CN106831803B - Preparation method and application of benzophenanthridine alkaloid molecularly imprinted magnetic microspheres - Google Patents
Preparation method and application of benzophenanthridine alkaloid molecularly imprinted magnetic microspheres Download PDFInfo
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Abstract
The invention relates to a preparation method and application of benzophenanthridine alkaloid (such as sanguinarine, chelerythrine and the like) molecularly imprinted magnetic polymer microspheres, and the method comprises the following steps of (1) Fe3O4Preparing nano particles; (2) fe3O4@SiO2Preparing particles; (3) Vinyl-Fe3O4@SiO2Preparing particles; (4) synthesizing a surface molecularly imprinted magnetic polymer; (5) separating and purifying to obtain benzophenanthridine alkaloids (sanguinarine and chelerythrine). The molecular imprinting magnetic polymer microsphere of benzophenanthridine alkaloids prepared by the invention has good magnetism, can realize the specific separation of a plurality of benzophenanthridine alkaloids, and has the advantages of high purity of the obtained alkaloids, simple operation, cheap and easily obtained raw materials and low cost. Has wide application prospect in the aspects of separation, enrichment, detection and the like of benzophenanthridine alkaloids and analogues thereof.
Description
Technical Field
The invention relates to the fields of medicinal chemistry, organic chemistry and analytical chemistry, in particular to a preparation method and application of benzophenanthridine alkaloid (such as sanguinarine, chelerythrine and the like) molecularly imprinted magnetic polymer microspheres (for short).
Background
The medicinal plants such as macleaya cordata, macleaya microcarpa, sanguinea japonica, greater celandine and chelidonium and the like are rich in various benzophenanthridine alkaloids (such as sanguinarine, chelerythrine, dihydrosanguinarine, dihydrochelerythrine, oxymatrine and the like), wherein the alkaloids such as sanguinarine and chelerythrine are concerned by people due to the pharmacological activities of resisting viruses, killing bacteria, resisting cancers and the like, and the separation and purification of the alkaloids are also the hot problems of alkaloid medicament research. The traditional method for separating benzophenanthridine alkaloids mainly comprises the technologies of column chromatography, macroporous adsorption resin, supercritical fluid extraction, preparative chromatography, molecular imprinting and the like. The column chromatography has the advantages of comprehensiveness and system in the aspect of separation and purification, but is complex to operate and long in period; the macroporous adsorption resin and the membrane separation technology are difficult to separate to obtain a high-purity product; whereas supercritical fluid extraction is only suitable for separating and purifying low-polarity or non-polar alkaloids; high-purity products can be obtained by high performance liquid chromatography, but the cost is high, and industrialization is difficult to realize. In order to solve these problems, many advanced separation methods have been rapidly developed, and among them, a selective separation technique using a molecularly imprinted magnetic polymer as a carrier shows a good application prospect in the research of separation and purification of benzophenanthridine alkaloids and analogues thereof.
The molecular imprinting technology is a new high-selectivity solid-phase extraction technology appearing at the end of the 20 th century. The new Molecular Imprinted Polymer (MIPs) material has specific selectivity and identification on imprinted molecules and guest molecules with similar structures, good physical and chemical stability, low cost and easy preparation, thereby showing good application prospects in the fields of chromatographic separation, solid-phase extraction, natural active ingredient separation and the like, while Fe3O4The magnetic nano-particles have the characteristics of special magnetic guidance, superparamagnetism, capability of connecting biochemical active functional groups on the surface and the like, so that the application of the magnetic nano-particles in the fields of biochemical separation, analysis, targeted drugs, enzymes, cell immobilization and the like is widely developed. Therefore, the polymer is coated on the outer surface of the magnetic nano particle and the surface molecular imprinting treatment is carried out to synthesize the magnetic molecular imprinting polymer core-shell microsphere, so that the magnetic molecular imprinting polymer core-shell microsphere has two advantages of good superparamagnetism and high selective adsorbability, the application of the molecular imprinting and the magnetic microsphere is further expanded, and the magnetic molecular imprinting polymer core-shell microsphere is expected to play a great role in promoting the development of the separation and purification technology of natural medicines.
We develop a new method of molecular imprinting magnetic microspheres based on benzophenanthridine alkaloid (such as sanguinarine, chelerythrine and the like) medicaments, can be applied to separation of sanguinarine components in a sanguinarine-containing traditional Chinese medicine extracting solution, and is good in effect, low in separation cost and environment-friendly. Through the domestic and foreign literature search, no relevant report on the preparation of benzophenanthridine alkaloid molecularly imprinted magnetic microspheres such as sanguinarine, chelerythrine and the like is found.
Disclosure of Invention
The invention aims to provide a preparation method of benzophenanthridine alkaloid molecularly imprinted magnetic microspheres, which has excellent selection and recognition capabilities on target molecules, and the prepared microspheres can be recycled and meet the requirements of environmental protection. The benzophenanthridine alkaloid magnetic molecularly imprinted polymer microsphere prepared by the invention can quickly adsorb and separate sanguinarine components in sanguinarine-containing traditional Chinese medicine extracting solutions such as macleaya cordata, macleaya microcarpa, herba Eomenii, greater celandine and the like, and can be directly applied to selective separation and efficient enrichment of sanguinarine.
The technical scheme of the invention is as follows:
（1）Fe3O4nanoparticle preparation
FeCl is added3·6H2And O is ultrasonically dispersed in ethylene glycol. Then trisodium citrate, PEG-2000 and anhydrous sodium acetate are added into the solution in sequence, and ultrasonic dispersion is carried out. After stirring until the solution is clear and transparent, the solution is transferred to a reaction kettle and reacted for 8 hours at 200 ℃. After the reaction is finished, Fe is obtained after separation, washing and drying3O4Magnetic nanoparticles.
（2）Fe3O4@SiO2Preparation of granules
Mixing Fe3O4The particles are dispersed in a mixed solution of ethanol-water. Transferring the obtained solution into a three-neck flask, adding ammonia water while stirring at 500r/min, and dropwise adding TEOS (tetraethyl orthosilicate). The mixture was reacted at 40 ℃ for 12 h. After the reaction is finished, Fe is obtained after separation, washing and drying3O4@SiO2Magnetic nanoparticles.
（3）Vinyl- Fe3O4@SiO2Preparation of granules
MPS (methacryloxypropyltrimethoxysilane) was added dropwise to the acetic acid-water mixed solution, and stirred at 25 ℃ for 5 hours. Subsequently, Fe was added3O4@SiO2The nanoparticles were stirred in solution at 60 ℃ for 5.5 h. After the reaction is finished, the Vinyl-Fe is obtained after separation, washing and drying3O4@SiO2Magnetic nanoparticles.
(4) Synthesis of surface molecularly imprinted magnetic polymer
Adding template alkaloid (such as sanguinarine, chelerythrine, etc.) and functional monomer 4-VP (4-vinylpyridine) into acetonitrile, standing at 4 deg.C for 12h to form pre-assembled solution, Vinyl-Fe3O4@SiO2Ultrasonic dispersion in acetonitrile followed by addition of crosslinker EGDMA (ethylene glycol dimethacrylate), initiator AIBN (azobisisobutyronitrile) and pre-assembly solution. Stirring at 60 ℃ and 500r/min for 24 h. And after the reaction is finished, washing the mixture by using a detergent until the supernatant is clear, eluting the mixture by using an eluent until the template is removed, and finally washing the particles to be neutral and drying the particles to obtain the benzophenanthridine alkaloid (sanguinarine and chelerythrine) molecularly imprinted magnetic polymer microspheres.
According to the present invention, it is preferred that FeCl in step (1)3·6H2O is 1.08g, and ethylene glycol is 80 ml.
Preferably, the mass ratio of the added trisodium citrate, PEG-2000 and anhydrous sodium acetate is 1:2: 9.
Preferably, the method of separation is magnetic separation.
Preferably, the washing agent used for washing is absolute ethyl alcohol and distilled water.
Preferably, the drying method is freeze drying.
According to the present invention, it is preferred that the ratio of ethanol-water solution in step (2) is absolute ethanol: water =4: 1.
Preferably, Fe is added3O4And TEOS at a mass ratio of 25: 6.
Preferably, the washing agent used for washing is absolute ethyl alcohol and distilled water.
Preferably, the drying method is freeze drying.
According to the present invention, it is preferable that the ratio of the acetic acid-water solution in step (3) is water: glacial acetic acid =10: 1.
Preferably, MPS and Fe are added3O4@SiO2In a mass ratio of 1: 14.
Preferably, the washing agent used for washing is absolute ethyl alcohol and distilled water.
Preferably, the drying method is freeze drying.
According to the present invention, it is preferable that the template in the step (4): functional monomer: the molar ratio of the cross-linking agent is sanguinarine: 4-vp: EGDMA = 1: 10: 50.
preferably, the reaction is a closed reaction
Preferably, the eluent is selected from a methanol-acetic acid solution, further preferably, methanol: the volume ratio of acetic acid was 9: 1. Here the washing to remove the template molecule was performed at 70 ℃ under reflux for 2 h.
By applying the technical scheme of the invention, SiO is prepared by using a sol-gel method2Shell coating of Fe prepared by hydrothermal method3O4The surface of the nano-particles is not easy to oxidize and is easier to be modified in the next step. Further, the surface thereof was C = C modified with MPS. Further, the modified magnetic microspheres and sanguinarine are subjected to a polymerization reaction initiated by an initiator AIBN in the presence of a 4-vp functional monomer and a cross-linking agent EGDMA to generate the core-shell imprinted magnetic microspheres with the surface containing sanguinarine template molecules. After the eluent elutes the template, sanguinarine template molecule specific holes with fixed shape and size are generated on the surface of the magnetic microsphere, and the sanguinarine molecularly imprinted magnetic polymer microsphere is generated.
The invention has the advantages that:
1. the benzophenanthridine alkaloid (sanguinarine or chelerythrine and the like) molecularly imprinted magnetic polymer microsphere prepared by the method has the advantages of mild reaction conditions, economy, environmental protection, good reproducibility and good application prospect.
2. The obtained particles have uniform size, good monodispersity and good balling property, and have high adsorption capacity to realize the specific separation of sanguinarine.
3. The particles prepared by the invention have stronger magnetism and are easy to separate under an external magnetic field, and the problem that the traditional adsorbing material is difficult to separate is greatly improved.
4. The sanguinarine molecularly imprinted magnetic polymer microsphere prepared by the invention can be applied to extracting solutions containing benzophenanthridine alkaloids such as macleaya cordata, macleaya microcarpa, sanguinarine and the like, and can be used for quickly and efficiently purifying the benzophenanthridine alkaloids such as sanguinarine, chelerythrine and the like.
Description of the drawings:
FIG. 1 shows Fe obtained3O4SEM image of the particles.
FIG. 2 is a TEM image of the resulting MMIPs.
The specific implementation scheme is as follows:
the present invention is further illustrated by, but is not limited to, the following specific examples.
The raw materials used in the examples are conventional reagents, commercial products, and the equipment used is conventional equipment.
Example 1
1. Fe3O4Nanoparticle preparation
1.08g of FeCl3·6H2O is dispersed in 80ml of ethylene glycol by ultrasonic. Then 0.5g of trisodium citrate and 1g of PEG-2000 are added to the solution in succession and dispersed by ultrasound. Finally, 4.5g of anhydrous sodium acetate was added. After the solution was stirred to be clear and transparent, the solution was transferred to a 100ml reaction vessel and reacted at 200 ℃ for 8 hours. After magnetic separation, the mixture was washed three times with water and absolute ethanol alternately. Freeze drying to obtain Fe3O4And (3) nanoparticles.
2. Fe3O4@SiO2Preparation of granules
0.25g of Fe3O4The particles were added to a mixed solution of ethanol-water (160 ml absolute ethanol/40 ml water) and dispersed by ultrasound for 30 min. The resulting solution was transferred to a 250ml three-necked flask, stirred at 500r/min for 15min, then 5ml of ammonia water was added, stirred for 10min, and then 0.6ml of TEOS (tetraethyl orthosilicate) was added dropwise. The mixture reacts for 12 hours at 40 ℃ and 500r/min, the mixture is magnetically separated, and after absolute ethyl alcohol and water are alternately washed for three times, the mixture is frozen and dried to obtain Fe3O4@SiO2And (3) nanoparticles.
3. Vinyl- Fe3O4@SiO2Preparation of granules
250ul MPS (methacryloxypropyltrimethoxysilane) was added dropwise to 55ml of an acetic acid-water mixed solution (50 ml of water, glacial acetic acid) containing 10% acetic acidAcid 5 ml) and stirred at 700r/min for 5h at 25 ℃. Subsequently, 0.34g of Fe was added3O4@SiO2The nanoparticles were stirred in the solution at 60 ℃ at 700r/min for 5.5 h. Magnetic separation, alternately washing with anhydrous ethanol and water for three times, and freeze drying to obtain Vinyl-Fe3O4@SiO2And (3) nanoparticles.
4. Synthesis of surface molecularly imprinted polymer MMIPs
0.01g of template chelerythrine base and 0.1ml of functional monomer 4-VP (4-vinylpyridine) were added to 50ml of acetonitrile and left at 4 ℃ for 12 hours to form a pre-assembled solution of 50 mg of Vinyl-Fe3O4@SiO2Ultrasonic dispersion in 10 ml of acetonitrile was followed by addition of 947ul of crosslinker EGDMA (ethylene glycol dimethacrylate), 0.2g of initiator AIBN (azobisisobutyronitrile) and preassembly solution. Stirring at 500r/min for 24h at 60 ℃ under the protection of nitrogen. Finally, after magnetic separation of the product, the product was washed with acetonitrile until the supernatant was clarified, then eluted with a mixture of methanol and acetic acid (90:10, V/V) until the template was removed, and the particles were washed neutral with methanol and then lyophilized.
Example 2
1. Fe3O4Nanoparticle preparation
1.08g of FeCl3·6H2O is dispersed in 80ml of ethylene glycol by ultrasonic. Then 0.5g of trisodium citrate and 1g of PEG-2000 are added to the solution in succession and dispersed by ultrasound. Finally, 4.5g of anhydrous sodium acetate was added. After the solution was stirred to be clear and transparent, the solution was transferred to a 100ml reaction vessel and reacted at 200 ℃ for 8 hours. After magnetic separation, the mixture was washed three times with water and absolute ethanol alternately. Freeze drying to obtain Fe3O4And (3) nanoparticles.
2. Fe3O4@SiO2Preparation of granules
0.25g of Fe3O4The particles were added to a mixed solution of ethanol-water (160 ml absolute ethanol/40 ml water) and dispersed by ultrasound for 30 min. The resulting solution was transferred to a 250ml three-necked flask, stirred at 500r/min for 15min, then 5ml of ammonia water was added, stirred for 10min, and then 0.6ml of TEOS (tetraethyl orthosilicate) was added dropwise. The mixture is reacted for 12 hours at 40 ℃ and 500r/min, and then is separated magnetically and is made into absolute ethyl alcoholWashing with water for three times, and freeze drying to obtain Fe3O4@SiO2And (3) nanoparticles.
3. Vinyl- Fe3O4@SiO2Preparation of granules
550ul MPS (methacryloxypropyltrimethoxysilane) was added dropwise to 55ml of an acetic acid-water mixed solution (50 ml of water, 5ml of glacial acetic acid) containing 10% acetic acid, and the mixture was stirred at 700r/min at 25 ℃ for 5 hours. Subsequently, 0.34g of Fe was added3O4@SiO2The nanoparticles were stirred in the solution at 60 ℃ at 700r/min for 5.5 h. Magnetic separation, alternately washing with anhydrous ethanol and water for three times, and freeze drying to obtain Vinyl-Fe3O4@SiO2And (3) nanoparticles.
4. Synthesis of surface molecularly imprinted polymer MMIPs
0.03g of template sanguinarine and 0.1ml of the functional monomer 4-VP (4-vinylpyridine) are added to 50ml of acetonitrile and left at 4 ℃ for 12 hours to form a pre-assembled solution, 50 mg of Vinyl-Fe3O4@SiO2Ultrasonic dispersion in 10 ml acetonitrile followed by 947ul crosslinker EGDMA, 0.2g initiator AIBN and preassembly solution. Stirring at 500r/min for 24h at 60 ℃ under the protection of nitrogen. Finally, after magnetic separation of the product, the product was washed with acetonitrile until the supernatant was clarified, then eluted with a mixture of methanol and acetic acid (90:10, V/V) until the template was removed, and the particles were washed neutral with methanol and then lyophilized.
Example 3
1. Preparation of macleaya cordata extract
Collecting Macleaya cordata fruit pod 200g, percolating with 5 times of 1% hydrochloric acid water at 90 deg.C for 3 times, each for 1 hr. After solid-liquid separation, the filtrate was diluted 3 times and used as an extract.
2. Separating and purifying sanguinarine and chelerythrine in extractive solution
Adding 10g of sanguinarine surface molecularly imprinted polymer microspheres into the extracting solution, fully shaking for 30min, standing for 30min, inserting strong magnets into the extracting solution, adsorbing the sanguinarine surface molecularly imprinted polymer microspheres, putting the microspheres into a chromatographic column with the diameter of 1cm, continuously and slowly eluting (leaching) for 2 times by using 100ml of acidic methanol of 2% hydrochloric acid, concentrating the eluent, and recrystallizing to obtain 1.1g of 98% sanguinarine. Adding 10g chelerythrine surface molecularly imprinted polymer microspheres into the extraction solution after removing sanguinarine again, and performing the same method to obtain 98% chelerythrine 0.5 g.
Claims (1)
1. The method for separating benzophenanthridine alkaloids by utilizing the molecularly imprinted polymer magnetic microspheres is characterized by comprising the following operation steps of:
A：Fe3O4nanoparticle preparation
1.08g of FeCl3•6H2Ultrasonically dispersing O in 80mL of glycol, and then sequentially adding 0.5g of trisodium citrate and 1g of PEG-2000 into the solution for ultrasonic dispersion; finally, 4.5g of anhydrous sodium acetate is added, the solution is stirred until the solution is clear and transparent, and then the solution is transferred to a 100ml reaction kettle to react for 8 hours at 200 ℃; after magnetic separation, alternately washing the mixture for three times by using water and absolute ethyl alcohol; freeze drying to obtain Fe3O4A nanoparticle;
B：Fe3O4@SiO2preparation of granules
0.25g of Fe3O4Adding the particles into an ethanol-water mixed solution, wherein the volume ratio of absolute ethanol to water is 160mL absolute ethanol/40 mL water, and performing ultrasonic dispersion for 30 min; transferring the obtained solution into a 250mL three-necked bottle, stirring at 500r/min for 15min, adding 5mL ammonia water, stirring for 10min, and dropwise adding 0.6mL ethyl orthosilicate; the mixture reacts for 12 hours at 40 ℃ and 500r/min, the mixture is magnetically separated, and after absolute ethyl alcohol and water are alternately washed for three times, the mixture is frozen and dried to obtain Fe3O4@SiO2A nanoparticle;
C：Vinyl- Fe3O4@SiO2preparation of granules
Dropwise adding 250ul of methacryloxypropyl trimethoxysilane into 55mL of acetic acid-water mixed solution containing 10% acetic acid, wherein the acetic acid-water mixed solution contains 50mL of water and 5mL of glacial acetic acid, and stirring for 5h at 25 ℃ and 700 r/min; subsequently, 0.34g of Fe was added3O4@SiO2Stirring the nano particles in the solution for 5.5 hours at the temperature of 60 ℃ and at the speed of 700 r/min; magnetic separation, anhydrousWashing with alcohol and water alternately for three times, and freeze drying to obtain Vinyl-Fe3O4@SiO2A nanoparticle;
d: synthesis of benzophenanthridine alkaloid surface molecularly imprinted polymer
Adding 0.03g sanguinarine or chelerythrine and 0.1mL functional monomer 4-vinylpyridine into 50mL acetonitrile, standing at 4 deg.C for 12h to form pre-assembled solution, 50 mg Vinyl-Fe3O4@SiO2Ultrasonically dispersing in 10 mL of acetonitrile, and then adding 947ul of cross-linking agent ethylene glycol dimethacrylate, 0.2g of initiator azobisisobutyronitrile and a pre-assembly solution; stirring for 24 hours at the temperature of 60 ℃ and at the speed of 500r/min under the protection of nitrogen; finally, after magnetic separation of the product, washing the product with acetonitrile until supernatant is clear, eluting the product with a mixed solution of methanol and acetic acid until a template is removed, washing the particles to be neutral with methanol, and then freeze-drying the particles; wherein the volume ratio of methanol to acetic acid in the mixed solution of methanol and acetic acid is 90: 10;
the benzophenanthridine alkaloid is sanguinarine or chelerythrine;
e: adsorption experiments
1) Preparing a macleaya cordata extracting solution: percolating herba Macleayae Cordatae fruit pod 200g with 5 times of 1% hydrochloric acid water at 90 deg.C for 3 times, each for 1 hr; after solid-liquid separation, diluting the filtrate by 3 times to obtain an extract for later use;
2) separating and purifying sanguinarine and chelerythrine in the extracting solution: adding 10g of sanguinarine surface molecularly imprinted magnetic imprinted polymer microspheres into the extracting solution, fully shaking for 30min, standing for 30min, inserting strong magnets into the extracting solution, adsorbing the sanguinarine surface molecularly imprinted magnetic imprinted polymer microspheres, putting the microspheres into a chromatographic column with the diameter of 1cm, continuously and slowly eluting for 2 times by using 100mL of acidic methanol of 2% hydrochloric acid, concentrating the eluent, and recrystallizing to obtain 1.1g of 98% sanguinarine; adding 10g chelerythrine surface molecularly imprinted polymer microspheres into the extraction solution after removing sanguinarine again, and performing the same method to obtain 98% chelerythrine 0.5 g.
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