CN101712731B - Preparation and application of emodin molecular imprinted polymer - Google Patents
Preparation and application of emodin molecular imprinted polymer Download PDFInfo
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- CN101712731B CN101712731B CN2009101290299A CN200910129029A CN101712731B CN 101712731 B CN101712731 B CN 101712731B CN 2009101290299 A CN2009101290299 A CN 2009101290299A CN 200910129029 A CN200910129029 A CN 200910129029A CN 101712731 B CN101712731 B CN 101712731B
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- schuttgelb
- emodin
- imprinted polymer
- methyl alcohol
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Abstract
The invention aims at providing a method for preparing molecular imprinted polymer by taking emodin as a template and for separating and purifying emodin in traditional Chinese medicine, which belongs to the technical field of chemical industrial separation. The method comprises the following steps: (1) dissolving emodin, functional monomer (acrylamide) and cross linker (ethylene glycol dimethacrylate) in pore-foaming agent acetone solution in the mol ratio of 1:3 to 5:20; adding azo diisobutyronitrile initiating agent for initiating polymerization at 56 to 60 DEG C; grinding polymer and sieving, and removing template molecule, unpolymerized functional monomer, cross linker and initiating agent by washing to obtain the emodin molecular imprinted polymer; and (2), taking the emodin molecular imprinted polymer as solid phase to extract fixed phase to separate and purify the emodin components in crude extracts of rhubarb and polygonum cuspidatum which are both traditional Chinese medicines. The prepared molecular imprinted polymer has good identification effect to emodin, and can effectively remove impurity to obtin high-purity emodin.
Description
Affiliated technical field:
What patent of the present invention related to is a kind of method of medical chemistry field of engineering technology, is specifically related to the preparation of Schuttgelb molecularly imprinted polymer and utilizes this polymkeric substance to be the method for emodin in solid extracting agent separation, the purifying natural product.
Background technology:
Schuttgelb belongs to anthraquinone component, and modern pharmacology research shows, rheum officinale have that broad-spectrum antimicrobial, hepatic cholagogic, antitumor, reducing blood-fat, hemostasis are invigorated blood circulation, easing pain and diminishing inflammation is sent out, diuresis, improve renal function, improve many-sided effect such as immunizing power.Schuttgelb has the growth-inhibiting effect of varying strength to the cancer cells of vitro culture, and is stronger to the restraining effect of suspension type growth of cancer cells, and has selectivity and suppress the active effect of neuroectodermal tumors, is a new type anticancer agent.
The effect of Chinese medicine in disease treatment more and more obtains the approval in the world, and its status is promoted significantly, but the ball of traditional Chinese medicine, loose, most formulations such as cream, pellet by the Chinese medicine leaching liquid without extracting or only extracting and process through thick.Along with era development and technical progress, its drawback is outstanding gradually: effective constituent concentration is very low, causes dosage very big, and onset is slow, and absorption and availability are bad, particularly to severe case or the oral patient's unsatisfactory curative effect of inconvenience; Effective constituent and impurity mix does not have the degree of depth to distinguish, and uncertain therapeutic efficacy is cut; Conventional dosage forms is rich in the nutritive ingredient that carbohydrate etc. can supply microbial growth, produce or use in contaminated easily, do not reach the medical and health standard, be difficult to prolonged preservation; Dense taste is difficult to accepted by Hesperian patient.
The traditional Chinese medicines extracts active ingredients exists problems such as complicated steps, energy consumption is high, purity is low, the organic solvent consumption is big; Often need expensive plant and instrument if reach the purpose that is further purified; And expensive, therefore the exploitation of the novel method of more efficiently Chinese medicine extracts active ingredients purifying is particularly important.Molecular imprinting is a kind of preparation process based on the molecularly imprinted polymer on the molecular recognition basis; The molecularly imprinted polymer inside that obtains has and template molecules of interest complementary space structure and functional group; Have memory and recognition function, the template molecules of interest is had specific selectivity.Molecularly imprinted polymer has that selectivity is good, acid and alkali-resistance, organic solvent-resistant, characteristics such as reusable, has than wide application prospect.
Summary of the invention:
The object of the present invention is to provide a kind of method for preparing the Schuttgelb molecularly imprinted polymer, and provide a kind of this polymkeric substance that utilizes to make the separation from the Chinese medicine crude extract of SPE stationary phase, enrichment, purifying method for emodin.The present invention realizes through following technical scheme, comprises that specifically step is following:
1, the preparation of Schuttgelb molecularly imprinted polymer
(1) is that Schuttgelb, function monomer acrylic amide (AM) and linking agent ethylene glycol dimethacrylate (EDMA) are in the acetone soln that was dissolved in as pore-creating agent in 1: 3.5～4.5: 20 according to mol ratio with template molecule, adds initiator Diisopropyl azodicarboxylate (AIBM);
(2) ultrasonic mixing 10min pours solution in the test tube into then, sealing, and logical argon gas (or nitrogen) deoxidation 15min puts into 56～60 ℃ water-bath with the test tube of good seal, and constant temperature polymerization 24h obtains bulk polymer;
(3) polymkeric substance that makes is ground, cross 200 mesh sieves, obtaining particle diameter is less than 74 μ m particles.
(4) use methyl alcohol: acetic acid (8: 1～8: 3) mixed solution is an extraction agent, through cable-styled extraction flush away template molecule and do not have polymeric function monomer and linking agent, checks with UV spectrum, removes residual acetic acid with methyl alcohol then;
(5) polymkeric substance that will remove template molecule obtains the molecularly imprinted polymer of Schuttgelb at 60 ℃ of dry 24h.
(6) preparation method of non-imprinted polymer, except that not adding the template molecule, all the other steps are the same.
2, the Schuttgelb in the SPE separation and purification Chinese medicine crude extract
(1) takes by weighing Chinese medicine giant knotweed or rheum officinale 5g, add people 20% sulfuric acid 10mL, add people's 60% ethanol water 6ml solution; After 45 minutes, divide three extractions with ultrasonic echography, the extracting solution rotary evaporation is removed the back drying in vacuum drying oven of desolvating with the 150mL chloroform; Obtain the Schuttgelb crude extract, subsequent use.
(2) adopt dry column-packing to be filled in the solid-phase extraction column the above-mentioned Schuttgelb molecularly imprinted polymer that obtains, drench pillar with methanol solution after, the upper strata adds a spot of silica sand.
(3) tiger battle or rheum officinale crude extract are dissolved in the methyl alcohol; Last appearance back is with chloroform drip washing solid-phase extraction column; Confirm that with the inspection of some plate impurity is by after wash-out is removed fully; Use methyl alcohol: acetic acid (8: 2) wash-out is retained in the Schuttgelb in the column extractor, with elutriant collection and concentrated, dry, promptly obtains highly purified Schuttgelb.
The molecularly imprinted polymer of the present invention's preparation has the porous surface structure, and Schuttgelb is had good recognition performance, as the filler of SPE, can be used for high efficiency separation, enrichment and the purifying of Schuttgelb composition in the Chinese medicine.
Embodiment
Elaborate in the face of embodiments of the invention down: present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1:
1, the preparation of Schuttgelb molecularly imprinted polymer
Schuttgelb 4mmol, function monomer acrylic amide 14mmol and linking agent EDMA 80mmol mix, and fully are dissolved in the pore-creating agent acetone of 32mL, add initiator A IBN 260mg.Above mixed solution is poured in the test tube, ultrasonic vibration degassing 10min, logical argon gas deoxidation 15min seals rapidly under argon shield.The test tube of good seal put into 56 ℃ water-bath constant temperature polymerization 24h.After the polymerization fully, get firm bar-shaped solid polymer.Polymkeric substance is ground; Cross 200 mesh sieves; Polymkeric substance is put into cable type extractor according, use methyl alcohol: the eluant solution of acetate=8: 1 is removed template molecule and is not had polymeric function monomer and linking agent, uses the residual acetate of methyl alcohol flush away again; Dry 24h under 60 ℃ obtains the Schuttgelb molecularly imprinted polymer.
2, the Schuttgelb in the SPE separation and purification Chinese medicine crude extract
Take by weighing Chinese herb rhubarb 5g, add people 20% sulfuric acid 10mL, add people's 60% ethanol water 6ml solution; Put into UW after ultrasonic 45 minutes; Divide three extractions with the 150mL chloroform, the extracting solution rotary evaporation is removed the back drying in vacuum drying oven of desolvating, obtain the rheum officinale crude extract.Take by weighing the good Schuttgelb imprinted polymer of 1.2mg wash-out, adopt dry column-packing, after the adding methanol solution drenched solid-phase extraction column, the upper strata added a spot of silica sand.Take by weighing rheum officinale crude extract 4mg; Wetted with methanol sample with 1mL; Last appearance, sample introduction pressurizes in the post, and the control flow velocity is 0.8mL/min; After removing impurity with chloroform drip washing (with the check of some plate), using volume ratio again is 8: 2 methyl alcohol: the acetic acid soln wash-out is retained in the Schuttgelb (with the check of some plate) on the column extractor.Obtaining the pure article of Schuttgelb through concentrated, drying is 161.6 μ g.
Embodiment 2:
1, the preparation of Schuttgelb molecularly imprinted polymer
Schuttgelb 2mmol, function monomer acrylic amide 8mmol and linking agent EDMA 40mmol mix, and fully are dissolved in the acetone of 16mL, add initiator A IBN 130mg.
Above mixed solution is poured in the test tube, ultrasonic vibration degassing 10min, logical argon gas deoxidation 15min seals rapidly under argon shield.The test tube of good seal put into 60 ℃ water-bath constant temperature polymerization 24h.The firm bar-shaped solid polymer that polymerization is obtained grinds, and crosses 200 mesh sieves, and polymkeric substance is put into cable type extractor according; Use methyl alcohol: the eluant solution of acetate=8: 2, extraction 32h extracts four times; Each 8h, each solution usage is 80mL, uses the residual acetate of methyl alcohol flush away again; Dry 24h under 60 ℃ obtains the Schuttgelb molecularly imprinted polymer.
2, the Schuttgelb in the SPE separation and purification Chinese medicine crude extract
Adopt dry column-packing, take by weighing the good Schuttgelb imprinted polymer of 600mg wash-out, in the solid-phase extraction column of packing into, after the adding methanol solution drenched solid-phase extraction column, the upper strata added a spot of silica sand.Take by weighing 2mg rheum officinale crude extract, with the wetted with methanol sample of 1mL, sample introduction pressurization in the post, the control flow velocity is 0.6mL/min, and removes impurity with chloroform drip washing successively, using volume ratio again is 8: 2 methyl alcohol: the acetate wash-out is retained in the Schuttgelb on the column extractor.Obtaining the pure article of Schuttgelb through concentrated, drying is 84.5 μ g.
Embodiment 3:
1, the preparation of Schuttgelb molecularly imprinted polymer
Schuttgelb 4mmol, function monomer acrylic amide 18mmo1 and linking agent EDMA 80mmol mix, and fully are dissolved in the pore-creating agent acetone of 32mL, add initiator A IBN 260mg.Above mixed solution is poured in the test tube, ultrasonic vibration degassing 10min, logical argon gas deoxidation 15min seals rapidly under argon shield.The test tube of good seal put into 58 ℃ water-bath constant temperature polymerization 24h.The firm bar-shaped solid polymer that polymerization is obtained grinds, and crosses 200 mesh sieves, and polymkeric substance is put into cable type extractor according; Use methyl alcohol: the eluant solution of acetate=8: 3, extraction 40h extracts five times; Each 8h, each solution usage is 160mL, uses the residual acetate of methyl alcohol flush away again; 60 ℃ of dry 24h obtain the Schuttgelb molecularly imprinted polymer.
2, the Schuttgelb in the SPE separation and purification Chinese medicine crude extract
Adopt dry column-packing, take by weighing the good Schuttgelb imprinted polymer of 600mg wash-out, in the solid-phase extraction column of packing into, after the adding methanol solution drenched solid-phase extraction column, the upper strata added a spot of silica sand.Take by weighing 2mg tiger battle crude extract, pipette the methyl alcohol of about 1mL, wetting sample with transfer pipet; Sample introduction pressurization in the post; The control flow velocity is 0.8mL/min, remove impurity with chloroform drip washing after, using volume ratio again is 8: 2 methyl alcohol: the acetate wash-out is retained in the Schuttgelb on the column extractor.Obtaining the pure article of Schuttgelb through concentrated, drying is 47.3 μ g.
Embodiment 4:
1, the preparation of Schuttgelb molecularly imprinted polymer
Schuttgelb 1mmol, function monomer methylacrylic acid 4mmol and linking agent EDMA 20mmol mix, and fully are dissolved in the acetone of 8mL, add initiator A IBN 65mg.Above mixed solution is poured in the test tube, ultrasonic vibration degassing 10min, logical argon gas deoxidation 15min seals rapidly under argon shield.The test tube of good seal put into 60 ℃ water-bath constant temperature polymerization 24h.After the polymerization fully, get firm bar-shaped solid polymer.Polymkeric substance is ground, cross 200 mesh sieves, polymkeric substance is put into cable type extractor according, use methyl alcohol: the eluant solution of acetate=8: 2; Extraction 24h extracts three times, each 8h, and each solution usage is 40mL; Use the residual acetate of methyl alcohol flush away again, 60 ℃ of dry 24h obtain desired molecularly imprinted polymer.
2, the Schuttgelb in the SPE separation and purification Chinese medicine crude extract
(1) adopt dry column-packing, take by weighing the good Schuttgelb imprinted polymer of 600mg wash-out, in the solid-phase extraction column of packing into, after the adding methanol solution drenched solid-phase extraction column, the upper strata added a spot of silica sand.Take by weighing 1mg tiger battle crude extract, pipette the methyl alcohol of about 1mL, wetting sample with transfer pipet; Sample introduction pressurization in the post; The control flow velocity is 0.8mL/min, remove impurity with chloroform drip washing after, using volume ratio again is 8: 2 methyl alcohol: the acetate wash-out is retained in the Schuttgelb on the column extractor.Obtaining the pure article of Schuttgelb through concentrated, drying is 24.9 μ g.
Description of drawings:
Fig. 1 Schuttgelb molecularly imprinted polymer synthesizes synoptic diagram
The mode of appearance sem photograph of Fig. 2 polymkeric substance
A, Schuttgelb molecularly imprinted polymer b, non-imprinted polymer
Fig. 3 separates the ultraviolet-visible spectrogram that obtains Schuttgelb
Fig. 4 separates the infrared spectrogram of the Schuttgelb that obtains
Claims (2)
1. a method for preparing the Schuttgelb molecularly imprinted polymer is characterized in that, may further comprise the steps:
With template molecule Schuttgelb, function monomer acrylic amide and linking agent ethylene glycol dimethacrylate is in the acetone soln that was dissolved in as pore-creating agent in 1: 3.5～4.5: 20 according to mol ratio, adds the initiator Diisopropyl azodicarboxylate, ultrasonic mixing 10min; Then solution is poured in the test tube into sealing, logical argon gas or nitrogen deoxidation 15min; The test tube of good seal put into 56～60 ℃ water-bath; Constant temperature polymerization 24h obtains bulk polymer, and the polymkeric substance that makes is ground; Cross 200 mesh sieves, obtain particle diameter less than 74 μ m particles; The ratio of using methyl alcohol and acetic acid is that 8: 1～8: 3 solution is as extraction agent; Through cable-styled extraction flush away template molecule and do not have polymeric function monomer and linking agent; Check with UV spectrum; Remove residual acetic acid with methyl alcohol then, the polymkeric substance of removing template molecule at 60 ℃ of dry 24h, is obtained the molecularly imprinted polymer of Schuttgelb.
2. a separation and purification method for emodin is characterized in that, may further comprise the steps:
The Schuttgelb molecularly imprinted polymer that will prepare by method in the claim 1 is filled in the solid-phase extraction column with the dry column-packing method, drench pillar with methanol solution after; The upper strata adds a spot of silica sand; Tiger battle or rheum officinale crude extract are dissolved in the methyl alcohol, after the last appearance, with chloroform drip washing solid-phase extraction column; Confirm that with the inspection of some plate impurity is by after wash-out is removed fully; The ratio of using methyl alcohol and acetic acid is that 8: 2 eluant solution is retained in the Schuttgelb in the column extractor, with elutriant collection and concentrated, dry, promptly obtains highly purified Schuttgelb.
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| CN2009101290299A CN101712731B (en) | 2009-03-13 | 2009-03-13 | Preparation and application of emodin molecular imprinted polymer |
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| CN2009101290299A CN101712731B (en) | 2009-03-13 | 2009-03-13 | Preparation and application of emodin molecular imprinted polymer |
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| CN101712731A CN101712731A (en) | 2010-05-26 |
| CN101712731B true CN101712731B (en) | 2012-11-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102344568B (en) * | 2011-06-10 | 2013-03-06 | 北京大学 | Molecularly imprinted polymer chromatographic column, its preparation method and application |
| CN103554329A (en) * | 2013-10-17 | 2014-02-05 | 江南大学 | Molecularly imprinted polymer based aloe-emodin removal technology |
| CN106417843A (en) * | 2016-09-30 | 2017-02-22 | 许启太 | Betel nut and peony seed coffee and preparation method thereof |
| CN107652463B (en) * | 2017-10-30 | 2019-11-05 | 江苏大学 | A kind of preparation method and application of the molecular engram composite sponge film for Selective Separation rheum emodin |
| CN110567903B (en) * | 2019-08-08 | 2022-03-15 | 安徽师范大学 | Ferroferric oxide modified graphite paper-based molecular imprinting sensor and preparation method and application thereof |
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| CN1718593A (en) * | 2004-07-06 | 2006-01-11 | 中国科学院化学研究所 | A kind of preparation method of molecularly imprinted polymer |
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| CN1718593A (en) * | 2004-07-06 | 2006-01-11 | 中国科学院化学研究所 | A kind of preparation method of molecularly imprinted polymer |
Non-Patent Citations (1)
| Title |
|---|
| 尹艳凤等.大黄素分子印迹整体柱的合成及性能表征.《分析测试学报》.2008,第27卷(第7期),758-761. * |
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