording its molecular formula with elemental analyser and single crystal diffraction analyzer is C
12H
19BrN
2O
2, wherein the mass fraction of C is 47.54%; The mass fraction 6.32% of H; The mass fraction 9.24% of N.
{ [ZnL] H that embodiment 1 or embodiment 2 or embodiment 3 synthesize
2O}n records its lattice through the single crystal diffraction analyzer and exists with P61 chirality space group, is the 3D porous framework of non-IPN; Its asymmetric construction unit contains a Zn
2+, a L part, a Br
-With an object water; Its 1D chiral helical passage is occupied by object water, has
Aperture and aperture, if consider van der Waals radius, have
Duct and aperture; Its
Symbol is 8
3Its heat endurance reaches 270 ℃; This chirality MOF is water insoluble, ethanol, methyl alcohol, oxolane, dimethyl formamide and dimethyl thionyl chloride.
Application among the HPLC
Use sample 1
The chirality MOF{[ZnL that embodiment 1 or embodiment 2 or embodiment 3 are made] H
2O}n, at 35 ℃ of vacuum drying 24h, activation makes chirality MOF[ZnL] n;
With 2.0g[ZnL] n joins the suspension that 20mL flies to make in the methyl alcohol [ZnL] n, and this suspension is pressed into the pressure of 5000psi makes chirality MOF chromatographic stationary phase in the stainless steel chromatogram post;
Described stainless steel column, its internal diameter are 4.6mm, length 100mm;
Use sample 2
The chirality MOF{[ZnL that embodiment 4 or embodiment 5 or embodiment 6 are made] H
2O}n, at 45 ℃ of vacuum drying 20h, activation makes chirality MOF[ZnL] n;
With 2.5g[ZnL] n joins the suspension of making [ZnL] n in the 25mL methyl alcohol, and this suspension is pressed into the pressure of 5000psi makes chirality MOF chromatographic stationary phase in the stainless steel chromatogram post;
Described stainless steel column, its internal diameter are 4.6mm, length 150mm;
Use sample 3
The chirality MOF{[ZnL that embodiment 7 or embodiment 8 or embodiment 9 are made] H
2O}n, at 60 ℃ of vacuum drying 18h, activation makes chirality MOF[ZnL] n;
With 3.0g[ZnL] n joins the suspension of making [ZnL] n among the methyl alcohol 30mL, and this suspension is pressed into the pressure of 5000psi makes chirality MOF chromatographic stationary phase in the stainless steel chromatogram post;
Described stainless steel column, its internal diameter are 4.6mm, length 200mm;
The chirality MOF chromatographic stationary that application sample 1-3 is made is used for HPLC fractionation brufen enantiomer mutually, and it flows is the mixture of cyclohexane and isopropyl alcohol mutually, and the volume ratio of cyclohexane and isopropyl alcohol is 100:1-10, brufen enantiomer baseline separation.It is carboxylic acid that brufen contains functional group, its minimum power diameter
Less than described chirality MOF chirality passage and aperture
Size.
To use sample 1-3 and make chirality MOF chromatographic stationary mutually for HPLC fractionation benzyl carbinol enantiomer, it flows is the mixture of cyclohexane and isopropyl alcohol mutually, and the volume ratio of cyclohexane and isopropyl alcohol is 100:1-10, benzyl carbinol enantiomer baseline separation.It is hydroxyl that benzyl carbinol contains functional group, its minimum power diameter
Less than described chirality MOF chirality passage and aperture
Size.
To use sample 1-3 and make chirality MOF chromatographic stationary mutually for HPLC fractionation phenyl ethylamine enantiomer, it flows is the mixture of cyclohexane and isopropyl alcohol mutually, and the volume ratio of cyclohexane and isopropyl alcohol is 100:1-10, phenyl ethylamine enantiomer baseline separation.Phenyl ethylamine contains functional group for amino, its minimum power diameter
Less than described chirality MOF chirality passage and aperture
Size.
To use sample 1-3 and make chirality MOF chromatographic stationary mutually for HPLC fractionation styrax enantiomer, it flows is the mixture of cyclohexane and isopropyl alcohol mutually, and the volume ratio of cyclohexane and isopropyl alcohol is 100:1-10, styrax enantiomer baseline separation.Its minimum power diameter of styrax
Less than described chirality MOF chirality passage and aperture
Size.
Claims (9)
1. the fixing phase of a no IPN chirality MOF, it is that structural formula is { [ZnL] H
2The three-dimensional porous frame complex of non-IPN chirality of O}n; An its asymmetric construction unit { [ZnL] H
2O} is by a Zn
2+, a L part and an object hydrone form; The L part is to contain-the chiral pyridyl carboxylic acid of NH-, and its chemical composition is [(N-(4-picolyl)-L-leucine HBr)], and molecular formula is C
12H
19BrN
2O
2The three-dimensional porous frame complex of described non-IPN chirality has the chiral helical passage of homogeneous, and this chiral helical passage has
Aperture and aperture, if consider van der Waals radius, have
Duct and aperture, is occupied by object water in the helical duct.
2. the fixing phase of a kind of no IPN chirality MOF according to claim 1 is characterized in that its molecular formula is C
12H
19N
2O
3ZnBr, wherein the mass fraction of C is that the mass fraction of 37.48%, H is that the mass fraction of 4.98%, N is 7.28%.
3. one kind is not had the fixedly preparation method of phase of IPN chirality MOF, it is characterized in that, comprises that step is as follows:
(1) Xiang Shuizhong adds the mixed liquor of L-leucine, sodium carbonate, 4-aldehyde radical pyridine and methyl alcohol successively, stirs 1-3h under the room temperature; The ice bath cooling slowly adds sodium borohydride aqueous solution again, continues to stir 0.5-1.5h; Being acidified to pH with hydrobromic acid is 3-6, continues to stir 1-3h; Then, decompression distillation is to solid-state; With methanol extraction repeatedly, filter, filtrate is revolved steaming, make chiral ligand l – HL;
(2) in secondary ion water, add step (1) synthetic chiral ligand l-HL, zinc acetate, be placed in the small beaker, and small beaker put into the large beaker that fills methyl alcohol, sealing, at room temperature spread 2-3d, with in the small beaker the mixed liquor of crystallization filter, and the crystal that leaches with the methanol aqueous solution washing respectively repeatedly, makes chirality MOF{[ZnL] H
2O}n.
4. a kind of fixedly preparation method of phase of IPN chirality MOF that do not have according to claim 3, it is characterized in that the mass ratio of the described water of step (1), L-leucine, sodium carbonate, 4-aldehyde radical pyridine, sodium borohydride aqueous solution is 30-50:1.0-3.0:0.5-1.5:1.0-3.0:5-15; 4-aldehyde radical pyridine concentration is 0.2g/mL in the mixed liquor of 4-aldehyde radical pyridine and methyl alcohol; The mass concentration of sodium borohydride aqueous solution is 7%-15%.
5. a kind of fixedly preparation method of phase of IPN chirality MOF that do not have according to claim 3 is characterized in that the mass ratio of the described secondary ion water of step (2), chiral ligand l-HL, zinc acetate is 8-10:0.3-0.5:0.15-0.35; The volume ratio of described methanol aqueous solution methyl alcohol and water is 0.5-1.5:1.
6. the fixing application that in HPLC, splits drug enantiomer or other enantiomer as chromatographic stationary mutually of the described no IPN chirality MOF of claim 1.
7. application according to claim 6 is characterized in that, concrete grammar is: with chirality MOF{[ZnL] H
2O}n activates at 35-60 ℃ of vacuum drying 18-24h, joins in the methyl alcohol suspension of making [ZnL] n then, and the pressure of this suspension with 5000psi is pressed in the stainless steel chromatogram post; Mixture with cyclohexane and isopropyl alcohol is the phase that flows, and will treat that the branch sample crosses post.
8. application according to claim 7 is characterized in that, the concentration of the suspension of described [ZnL] n is 1.0g/mL.
9. application according to claim 7 is characterized in that, the volume ratio of described cyclohexane and isopropyl alcohol is 100:1-10.
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| CN114504843A (en) * | 2021-12-24 | 2022-05-17 | 上海大学 | Preparation method of capillary open-tube chromatographic column based on metal organic framework material |
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| CN114504843B (en) * | 2021-12-24 | 2023-05-02 | 上海大学 | Preparation method of capillary open-tube chromatographic column based on metal organic framework material |
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