Modified zein chiral separation membrane and application thereof

Abstract

The application discloses a modified corn protein zein chiral separation membrane and belongs to the technical field of functional high polymer materials. The modified corn protein zein chiral separation membrane is prepared by the following steps: 1) mixing and stirring nano corn protein zein, chiral resolution material and an ethanol solution, adding acid to adjust the pH to 5-10, and then performing ultrasonic oscillation, and then flowing the solution on a film preparation plate to form a nano membrane material; the chiral resolution material is polysaccharide or a supramolecular compound; 2) drying and peeling the nano membrane material to obtain the modified corn protein zein chiral separation membrane. The modified corn protein zein chiral separation membrane provided by the application has high separation performance when applied to the separation of racemic compounds.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional polymer materials, in particular to a modified zein chiral separation membrane and application thereof. BACKGROUND

[0002] Chirality is the essential property of nature, especially of living organisms. Enantiomers have great differences in biological activity, physiological activity and pharmacological activity, and even opposite effects. Obtaining single enantiomers is of great significance to physiological and pharmacological research. Therefore, chiral separation has always been the focus and difficulty of separation and analysis research. In recent years, the technology of chiral recognition and separation has developed rapidly. Chromatography, sensor method and spectroscopy have good applicability, wide application range, high sensitivity and fast detection speed, and have attracted great attention from researchers in the separation and identification and purification of chiral compounds. The core of chiral separation is the preparation and application of chiral separation materials, and the development of chiral separation materials is changing rapidly.

[0003] Zein is a food protein widely existing in plants, which has a unique amino acid composition. Its three-dimensional structure is a spiral wheel. Circular dichroism and rotation scattering show that Zein has a nearly spherical conformation in 50-80% ethanol solution. When the ethanol concentration decreases, the conformation of Zein changes, and it has good film-forming properties. When the solvent effect is generated, Zein is easy to be nano-sized, and has the properties of high specific surface area, high reactivity, small size effect and quantum tunneling effect. Zein has emulsification, ligand binding, gelation and other properties, and has been used to construct various mechanism carrier materials. More and more studies have shown that protein membranes have a special effect on the embedding, protection and delivery of functional materials. However, so far, it has not been used in the application field of chiral separation membrane. The reason is that although the Zein has good spiral performance, it lacks chiral structure, resulting in insufficient chiral separation performance. SUMMARY

[0004] The purpose of the present application is to provide a modified Zein chiral separation membrane and application thereof. The chiral separation of chiral compounds is completed by using the chiral separation performance of chiral materials and the spiral structure of Zein itself. The separation performance of Zein membrane is improved, and the separation performance of chiral membrane material is improved.

[0005] To achieve the above purpose, the present application provides a modified Zein chiral separation membrane, which is prepared by the following steps:

[0006] 1) mixing nano zein, chiral resolution material and ethanol solution, adding acid to adjust pH to 5-10, ultrasonic oscillation, and then casting the solution on a film making plate to form a nano membrane material; the chiral resolution material is polysaccharide or supramolecular compound;

[0007] 2) drying and peeling the nano membrane material to obtain a modified zein chiral separation membrane.

[0008] Preferably, the nano zein is prepared by the following steps:

[0009] Mixing zein solution and ethanol solution, adjusting the pH of the mixture to 9-11, adding deionized water while stirring, and then sequentially performing rotary evaporation and drying to obtain nano zein.

[0010] Preferably, the concentration of the ethanol solution is 60wt%-90wt%, and the mass ratio of the ethanol solution to zein is 70-100:1.0-2.0.

[0011] Preferably, the temperature during rotary evaporation is 70-90℃, and the pressure is 0.8-1.0Mpa.

[0012] Preferably, the mass ratio of the chiral resolution material to nano zein in step 1) is 1:1-1:10.

[0013] Preferably, the concentration of the ethanol solution in step 1) is 60wt%-80wt%, and the mass ratio of the ethanol solution to nano zein is 70-100:0.1-2.0.

[0014] Preferably, the polysaccharide includes nano cellulose, nano amylose and chitosan.

[0015] Preferably, the supramolecular compound is β-cyclodextrin and β-cyclodextrin derivative.

[0016] The application provides application of the modified zein chiral separation membrane in separating racemic compounds.

[0017] Preferably, the racemic compound includes ibuprofen drug, pasufoxacin, albendazole sulfoxide, terbutaline or propranolol.

[0018] The modified zein chiral separation membrane provided by the application is prepared by modifying nano zein with chiral resolution materials, so that the surface of the nano zein is enhanced with chiral functionalization, and the chiral separation capacity is improved in combination with the spiral structure of the nano zein membrane itself. The modified zein chiral separation membrane prepared by the method not only loads more chiral resolution materials on the active sites of the zein, but also improves the chiral separation capacity by using the spiral structure of the membrane itself. The modified zein chiral separation membrane has good separation efficiency for the separation and analysis of chiral compounds. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 Liquid chromatogram of ibuprofen separation of Example 7;

[0020] Figure 2 Liquid chromatogram of albendazole sulfoxide separation of Example 7. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the application will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0022] The application provides a modified zein chiral separation membrane, which is prepared by the following steps:

[0023] 1) mixing and stirring nano zein, chiral resolution materials and an ethanol solution, adding acid to adjust the pH to 5-10, and then performing ultrasonic oscillation and solution casting on a membrane preparation plate to form a nano membrane material;

[0024] 2) drying and peeling the nano membrane material to obtain a modified zein chiral separation membrane.

[0025] The application mixes and stirs nano zein, chiral resolution materials and an ethanol solution, adds acid to adjust the pH to 5-10, and then performs ultrasonic oscillation and solution casting on a membrane preparation plate to form a nano membrane material; the chiral resolution materials are polysaccharides or supramolecular compounds.

[0026] In the present application, the nano zein is preferably prepared by the following steps: mixing a zein solution and an ethanol solution, adjusting the pH of the mixture to 9-11, adding deionized water while stirring, and then sequentially performing rotary evaporation and drying after a large amount of flocculent precipitate is generated, to obtain the nano zein. In the present application, the concentration of the ethanol solution is preferably 60wt%-90wt%, and the mass ratio of the ethanol solution to the zein is preferably 70-100:1.0-2.0. In the present application, the temperature during rotary evaporation is preferably 70-90℃, and the pressure is preferably 0.8-1.0 Mpa. In the present application, the nano zein prepared by the method has the advantages of simple method, convenient preparation, and uniform particle size.

[0027] In the present application, the chiral resolution material is a polysaccharide or a supramolecular compound. In the present application, the polysaccharide is preferably nano cellulose, nano amylose or chitosan. The present application does not have special limitations on the source of the nano cellulose, which can be prepared by a conventional acid hydrolysis method. The present application does not have special limitations on the source of the nano amylose, which can be prepared by a conventional acid hydrolysis method. In the present application, the supramolecular compound includes β-cyclodextrin and β-cyclodextrin derivatives.

[0028] In the present application, the mass ratio of the chiral resolution material to the nano zein is preferably 1:1-1:10. In the present application, the concentration of the ethanol solution is preferably 60wt%-80wt%, and the mass ratio of the ethanol solution to the nano zein is preferably 70-100:0.1-2.0.

[0029] In the present application, when the ultrasonic oscillation is performed, the power of the ultrasonic wave is 200-360w, and the time is 5-10min. In the present application, the material of the film plate is preferably polyethylene, polytetrafluoroethylene, quartz or glass.

[0030] After the nano membrane material is obtained, the nano membrane material is dried and peeled to obtain a modified zein chiral separation membrane. In the present application, the drying method is natural drying.

[0031] In the present application, the chiral resolution material is used to modify the nano zein, so that the surface of the nano zein is functionalized to enhance the chiral function, and the spiral structure of the nano zein membrane itself is combined to improve the chiral separation capacity. The modified zein chiral separation membrane prepared by the method not only uses the active sites of the zein to load more chiral resolution materials, but also uses the spiral structure of the membrane itself to improve the chiral separation capacity. The modified zein chiral separation membrane has good separation efficiency for the separation and analysis of chiral compounds.

[0032] The application provides application of the modified zein chiral separation membrane in separation of a racemic compound.

[0033] In the application, the racemic compound includes ibuprofen drugs, pasuoxacin, albendazole sulfoxide, terbutaline or propranolol, and is more preferably ibuprofen drugs.

[0034] In order to further illustrate the application, the technical solutions provided by the application are described in detail below in combination with examples, but they should not be understood as limiting the protection scope of the application.

[0035] In the following examples and comparative examples, the zein is purchased from Sigma-aldrich, the β-cyclodextrin is purchased from Shanghai Aladdin Biomedical Technology Co., the nanocellulose is purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd., and the nanostarch is purchased from Shanghai Yuanye Biotechnology Co., Ltd.

[0036] Example 1

[0037] (1) 1.0 g of zein was taken, the zein was dissolved in 80 mL of 60 wt% ethanol solution to be fully dissolved, the pH was adjusted to 10, deionized water was added while stirring, a large amount of flocculent precipitate was generated, the solvent was rotary evaporated (the temperature was 80℃, and the pressure was 0.9 MPa), the concentrated material after rotary evaporation was freeze-dried at-50℃ for 5 h, and 0.9 g of nanometer zein material was prepared.

[0038] (2) 0.1 g of nanocellulose and 0.5 g of nanometer zein were taken and dissolved in 100 mL of 70 wt% ethanol aqueous solution, fully stirred, hydrochloric acid was added to adjust the pH to 5.0, and after ultrasonic oscillation at a power of 300 w for 8 min, the solution was cast on a flat plate of polyethylene material to form a nanometer film, and after natural drying, the film was peeled off, and a modified zein chiral separation membrane was obtained. The modified zein chiral separation membrane is used for separation of chiral drugs ibuprofen, and the resolution degree is 1.0.

[0039] Example 2

[0040] (1) 1.0 g of zein was taken, the zein was dissolved in 70 mL of 90 wt% ethanol solution to be fully dissolved, the pH was adjusted to 9, deionized water was added while stirring, a large amount of flocculent precipitate was generated, the solvent was rotary evaporated (the temperature was 80℃, and the pressure was 0.9 MPa), the concentrated material after rotary evaporation was freeze-dried at-50℃ for 5 h, and 0.9 g of nanometer zein material was prepared.

[0041] (2) Take 0.1 g of nanometer amylose and 0.6 g of nanometer zein to be dissolved in 70 mL of 70 wt% ethanol aqueous solution, fully stir, add hydrochloric acid to adjust pH to 6.0, ultrasonic oscillation at 300 w for 5 min, then flow cast the solution on a flat plate of polytetrafluoroethylene material to form a nanometer film, after natural drying, peel off the film to obtain a modified zein chiral separation film. The modified zein chiral separation film is used for separation of chiral drug ibuprofen, and the separation degree is 1.2.

[0042] Example 3

[0043] (1) Take 1.0 g of zein, dissolve the zein in 100 mL of 80 wt% ethanol solution, fully dissolve, adjust pH to 11, add deionized water while stirring, a large amount of flocculent precipitate is generated, rotary evaporation of the solvent (temperature is 80℃, pressure is 0.9 MPa), freeze-drying of the concentrated material at -50℃ for 5 h to obtain 0.9 g of nanometer zein material.

[0044] (2) Take 0.1 g of β-cyclodextrin and 0.8 g of nanometer zein to be dissolved in 90 mL of 80 wt% ethanol aqueous solution, fully stir, add hydrochloric acid to adjust pH to 7.0, ultrasonic oscillation at 300 w for 5 min, then flow cast the solution on a flat plate of quartz material to form a nanometer film, after natural drying, peel off the film to obtain a modified zein chiral separation film. The modified zein chiral separation film is used for separation of chiral drug ibuprofen, and the separation degree is 1.3.

[0045] Example 4

[0046] (1) Same as Example 1.

[0047] (2) Take 0.1 g of nanometer cellulose and 0.5 g of nanometer zein to be dissolved in 100 mL of 80 wt% ethanol aqueous solution, fully stir, add hydrochloric acid to adjust pH to 8.0, ultrasonic oscillation at 360 w for 8 min, then flow cast the solution on a flat plate of glass material to form a nanometer film, after natural drying, peel off the film to obtain a modified zein chiral separation film. The modified zein chiral separation film is used for separation of chiral drug ibuprofen, and the separation degree is 1.3.

[0048] Example 5

[0049] (1) Same as Example 2.

[0050] (2) Take 0.1 g of nanometer straight-chain amylose and 0.5 g of nanometer zein to be dissolved in 70 mL of 80 wt% ethanol aqueous solution, fully stir, add hydrochloric acid to adjust pH to 8.0, ultrasonic oscillation at 360 w for 8 min, then flow the solution to a flat plate of glass material to form nanometer film, after natural drying, the film can be peeled off to obtain modified zein chiral separation film. The modified zein chiral separation film is used for separation of chiral drug ibuprofen, and the separation degree is 1.5.

[0051] Example 6

[0052] (1) Take 1.0 g of zein, dissolve the zein in 100 mL of 80 wt% ethanol solution, fully dissolve, adjust pH to 10, add deionized water while stirring, a large amount of flocculent precipitate is generated, rotary evaporation of the solvent (temperature is 80℃, pressure is 0.9 MPa), the concentrated material after rotary evaporation is freeze-dried at -50℃ for 6 h to prepare 0.9 g of nanometer zein material.

[0053] (2) Take 0.1 g of β-cyclodextrin and 0.6 g of nanometer zein to be dissolved in 100 mL of 80 wt% ethanol aqueous solution, fully stir, add hydrochloric acid to adjust pH to 10.0, ultrasonic oscillation at 200 w for 3 min, then flow the solution to a flat plate of glass material to form nanometer film, after natural drying, the film can be peeled off to obtain modified zein chiral separation film. The modified zein chiral separation film is used for separation of chiral drug ibuprofen, and the separation degree is 1.5.

[0054] Example 7

[0055] (1) The same as Example 1.

[0056] (2) Take 0.1 g of nanometer cellulose and 0.8 g of nanometer zein to be dissolved in 100 mL of 60 wt% ethanol aqueous solution, fully stir, add hydrochloric acid to adjust pH to 8.0, ultrasonic oscillation at 360 w for 8 min, then flow the solution to a flat plate of polytetrafluoroethylene to form nanometer film, after natural drying, the film can be peeled off to obtain modified zein chiral separation film. The modified zein chiral separation film is used for separation of chiral drug ibuprofen, and the separation degree is 1.6, and the liquid chromatogram thereof is shown in Figure 1 . The modified zein chiral separation film is used for separation of albendazole sulfoxide, and the separation degree is 1.5, and the liquid chromatogram thereof is shown in Figure 2 .

[0057] Example 8

[0058] (1) The same as Example 2.

[0059] (2) Take 0.1 g nanometer amylose and 0.8 g nanometer zein to be dissolved in 70 mL 80 wt% ethanol aqueous solution, fully stir, add hydrochloric acid to adjust pH to 10.0, ultrasonic oscillation for 10 min at 360 w power, then flow cast the solution to polytetrafluoroethylene flat plate to form nanometer film, after natural drying, the film can be peeled off to obtain modified zein chiral separation film. The modified zein chiral separation film is used for separation of chiral drug ibuprofen, and the resolution is 1.8.

[0060] Comparative Example 1

[0061] The difference from Example 1 is that nanocellulose is not used for modification, and the specific operation is as follows:

[0062] (1) Take 1.0 g zein, dissolve the zein in 80 mL 60 wt% ethanol solution, fully dissolve, adjust pH to 10, add deionized water while stirring, a large amount of flocculent precipitate is generated, rotary evaporation (temperature is 80℃, pressure is 0.9 MPa) is performed, the concentrated material after rotary evaporation is freeze-dried at-50℃ for 5 h to obtain 0.9 g nanometer zein material.

[0063] (2) 0.5 g nanometer zein is dissolved in 100 mL 70 wt% ethanol aqueous solution, fully stir, add hydrochloric acid to adjust pH to 5.0, ultrasonic oscillation for 8 min at 300 w power, then flow cast the solution to polyethylene material flat plate to form nanometer film, after natural drying, the film is peeled off to obtain zein chiral separation film. The zein chiral separation film is used for separation of chiral drug ibuprofen, and the resolution is 0.6.

[0064] Comparative Example 2

[0065] Nanocellulose film is used for separation, and the specific operation is as follows:

[0066] Take 0.5 g nanocellulose to be dissolved in 100 mL 70 wt% ethanol aqueous solution, fully stir, add hydrochloric acid to adjust pH to 5.0, ultrasonic oscillation for 8 min at 300 w power, then flow cast the solution to polyethylene material flat plate to form nanometer film, after natural drying, the film is peeled off to obtain nanocellulose film. The nanocellulose film is used for separation of chiral drug ibuprofen, and the resolution is 0.8.

[0067] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application, but not to limit them. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can still be modified or equivalently replaced, and these modifications or equivalent replacements cannot make the modified technical solutions deviate from the spirit and scope of the technical solutions of the present application.

Claims

1. A modified zein chiral separation membrane, characterized in that, The modified zein chiral separation membrane is prepared by the following steps: 1) mixing nano zein, chiral resolution material and ethanol solution, stirring, adding acid to adjust pH to 5-10, ultrasonic oscillation, and then casting the solution on a film preparation plate to form a nano membrane material; the chiral resolution material is polysaccharide or supramolecular compound; 2) drying and peeling the nano membrane material to obtain the modified zein chiral separation membrane.

2. The modified com prolamin chiral separation membrane according to claim 1, characterized by, The nano zein is prepared by the following steps: mixing zein and ethanol solution, adjusting the pH of the mixture to 9-11, adding deionized water while stirring, and then sequentially performing rotary evaporation and drying to obtain nano zein.

3. The modified com prolamin chiral separation membrane according to claim 2, characterized by, The concentration of the ethanol solution in the preparation of nano zein is 60wt%-90wt%, and the mass ratio of the ethanol solution to zein is 70-100:1.0-2.

0.

4. The modified com prolamin chiral separation membrane according to claim 2, characterized by, The temperature during rotary evaporation is 70-90℃, and the pressure is 0.8-1.0Mpa.

5. The modified com prolamin chiral separation membrane according to claim 1, wherein The mass ratio of the chiral resolution material to nano zein in step 1) is 1:1-1:

10.

6. The modified com prolamin chiral separation membrane according to claim 1, wherein The concentration of the ethanol solution in step 1) is 60wt%-80wt%, and the mass ratio of the ethanol solution to nano zein is 70-100:0.1-2.

0.

7. The modified zein chiral separation membrane according to claim 1, wherein, The polysaccharide includes nano cellulose, nano amylose and chitosan.

8. The modified com prolamin chiral separation membrane according to claim 1, wherein The supramolecular compound is β-cyclodextrin and β-cyclodextrin derivative.

9. Use of the modified zein chiral separation membrane according to any one of claims 1-8 in the separation of racemic compounds.

10. Use according to claim 9, characterized in that, The racemic compounds include ibuprofen drug, pasufoxacin, albendazole sulfoxide, terbutaline or propranolol.

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