CN102167777B - Preparation method and application of molecularly imprinted polymer - Google Patents
Preparation method and application of molecularly imprinted polymer Download PDFInfo
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- CN102167777B CN102167777B CN2010106132557A CN201010613255A CN102167777B CN 102167777 B CN102167777 B CN 102167777B CN 2010106132557 A CN2010106132557 A CN 2010106132557A CN 201010613255 A CN201010613255 A CN 201010613255A CN 102167777 B CN102167777 B CN 102167777B
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Abstract
The invention provides a method for refining a molecularly imprinted polymer. The method comprises the following steps of: mixing tanshinone IIA serving as a template, a functional monomer, a cross-linking agent, an initiator and a pore-forming agent to prepare a homogeneous system; performing polymerization under the protection of nitrogen; grinding the prepared material into powder and sieving; and soaking, washing and eluting the powder with an alcohol solvent to obtain the molecularly imprinted polymer. The molecularly imprinted polymer prepared by the method represents high affinity and selectivity on the tanshinone IIA in an aqueous mobile phase, serves as a specific separating material and has a wide application prospect on separation, enrichment and purification of the tanshinone IIA in the Chinese medicament. In the method, materials are mixed in one step during synthesis; the preparation process is obviously simplified; time is saved; and an aqueous phase elution system is adopted, so that the application range is enlarged and the elution effect is obvious. The tanshinone IIA provided by the invention can serve as a solid phase extraction material to separate and purify the tanshinone IIA from a salvia miltiorrhiza bunge ethanol crude extract.
Description
Technical field
The invention belongs to the preparation field of active ingredient of Chinese herbs, particularly a kind of method for preparing molecularly imprinted polymer, and the application of this polymkeric substance in refining tanshinone IIA.
Background technology
The red sage root has stasis-dispelling and pain-killing, promoting blood circulation to restore menstrual flow, the effect of the relieving restlessness that clears away heart-fire, and is the traditional Chinese medicine of treatment cardiovascular and cerebrovascular diseases.The chemical ingredients of the red sage root mainly is divided into fat-soluble component and water soluble component two big classes, and fat-soluble component is mainly diterpene-kind compound, like Tanshinone II A, VSZ3505, Tanshinone I etc.Tanshinone compound is fat-soluble staple, and meta-bolites in vivo shows multiple pharmacological effect, and cardiovascular and cerebrovascular diseases, hepatitis, white blood disease etc. are had the potential therapeutic action.
The process for refining bibliographical information of relevant TANSHINONES is a lot, mainly contains alcohol reflux or percolation and supercritical CO
2Extraction process etc.Above method all is to utilize the similar principle that mixes from extracting on the principle, the effect that dissolve repeatedly, steps such as crystallization, deposition finally reaches purifying.Because above method selectivity is not strong, and one type of fat-soluble composition such as TANSHINONES all has similar physico-chemical property in the red sage root, and the impurity of analog is higher, and the content of Tanshinone II A is on the low side comparatively speaking.Need pass through the multistep operation in addition, take time and effort, be not enough ideal methods therefore.
Molecular imprinting is a kind of novel technology, uses this technology and can adopt the synthetic molecularly imprinted polymer to different compounds of different templates targetedly.Owing in building-up process, add template molecule; Form interactional mixture with function monomer, and then add linking agent initiated polymerization under action of evocating, form high molecular polymkeric substance; Afterwards through grinding; Operations such as wash-out are removed template molecule, obtain having the polymkeric substance in the three-dimensional hole of template molecule, and therefore this polymkeric substance has specific recognition capability to template molecule.Because of it prepares simply, stable in properties, high temperature resistant, acid and alkali-resistance, advantages such as organic solvent-resistant make it all be widely used in fields such as chromatographic separation and SPEs.In recent years, begun to be used for the separation of active ingredient of Chinese herbs.
The application of molecular imprinting on the red sage root separates; What report was arranged is that people such as happy health utilize Tanshinone II A to be template; Methylacrylic acid is a monomer, and ethylene glycol dimethacrylate (EDMA) is a linking agent, and ratio is that molecularly imprinted polymer (West China pharmaceutical journal has been synthesized in thermopolymerization in 1: 4: 24; 2009,24 (5): 443～445).But the adsorption isothermal line described in this experiment measures that the strength of solution of employed template molecule is obviously excessive, and we can't repeat through test experiments, so its result's credibility is represented scrupulous suspection.Other has Chinese invention patent application 201010167614.0 to propose a kind of preparation method of core-shell structured composite nano surface molecular imprinted polymer, and this method prepares the process complicacy, and cost is high, is unfavorable for mass preparation and application.
Summary of the invention
The process for purification that the purpose of this invention is to provide a kind of molecularly imprinted polymer is a template with the Tanshinone II A, and the preparation method mainly comprises the following steps:
(1) Tanshinone II A, one or more function monomers, linking agent, initiator, pore-creating agent are mixed and made into homogeneous system according to a certain ratio, under nitrogen protection, in 55-75 ℃ of polymerization 4-24 hour.
(2) material of step (1) preparation is clayed into power; Sieve the back earlier with alcoholic solvent immersion, cleaning; Carry out wash-out with alcohol and organic acid mixing solutions then, in ultraviolet inspection elutriant, do not contain the Tanshinone II A molecule, obtain said target molecule imprinted polymer.
Wherein, said monomer has multiple choices, comprises acrylic acid or the like (for example methylacrylic acid, methyl acrylic ester, vinylformic acid or esters of acrylic acid), pyridines, amides and other types monomer etc.Preferably amides and pyridines, more preferably acrylic amide (AM), 2-vinyl pyridine (2-VP) and methylacrylic acid (MAA).
Linking agent commonly used comprises trimethylolpropane trimethacrylate (TRIM), ethylene glycol dimethacrylate (EDMA), Vinylstyrene (DVB), 3,5-two (acrylic amide) phenylformic acid etc.; Preferably ethylene glycol dimethacrylate (EDMA) and trimethylolpropane trimethacrylate (TRIM).
Pore-creating agent described in the present invention can adopt methylene dichloride, chloroform, acetonitrile, ETHYLE ACETATE, ethanol or methyl alcohol; Preferably methylene dichloride and acetonitrile.
Used initiator is generally organo-peroxide or azo cpd among the present invention; Be preferably Diisopropyl azodicarboxylate (AIBN).
Function monomer is 3-8 with the amount of substance ratio of Tanshinone II A in the step (1): 1; Linking agent is 12-30 with the amount of substance ratio of ginseng ketone IIA: 1; Linking agent is 2-5 with the amount of substance ratio of function monomer: 1; The pore-creating agent consumption is the 6-15mL/mmol Tanshinone II A; Initiator amount is the 60-200mg/mmol Tanshinone II A.
Step of the present invention (1) adopts thermal-initiated polymerization, reactive mode with reactant with ultrasonic mixing after, join in the container, feed airtight polymerization behind 3-5 minute the nitrogen.Reaction conditions is in 55-75 ℃ of polymerization 4-24 hour.
Polyreaction contains template molecule in the resulting polymkeric substance after accomplishing, and needs to remove template molecule through cleaning and just can use.Alcoholic solvent is methyl alcohol or alcohol solvent described in the step (2); Said organic acid is acetate or formic acid; Alcohol is 20-5 with the organic acid volume ratio in said alcohol and the organic acid mixing solutions: 1; Said elution process is cable-styled extraction or soaks suction filtration.
Another object of the present invention provides the application of molecularly imprinted polymer in refining tanshinone IIA that aforesaid method obtains.
Molecularly imprinted polymer provided by the invention can be used as the SPE material and comes the Tanshinone II A in the separation and purification red sage root ethanol crude extract.This method realizes through following steps: with described molecularly imprinted polymer dress post, then sample solution is crossed post, with wash-out, collection purified Tanshinone II A behind the alcoholic solvent cleaning and removing impurity.Sample solution according to the invention is the solution of red rooted salvia extracting solution or red sage root crude extract or other solution that contain Tanshinone II A.
Wherein, the used eluent of decon is that volume ratio is 10-0.5: the mixing solutions of 1 ethanol or methyl alcohol and water; Wash-out, the used eluent of collection Tanshinone II A are that volume ratio is 100-50: 5-50: the mixing solutions of 1 ethanol or methyl alcohol and water, acetate.
The present invention is template molecule with the Tanshinone II A; The molecularly imprinted polymer of preparation has shown good affinity and selectivity to Tanshinone II A in aqueous mobile phase, make it make it aspect separation, enrichment and the purification of species specific parting material Tanshinone II A in to Chinese medicine, wide application prospect arranged as a kind of.The present invention adopts molecular imprinting, prepares a kind ofly novel Tanshinone II A to be had the separating medium of specific selectivity, thereby reaches the effect of selective separation.Though what the present invention used also is the initiation mode of thermopolymerization, only need a step to mix when the present invention is synthetic, obviously simplify on the preparation process than the method for this bibliographical information; Saved required time greatly; And used monomer is also inequality, and application the present invention of polymkeric substance has been attempted multiple condition, confirms to have adopted the water elution system; Its practical ranges is obviously enlarged, and effect also obviously is superior to the result of above bibliographical information.
Description of drawings
Accompanying drawing 1 is the HPLC spectrogram of the sample solution of embodiment 8.
Accompanying drawing 2 is HPLC spectrograms of the extraction raffinate afterwards of embodiment 8.
Accompanying drawing 3 is HPLC spectrograms of removal of impurities liquid of 60% removal of impurities of embodiment 8.
Accompanying drawing 4 is HPLC spectrograms of removal of impurities liquid of 95% removal of impurities of embodiment 8.
Accompanying drawing 5 is HPLC spectrograms of the elutriant of embodiment 8.
Accompanying drawing 6 is HPLC spectrograms of the template molecule reference substance of embodiment 8.
Embodiment
The present invention combines accompanying drawing and embodiment to be further described.
Embodiment 1
Take by weighing 0.5mmol template molecule Tanshinone II A, 2.5mmol function monomer methylacrylic acid (MAA), 10mmol linking agent ethylene glycol dimethacrylate (EDMA), 0.05g initiator Diisopropyl azodicarboxylate (AIBN), 5mL pore-creating agent chloroform; Place 50mL ground round-bottomed flask, ultrasonic 10min is to mixing.Seal behind the logical nitrogen 10min in the ice bath; Put polymerization 24h in 60 ℃ of constant water bath box, obtain red bar polymers.Polymkeric substance is taken out, soak after drying, sieve with methyl alcohol.With the supersound washing of 2 * 100mL methyl alcohol, suction filtration is used 5 * 100mLl methyl alcohol: acetate (V: V=9: mixing solutions ultrasonic cleaning 1) more earlier; Centrifugal, discard the upper strata washings, use the supersound washing of 4 * 100mL methyl alcohol again; Suction filtration till being washed till ultraviolet 270nm repeatedly down no template molecule detecting, is put and is dried to constant weight in the vacuum drying oven; Obtain the Tanshinone II A molecularly imprinted polymer, MIP1.
Embodiment 2
Take by weighing 0.5mmol template molecule Tanshinone II A, 2.5mmol function monomer 2-vinyl pyridine (2-VP), 10mmol linking agent trimethylolpropane trimethacrylate (TRIM), 0.05g initiator Diisopropyl azodicarboxylate (AIBN), 5mL pore-creating agent methylene dichloride; Place 50mL ground round-bottomed flask, ultrasonic 10min is to mixing.Seal behind the logical nitrogen 10min in the ice bath; Put polymerization 8h in 65 ℃ of constant water bath box, obtain red bar polymers.Polymkeric substance is taken out, soak after drying, sieve with methyl alcohol.With the supersound washing of 2 * 100mL methyl alcohol, suction filtration is used 6 * 100mL methyl alcohol: acetate (V: V=9: mixing solutions ultrasonic cleaning 1) more earlier; Centrifugal, discard the upper strata washings, use the supersound washing of 5 * 100mL methyl alcohol again; Suction filtration till being washed till ultraviolet 270nm repeatedly down no template molecule detecting, is put and is dried to constant weight in the vacuum drying oven; Obtain the Tanshinone II A molecularly imprinted polymer, MIP2.
Embodiment 3
Take by weighing 0.5mmol template molecule Tanshinone II A, 2.5mmol function monomer acrylic amide (AM), 10mmol linking agent trimethylolpropane trimethacrylate (TRIM), 0.05g initiator Diisopropyl azodicarboxylate (AIBN), 5mL pore-creating agent acetonitrile; Place 50mL ground round-bottomed flask, ultrasonic 10min is to mixing.Seal behind the logical nitrogen 10min in the ice bath; Put polymerization 12h in 60 ℃ of constant water bath box, obtain red bar polymers.Polymkeric substance is taken out, soak after drying, sieve with methyl alcohol.With the supersound washing of 2 * 100mL methyl alcohol, suction filtration is used 6 * 100mL methyl alcohol: acetate (V: V=8.5: mixing solutions ultrasonic cleaning 1.5) more earlier; Centrifugal, discard the upper strata washings, use the supersound washing of 5 * 100mL methyl alcohol again; Suction filtration till being washed till ultraviolet 270nm repeatedly down no template molecule detecting, is put and is dried to constant weight in the vacuum drying oven; Obtain the Tanshinone II A molecularly imprinted polymer, MIP3.
Embodiment 4
Take by weighing 0.5mmol template molecule Tanshinone II A, 4mmol function monomer methylacrylic acid (MAA), 20mmol linking agent ethylene glycol dimethacrylate (EDMA), 0.04g initiator Diisopropyl azodicarboxylate (AIBN), 6mL pore-creating agent chloroform; Place 50mL ground round-bottomed flask, ultrasonic 10min is to mixing.Seal behind the logical nitrogen 10min in the ice bath; Put polymerization 24h in 55 ℃ of constant water bath box, obtain red bar polymers.Polymkeric substance is taken out, soak after drying, sieve with methyl alcohol.With the supersound washing of 3 * 100mL methyl alcohol, suction filtration is used 7 * 100mL methyl alcohol: acetate (V: V=8.5: mixing solutions ultrasonic cleaning 1.5) more earlier; Centrifugal, discard the upper strata washings, use the supersound washing of 5 * 100mL methyl alcohol again; Suction filtration till being washed till ultraviolet 270nm repeatedly down no template molecule detecting, is put and is dried to constant weight in the vacuum drying oven; Obtain the Tanshinone II A molecularly imprinted polymer, MIP4.
Embodiment 5
Take by weighing 0.5mmol template molecule Tanshinone II A, 4mmol function monomer 2-vinyl pyridine (2-VP), 20mmol linking agent ethylene glycol dimethacrylate (EDMA), 0.04g initiator Diisopropyl azodicarboxylate (AIBN), 6mL pore-creating agent chloroform; Place 50mL ground round-bottomed flask, ultrasonic 10min is to mixing.Seal behind the logical nitrogen 10min in the ice bath; Put polymerization 24h in 55 ℃ of constant water bath box, obtain red bar polymers.Polymkeric substance is taken out, soak after drying, sieve with methyl alcohol.With the supersound washing of 3 * 100mL methyl alcohol, suction filtration is used 7 * 100mL methyl alcohol: acetate (V: V=8.5: mixing solutions ultrasonic cleaning 1.5) more earlier; Centrifugal, discard the upper strata washings, use the supersound washing of 5 * 100mL methyl alcohol again; Suction filtration till being washed till ultraviolet 270nm repeatedly down no template molecule detecting, is put and is dried to constant weight in the vacuum drying oven; Obtain the Tanshinone II A molecularly imprinted polymer, MIP5.
Embodiment 6
Take by weighing 0.5mmol template molecule Tanshinone II A, 3mmol function monomer 2-vinyl pyridine (2-VP), 15mmol linking agent trimethylolpropane trimethacrylate (TRIM), 0.08g initiator Diisopropyl azodicarboxylate (AIBN), 5mL pore-creating agent methylene dichloride; Place 50mL ground round-bottomed flask, ultrasonic 10min is to mixing.Seal behind the logical nitrogen 10min in the ice bath; Put polymerization 24h in 55 ℃ of constant water bath box, obtain red bar polymers.Polymkeric substance is taken out, soak after drying, sieve with methyl alcohol.With the supersound washing of 4 * 100mL methyl alcohol, suction filtration is used 8 * 100mL methyl alcohol: acetate (V: V=8.5: mixing solutions ultrasonic cleaning 1.5) more earlier; Centrifugal, discard the upper strata washings, use the supersound washing of 5 * 100mL methyl alcohol again; Suction filtration till being washed till ultraviolet 270nm repeatedly down no template molecule detecting, is put and is dried to constant weight in the vacuum drying oven; Obtain the Tanshinone II A molecularly imprinted polymer, MIP6.
Embodiment 7
Use more than one mixing functions monomers to synthesize MIP
Take by weighing 0.5mmol template molecule Tanshinone II A, 2mmol function monomer 2-vinyl pyridine (2-VP) and 2mmol function monomer methylacrylic acid (MAA), 20mmol linking agent ethylene glycol dimethacrylate (EDMA), 0.06g initiator Diisopropyl azodicarboxylate (AIBN), 6mL pore-creating agent chloroform; Place 50ml ground round-bottomed flask, ultrasonic 10min is to mixing.Seal behind the logical nitrogen 10min in the ice bath; Put polymerization 24h in 55 ℃ of constant water bath box, obtain red bar polymers.Polymkeric substance is taken out, soak after drying, sieve with methyl alcohol.With the supersound washing of 3 * 100mL methyl alcohol, suction filtration is used 8 * 100mL methyl alcohol: acetate (V: V=8.5: mixing solutions ultrasonic cleaning 1.5) more earlier; Centrifugal, discard the upper strata washings, use the supersound washing of 5 * 100ml methyl alcohol again; Suction filtration till being washed till ultraviolet 270nm repeatedly down no template molecule detecting, is put and is dried to constant weight in the vacuum drying oven; Obtain the Tanshinone II A molecularly imprinted polymer, MIP7.
Embodiment 8 above molecularly imprinted polymers (MIP) are investigated the absorption property of target molecule
With 0.03g molecularly imprinted polymer of the present invention with and the blank polymkeric substance be immersed in the Tanshinone II A methanol solution that 5mL concentration is 0.5mmol/L, the 12h that vibrates under the room temperature makes it reach adsorption equilibrium.HPLC detects the concentration of the Tanshinone II A in the solution of absorption back, calculates adsorptive capacity.The result lists in table 1.The result shows that molecularly imprinted polymer of the present invention has bigger adsorptive capacity for target molecule.And blank polymkeric substance (promptly except not adding template molecule, the identical synthetic polymkeric substance of all the other conditions) then adsorptive capacity is less.This shows that this molecularly imprinted polymer has highly selective to template molecule.
Differing mol imprinted polymer (MIP) is investigated the result to the absorption property of target molecule among the table 1. embodiment 1-6
Embodiment 9 use the present invention made molecularly imprinted polymer solid-phase extraction column (MIP-SPE) enrichment tanshinol extract in Tanshinone II A
95% alcohol extract of the red sage root is made into 60% the ethanolic soln that dry substance concentration is 0.633mg/mL through dilution, as sample solution.
MIP5 is filled in the little glass column, is prepared as solid-phase extraction column (MIP-SPE) certainly, post is high 5 centimetres, and column diameter is 1.1 centimetres; Subsequent use with wetted with methanol.With 50mL sample solution upper prop.Collect effluent, as raffinate.Then earlier with 60% ethanol 40mL and 95% ethanol 40mL flush away impurity; Use 95% ethanol (containing 1% acetate) 100mL wash-out then, collect and respectively to go on foot removal of impurities liquid and elutriant, more than respectively go on foot flow point and detect through HPLC; Calculate the wherein content of Tanshinone II A, and calculate the recovery of Tanshinone II A.Referring to Fig. 1-6, be respectively sample solution, raffinate, removal of impurities liquid, the HPLC spectrogram of elutriant and reference substance.
The result shows, in the raffinate Tanshinone II A seldom, after the two step removal of impurities, the composition except that Tanshinone II A major part is eluted, Tanshinone II A then major part is retained on the pillar.The relative sample solution of the content of the Tanshinone II A in the elutriant improves obviously.Through calculating, the content of the Tanshinone II A in the elutriant reaches 95.3%, and the recovery reaches 92.1%.Explain that this molecularly imprinted polymer has the very high selectivity and the recovery for template molecule.
Claims (9)
1. the process for purification of the molecularly imprinted polymer of a Tanshinone II A is characterized in that, realizes through following steps:
(1) Tanshinone II A, one or more function monomers, linking agent, initiator, pore-creating agent are mixed and made into homogeneous system, under nitrogen protection, in 55-75 ℃ of polymerization 4-24 hour, said function monomer was 3-8 with the amount of substance ratio of Tanshinone II A: 1; Said linking agent is 12-30 with the amount of substance ratio of Tanshinone II A: 1; Linking agent is 2-5 with the amount of substance ratio of function monomer: 1; The pore-creating agent consumption is the 6-15mL/mmol Tanshinone II A; Initiator amount is the 60-200mg/mmol Tanshinone II A;
(2) material of step (1) preparation is clayed into power, sieve, soak, clean with alcoholic solvent earlier, carry out wash-out with alcohol and organic acid mixing solutions then, in ultraviolet inspection elutriant, do not contain Tanshinone II A, obtain molecularly imprinted polymer;
Said function monomer is methylacrylic acid, 2-vinyl pyridine, methacrylic diethylammonium salt ethyl ester, acrylic amide or 4-vinylpridine.
2. the process for purification of the molecularly imprinted polymer of a kind of Tanshinone II A according to claim 1; It is characterized in that: the said linking agent of step (1) is trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, Vinylstyrene or 3,5-two (acrylic amide) phenylformic acid.
3. the process for purification of the molecularly imprinted polymer of a kind of Tanshinone II A according to claim 1, it is characterized in that: the said pore-creating agent of step (1) is methylene dichloride, chloroform, acetonitrile, ETHYLE ACETATE, ethanol or methyl alcohol.
4. the process for purification of the molecularly imprinted polymer of a kind of Tanshinone II A according to claim 1, it is characterized in that: the said initiator of step (1) is organo-peroxide or azo cpd.
5. the process for purification of the molecularly imprinted polymer of a kind of Tanshinone II A according to claim 1; It is characterized in that: step (1) adopts thermal-initiated polymerization; With reactant with ultrasonic mixing after; Join in the container, feed airtight polymerization behind 3-5 minute the nitrogen, reaction conditions is in 55-75 ℃ of polymerization 4-24 hour.
6. the process for purification of the molecularly imprinted polymer of a kind of Tanshinone II A according to claim 1, it is characterized in that: the said alcoholic solvent of step (2) is methyl alcohol or alcohol solvent; Said organic acid is acetate or formic acid; Alcohol is 20-8 with the organic acid volume ratio in said alcohol and the organic acid mixing solutions: 1; Said elution process is cable-styled extraction or soaks suction filtration.
7. the application of molecularly imprinted polymer in refining tanshinone IIA that obtains according to the said method of claim 1; It is characterized in that; Realize through following steps: with described molecularly imprinted polymer dress post, then sample solution is crossed post, wash-out, collection purified Tanshinone II A behind the decon.
8. application according to claim 7 is characterized in that: the volume ratio of removing the used eluent of impurity is 10-0.5: the mixing solutions of 1 ethanol or methyl alcohol and water; Wash-out, the used eluent of collection are that volume ratio is 100-50: 5-50: the mixing solutions of 1 ethanol or methyl alcohol and water, acetate.
9. application according to claim 7 is characterized in that: said sample solution is the solution of red rooted salvia extracting solution or red sage root crude extract or other solution that contain Tanshinone II A.
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| CN102731706B (en) * | 2012-06-20 | 2015-01-21 | 浙江省农业科学院 | Carbofuran molecularly imprinted microspheres, preparation and application thereof |
| CN103232572B (en) * | 2013-04-15 | 2015-04-29 | 华南农业大学 | Molecular imprinting polymer for roxarsone detection, and preparation method thereof |
| CN103217332A (en) * | 2013-05-09 | 2013-07-24 | 曹君 | Pretreatment method of traditional Chinese medicine |
| CN103524676B (en) * | 2013-08-26 | 2014-09-17 | 陕西师范大学 | Preparation method and application of monolithic 2-[(6-oxo-6H-benzo[c]chroman-3-yl)oxyl] propanoic acid column |
| CN103881024B (en) * | 2014-03-07 | 2016-02-10 | 山东省分析测试中心 | Gastrodin molecular engram polymers and preparation method thereof and application |
| CN106117411B (en) * | 2016-06-27 | 2018-06-29 | 山东省分析测试中心 | A kind of covalent bond method danshensu molecularly imprinted polymer and preparation method and application |
| CN110437116B (en) * | 2019-08-05 | 2021-07-27 | 浙江李子园食品股份有限公司 | Method for preparing astaxanthin from haematococcus pluvialis |
| CN113173855B (en) * | 2021-04-13 | 2023-01-31 | 江南大学 | Method for accurately separating and identifying oxidized triglyceride in frying oil |
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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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