CN104710567B - A kind of preparation method and application of the molecularly imprinted polymer for extracting dencichine - Google Patents
A kind of preparation method and application of the molecularly imprinted polymer for extracting dencichine Download PDFInfo
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Abstract
The invention discloses the methods and applications of a kind of molecularly imprinted polymer for extracting dencichine, dencichine molecularly imprinted polymer is done column chromatography filler dress post, then with Radix Notoginseng extracting solution upper prop, again with the normal hexane/alcohol mixed solution drip washing of volume ratio 10:1, last chromatographic column alcohol eluting, effluent is dencichine, and wherein said alcohol is ethanol, isopropanol, normal propyl alcohol or n-butyl alcohol.Molecular imprinting is applied to the extraction of dencichine in Radix Notoginseng by the present invention first, compared with traditional extraction process, the present invention orienting enriching effect by molecularly imprinted solid phase extraction column, can quickly prepare highly purified dencichine, and the clinical pharmacology for dencichine studies offer raw material sources.
Description
Technical field
A kind of method that the present invention relates to technical field of pharmaceuticals, a kind of molecularly imprinted polymer for extracting dencichine
Preparation method and application.
Background technology
Rare Chinese medicine " Radix Notoginseng " has the functions such as blood circulation promoting and blood stasis dispelling, reducing swelling and alleviating pain, relaxing muscles and tendons and activating QI and blood in the collateral, especially the most famous with hemostatic function,
For one of famous Chinese medicine preparation " YUNNAN BAIYAO " raw material.Compendium of Material Medica claims " pseudo-ginseng hemostatic dissipates blood analgesic therapy ", and Radix Notoginseng has " hemostasis
Not staying the stasis of blood, blood stasis dispelling is not just being hindered " good name, the actually key medicine for the treatment of blood disorders.Ancient Chinese medicine doctor is top grade as hemostasis using Radix Notoginseng, is widely used in and falls
Beat the internal and external haemorrhage diseases such as damage, hemorrhage due to internal injury.The water soluble ingredient dencichine of Radix Notoginseng, is that the one separated from Radix Notoginseng is special
Aminoacid, it can shorten the clotting time of mice, and make platelet counts dramatically increase, but there is presently no dencichine preparation
Production and use.
In Radix Notoginseng the extraction process document report of dencichine and existing patent all use alcohol extraction, residue water extraction, filter, concentrate, positive fourth
Resin chromatography on alcohol extraction, Aqueous extracts, such as Chinese patent CN1267665A, Chinese patent CN1166679C, Chinese patent
CN1865232A etc..These report techniques basically identical, particularly all use in extraction process Sephadex LH-20 and
CM Sephadex C-25 resin column, and these two kinds of resins are the most expensive, relatively costly, and it is time-consuming to process sample, operates skill
Art requires height, to obtain highly purified dencichine, needs more extraction, crystallization, is a difficult problem for industrialized production.
Molecular imprinting (Molecular imprinting technology, MIT) is for obtaining on space structure and binding sites
With the experiment technology of preparing of the polymer that certain a part (commonly referred to template molecule) mates completely, belong to polymer chemistry, material
An interdisciplinary field between material science, biochemistry, analytical chemistry etc..Molecularly imprinted polymer (Molecular
Imprinting polymer, MIPs) refer to target molecule as template molecule, will have the functionalized polymer monomer of complementary structure
Be combined with template molecule by the way of covalently or non-covalently, add cross-linking agent and carry out polyreaction, after having reacted, template is divided
The class that son is formed after extracting has fixed cavitation size and shape and has the cross-linked polymer determining that arranging functional is rolled into a ball.Because system
Standby material has a molecular recognition performance of high selectivity and brilliance, quickly Solid-Phase Extraction, artificial zymetology, chiral separation,
The aspect such as biosensor, asymmetry catalysis is widely used.At natural active matter separation field, that is reported divides
Sub-engram technology is used for the isolated and purified of flavonoid, polyatomic phenol, alkaloids, steroid and Coumarins.
Have not yet to see the report utilizing method that molecular imprinting extracts dencichine from Radix Notoginseng.It is primarily present following reason:
Template " dencichine " is expensive, it is considered to cost and income, utilize template " dencichine " to prepare molecular engram polymerization on a large scale
Thing is irrational, if using general material to replace dencichine, it will the molecularly imprinted polymer selection to dencichine occur
Property poor, prepare dencichine purity the lowest, the most also there is no a kind of low-cost material to replace dencichine, and
The molecularly imprinted polymer selectivity arrived is strong, can be used for orienting enriching dencichine.
Summary of the invention
It is an object of the invention to provide a kind of molecularly imprinted polymer for extracting dencichine from Radix Notoginseng and method, on realizing
Stating purpose, the present invention adopts the following technical scheme that
The invention provides the preparation method of a kind of imprinted polymer for extracting dencichine, comprise the steps:
1) it is 1～3:2～6:15～30 in mass ratio by vacation template molecule, function monomer, cross-linking agent, initiator, perforating agent:
0.05～0.10:20～70 are mixed and made into homogeneous system, ultrasonic degassing, under nitrogen protection, are polymerized 18～24 hours in 40～60 DEG C；
Obtain the polymer of band template molecule；
2) by step 1) polymer prepared clays into power, and crosses 150～200 mesh sieves, then with the mixed solution of alcohol with organic acid
Carry out drip washing, leacheate is carried out efficient Liquid Detection, till detecting without template material, be dried, obtain dencichine molecule
Imprinted polymer.
Further, described false template molecule is phenylpyruvic acid, DL-tyrosine or glycine-DL-LEUCINE, the sweetest ammonia
Acid-DL-LEUCINE.
Further, described function monomer is acrylamide, methacrylic acid or 4-vinylpridine, preferably 4-vinyl
Pyridine.
Further, described cross-linking agent is N, N-dimethyl diacrylamine, Ethylene glycol dimethacrylate or divinyl
Benzene, preferably Ethylene glycol dimethacrylate.
Further, described perforating agent is chloroform；Described initiator is azodiisobutyronitrile or AMBN, is preferably
Azodiisobutyronitrile.
Further, the mixed solution of described alcohol and organic acid be volume fraction be the acetic acid methanol solution of 10%～20%, wherein,
The mol ratio of acetic acid and methanol is.
Further, 50～65 DEG C of drying under the condition of described dried is vacuum.
Imprinted polymer for extracting dencichine prepared by any of the above-described described method.
Present invention also offers the application in extracting dencichine of the above-mentioned imprinted polymer for extracting dencichine, it is characterised in that
Comprise the steps: to make column chromatography filler dress post with above-mentioned for extracting the molecularly imprinted polymer of dencichine, then use Radix Notoginseng
Root extracting solution upper prop, then with the normal hexane that volume ratio is 10:1/mixed alkoxide solution drip washing, last chromatographic column alcohol eluting, flow out
Liquid is dencichine.
Further, described alcohol is ethanol, isopropanol, normal propyl alcohol or n-butyl alcohol.
The dencichine molecularly imprinted polymer prepared by said method.
Beneficial effects of the present invention:
1. molecular imprinting is applied to the extraction of dencichine in Radix Notoginseng by the present invention first, compared with tradition dencichine extracting method,
The present invention orienting enriching effect by molecular engram-solid-phase extraction column, easy can prepare highly purified dencichine, for dencichine
Clinical pharmacology research provide raw material sources.
2. the present invention uses " false template " molecular imprinting, phenylpyruvic acid, DL-tyrosine or the glycine-DL-being easy to get by simplicity
The real replica " dencichine " that leucine fictitious hosts is expensive, can be to prepare molecularly imprinted polymer on a large scale to provide the most former
Material source, makes cost be substantially reduced.
3. the molecularly imprinted polymer selectivity of the present invention is strong, and when orienting enriching dencichine, only dencichine molecule can enter
Enter in the middle of trace, and other impurity molecule can not enter trace so that this molecularly imprinted polymer primary attachment dencichine, its
Its impurity absorption seldom so as to get the purity of dencichine can reach more than 98%.
4. the present invention's is the most renewable for extracting the molecularly imprinted polymer of dencichine, and its renovation process is simple,
Feasible.
5. the molecularly imprinted polymer that the method prepares, its material leaves hole (or referred to as trace), dencichine is had height
The selectivity of degree.
Accompanying drawing explanation
Fig. 1 is the eluent high-efficient liquid phase chromatogram that embodiment 1 prepares, i.e. Radix Notoginseng after molecular engram-solid phase extraction
Element liquid chromatogram；
Fig. 2 is the dencichine and the molecular structural formula of analog used in the present invention.
Fig. 3 embodiment 1 imprinted polymer Electronic Speculum figure
The imprinted polymer Electronic Speculum figure of Fig. 4 embodiment 2
The imprinted polymer Electronic Speculum figure of Fig. 5 embodiment 3
Process chart prepared by Fig. 6 present invention
Detailed description of the invention
The invention will be further described with embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The preparation of dencichine vacation template molecule imprinted polymer:
(1) get the raw materials ready
Each raw material components is by following consumption proportion dispensing: false template molecule phenylpyruvic acid, function monomer 4-vinylpridine 1.66g,
Cross-linking agent Ethylene glycol dimethacrylate 16.12g, initiator azodiisobutyronitrile 0.13g, perforating agent chloroform 45.34g；
(2) preparation is with the polymer of template molecule
The phenylpyruvic acid got ready above-mentioned, 4-vinylpridine, Ethylene glycol dimethacrylate, azodiisobutyronitrile, chloroform
Joining mix homogeneously in reactor, ultrasonic degassing 15min, then nitrogen charging deoxygenation 15 minutes, in 60 DEG C of waters bath with thermostatic control after sealing
It is polymerized 24 hours, obtains the polymer with template molecule；
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
By milled for the polymer of above-mentioned preparation 200 mesh sieves, i.e. obtain the polymer beads with false template molecule, use acetic acid body
Fraction is the methanol solution eluting of 10%, after being vacuum dried in 60 DEG C, obtains molecularly imprinted polymer 18.4g.
The application in dencichine extracts of the dencichine vacation template molecule imprinted polymer:
Take the molecularly imprinted polymer dress post that 15 grams of the present embodiment prepare, weigh 100g Radix Notoginseng and pulverize, add 500mL acetone
After heating and refluxing extraction 2h, filter, filtrate upper prop.After upper prop solution flows to end, enter with normal hexane/ethanol (10:1, v/v)
Row drip washing, obtains leacheate.Chromatographic column ethanol elution, obtains eluent.Eluent high-efficient liquid phase chromatogram is as it is shown in figure 1, wash
In de-liquid, dencichine purity is 99.6%.Result explanation molecular engram-Solid-Phase Extraction have preferable concentration effect to Radix Notoginseng.
The regeneration of dencichine vacation template molecule imprinted polymer: by the above-mentioned molecularly imprinted polymer washing away dencichine, use 95% second
Alcohol eluting, the most renewable extracts use for next time.
Embodiment 2
The preparation of dencichine vacation template molecule imprinted polymer:
(1) get the raw materials ready
The each component of the present embodiment is by following consumption proportion dispensing: template molecule DL-tyrosine 0.91g, function list acrylamide
1.83g, cross-linking agent N, N-dimethyl diacrylamine 24.00g, initiator azodiisobutyronitrile 0.15g, solvent chloroform 50.00g.
(2) preparation is with the polymer of template molecule
By the DL-tyrosine got ready in step (1), acrylamide, N, N-dimethyl diacrylamine, azodiisobutyronitrile and
Chloroform joins mix homogeneously in reactor, and ultrasonic degassing 15min, then nitrogen charging deoxygenation 15 minutes, in 60 DEG C of constant temperature after sealing
Water-bath is polymerized 24 hours, obtains the polymer with template molecule；
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
Milled 200 mesh sieves of polymer step (2) prepared, i.e. obtain the polymer beads with template molecule dencichine,
It is 18% methanol solution eluting by acetic acid volume fraction, after being vacuum dried in 60 DEG C, obtains molecularly imprinted polymer 21.1g.
Application in dencichine vacation template molecule imprinted polymer extraction dencichine:
Take the molecularly imprinted polymer dress post that 20 grams of the present embodiment prepare.Weigh 100g Radix Notoginseng to pulverize, add 500mL acetone
After heating and refluxing extraction 2h, filter, filtrate upper prop.After upper prop solution flows to end, molten with normal hexane/ethanol (10:1, v/v)
Liquid 300 milliliters carries out drip washing, obtains leacheate, chromatographic column n-butyl alcohol eluting, obtains eluent, and in eluent, dencichine purity is
99.1%.Result explanation molecular engram-Solid-Phase Extraction have preferable concentration effect to Radix Notoginseng.
The regeneration of dencichine vacation template molecule imprinted polymer: by the above-mentioned molecularly imprinted polymer washing away dencichine, use 95% second
Alcohol eluting, the most renewable extracts use for next time.
Embodiment 3
The preparation of dencichine vacation template molecule imprinted polymer:
(1) get the raw materials ready
The each component of the present embodiment is by following consumption proportion dispensing: template molecule glycine-DL-LEUCINE 0.85g, function monomer first
Base acrylic acid 1.66g, cross-linker divinylbenzene 21.10g, initiator (AMBN) 0.10g, solvent chloroform 47.00g.
(2) preparation is with the polymer of template molecule
By the glycine-DL-LEUCINE got ready in step (1), methacrylic acid, divinylbenzene, AMBN, chlorine
Mix homogeneously in imitative addition reactor, ultrasonic degassing 15min, then nitrogen charging deoxygenation 15 minutes, in 60 DEG C of waters bath with thermostatic control after sealing
It is polymerized 24 hours, obtains the polymer with template molecule；Then by its milled 200 mesh sieves, i.e. obtain with template molecule
The molecularly imprinted polymer granule of dencichine.
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
Milled 200 mesh sieves of polymer step (2) prepared, i.e. obtain the polymer beads with template molecule, use acetic acid
Volume fraction is 12% methanol solution eluting, after being vacuum dried in 60 DEG C, obtains molecularly imprinted polymer 19.8g.
Application in dencichine vacation template molecule imprinted polymer extraction dencichine:
Take the molecularly imprinted polymer dress post that 15 grams of the present embodiment prepare.Weigh 100g Radix Notoginseng to pulverize, add 500mL acetone
After heating and refluxing extraction 2h, filter, filtrate upper prop.After upper prop solution flows to end, molten with normal hexane/ethanol (10:1, v/v)
Liquid 300 milliliters carries out drip washing, obtains leacheate, chromatographic column isopropanol eluting, obtains eluent, and in eluent, dencichine purity is
98.1%.Result explanation molecular engram-Solid-Phase Extraction have preferable concentration effect to Radix Notoginseng.
The regeneration of dencichine vacation template molecule imprinted polymer: by the above-mentioned molecularly imprinted polymer washing away dencichine, use 95% second
Alcohol eluting, the most renewable extracts use for next time.
Embodiment 4
The preparation of dencichine vacation template molecule imprinted polymer:
(1) get the raw materials ready
The each component of the present embodiment is by following consumption proportion dispensing: template molecule glycine-DL-LEUCINE 1.97g, function monomer 4-
Vinylpyridine 3.63g, cross-linking agent N, N-dimethyl diacrylamine 31.00g, initiator azodiisobutyronitrile 0.10g, system
Hole agent chloroform 54.00g.
(2) preparation is with the polymer of template molecule
By the glycine-DL-LEUCINE got ready in step (1), 4-vinylpridine, N, N-dimethyl diacrylamine, azo
Bis-isobutyronitrile, chloroform join mix homogeneously in reactor, and ultrasonic degassing 15min, then nitrogen charging deoxygenation 15 minutes, after sealing
It is polymerized 24 hours in 60 DEG C of waters bath with thermostatic control, obtains the polymer with template molecule；
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
Milled 200 mesh sieves of polymer step (2) prepared, i.e. obtain the polymer beads with template molecule, use acetic acid
Volume fraction is 10% methanol solution eluting by the molecularly imprinted polymer granule with template molecule obtained by step (2), in
After 60 DEG C of vacuum drying, obtain molecularly imprinted polymer 28.4g.
Application in dencichine vacation template molecule imprinted polymer extraction dencichine:
Take the molecularly imprinted polymer dress post that 13 grams of the present embodiment prepare.Weigh 100g Radix Notoginseng to pulverize, add 500mL acetone
After heating and refluxing extraction 2h, filter, filtrate upper prop.After upper prop solution flows to end, molten with normal hexane/ethanol (10:1, v/v)
Liquid 300 milliliters carries out drip washing, obtains leacheate, chromatographic column isopropanol eluting, obtains eluent, and in eluent, dencichine purity is
98.6%.Result explanation molecular engram-Solid-Phase Extraction have preferable concentration effect to Radix Notoginseng.
The regeneration of dencichine vacation template molecule imprinted polymer: by the above-mentioned molecularly imprinted polymer washing away dencichine, use 95% second
Alcohol eluting, the most renewable extracts use for next time.
Embodiment 5
The preparation of dencichine vacation template molecule imprinted polymer:
(1) get the raw materials ready
The each component of the present embodiment is by following consumption proportion dispensing: template molecule glycine-DL-LEUCINE 2.27g, function monomer 4-
Vinylpyridine 3.63g, cross-linker divinylbenzene 34.00g, initiator azodiisobutyronitrile 0.12g, perforating agent chloroform 54.00g.
(2) preparation is with the molecularly imprinted polymer of template molecule
By template molecule 2-hydroxyl-6-alkoxybenzoic acid (n=7) got ready in step (1), 4-vinylpridine, divinyl
Base benzene, azodiisobutyronitrile, the mixed solvent of chloroform add mix homogeneously in reactor, ultrasonic degassing 15min, then nitrogen charging
Deoxygenation 15 minutes, is polymerized 24 hours in 60 DEG C of waters bath with thermostatic control after sealing, obtains the polymer with template molecule；
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
Milled 200 mesh sieves of polymer step (2) prepared, i.e. obtain the polymer beads with template molecule, use acetic acid
Volume fraction is 10% methanol solution eluting, after being vacuum dried in 60 DEG C, obtains molecularly imprinted polymer 25.7g.
Application in dencichine vacation template molecule imprinted polymer extraction dencichine:
Take the molecularly imprinted polymer dress post that 20 grams of the present embodiment prepare.Weigh 100g Radix Notoginseng to pulverize, add 500mL acetone
After reflux, extract, 2h, filter, filtrate upper prop.After upper prop solution flows to end, with normal hexane/ethanol (10:1, v/v) solution
300 milliliters carry out drip washing, obtain leacheate, chromatographic column n-butyl alcohol eluting, obtain eluent, and in eluent, dencichine purity is 99.1%.
Result explanation molecular engram-Solid-Phase Extraction have preferable concentration effect to Radix Notoginseng.
The regeneration of dencichine vacation template molecule imprinted polymer: by the above-mentioned molecularly imprinted polymer washing away dencichine, use 95% second
Alcohol eluting, the most renewable extracts use for next time.
Embodiment 6
The preparation of dencichine vacation template molecule imprinted polymer:
(1) get the raw materials ready
The each component of the present embodiment is by following consumption proportion dispensing: template molecule phenylpyruvic acid 2.57g, function monomer acrylamide
3.67g, cross-linking agent N, N-dimethyl diacrylamine 38.00g, initiator azodiisobutyronitrile 0.10g, perforating agent chloroform 50.00g.
(2) preparation is with the polymer of template molecule
By different to the template molecule phenylpyruvic acid got ready in step (1), acrylamide, N, N-dimethyl diacrylamine, azo two
Butyronitrile, the mixed solvent of chloroform add mix homogeneously in reactor, and ultrasonic degassing 15min, then nitrogen charging deoxygenation 15 minutes, close
It is honored as a queen and is polymerized 24 hours in 60 DEG C of waters bath with thermostatic control, obtain the polymer with template molecule；
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
Milled 200 mesh sieves of polymer step (2) prepared, i.e. obtain the polymer beads with template molecule, use acetic acid
Volume fraction is 10% methanol solution eluting, after being vacuum dried in 60 DEG C, obtains molecularly imprinted polymer 27.4g.
Application in dencichine vacation template molecule imprinted polymer extraction dencichine:
Take the molecularly imprinted polymer dress post that 20 grams of the present embodiment prepare.Weigh 100g Radix Notoginseng to pulverize, add 500mL acetone
After heating and refluxing extraction 2h, filter, filtrate upper prop.After upper prop solution flows to end, molten with normal hexane/ethanol (10:1, v/v)
Liquid 300 milliliters carries out drip washing, obtains leacheate, chromatographic column ethanol elution, obtains eluent, and in eluent, dencichine purity is 99.2%.
Result explanation molecular engram-Solid-Phase Extraction have preferable concentration effect to Radix Notoginseng.
The regeneration of dencichine vacation template molecule imprinted polymer: by the above-mentioned molecularly imprinted polymer washing away dencichine, use 95% second
Alcohol eluting, the most renewable extracts use for next time.
Embodiment 7
The preparation of dencichine vacation template molecule imprinted polymer:
(1) get the raw materials ready
The each component of the present embodiment is by following consumption proportion dispensing: template molecule DL-tyrosine 3.37g, function monomer 4-vinylpyridine
Pyridine 5.53g, cross-linking agent Ethylene glycol dimethacrylate 37.00g, initiator AMBN 0.10g, perforating agent chloroform
60.00g。
(2) preparation is with the polymer of template molecule
By the DL-tyrosine got ready in step (1), 4-vinylpridine, Ethylene glycol dimethacrylate, azo diisoamyl
Nitrile, chloroform join mix homogeneously in reactor, and ultrasonic degassing 15min, then nitrogen charging deoxygenation 15 minutes, in 60 DEG C after sealing
Water bath with thermostatic control is polymerized 24 hours, obtains the polymer with template molecule；
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
Milled 200 mesh sieves of polymer step (2) prepared, i.e. obtain the polymer beads with template molecule, use acetic acid
Volume fraction is 10% methanol solution eluting, after being vacuum dried in 60 DEG C, i.e. obtains molecularly imprinted polymer 28.7g.
Application in dencichine vacation template molecule imprinted polymer extraction dencichine:
Take the molecularly imprinted polymer dress post that 20 grams of the present embodiment prepare.Weigh 100g Radix Notoginseng to pulverize, add 500mL acetone
After heating and refluxing extraction 2h, filter, filtrate upper prop.After upper prop solution flows to end, molten with normal hexane/ethanol (10:1, v/v)
Liquid 300 milliliters carries out drip washing, obtains leacheate, chromatographic column ethanol elution, obtains eluent, and in eluent, dencichine purity is 98.7%.
Result explanation molecular engram-Solid-Phase Extraction have preferable concentration effect to Radix Notoginseng.
The regeneration of dencichine vacation template molecule imprinted polymer: by the above-mentioned molecularly imprinted polymer washing away dencichine, use 95% second
Alcohol eluting, the most renewable extracts use for next time.
Embodiment 8
The preparation of dencichine vacation template molecule imprinted polymer:
(1) get the raw materials ready
The each component of the present embodiment is by following consumption proportion dispensing: template molecule DL-tyrosine 3.57g, function monomer methacrylic acid
5.97g, cross-linking agent Ethylene glycol dimethacrylate 38.00g, initiator AMBN 0.10g, perforating agent chloroform 61.00g.
(2) preparation is with the polymer of template molecule
By the DL-tyrosine got ready in step (1), methacrylic acid, Ethylene glycol dimethacrylate, AMBN,
Chloroform joins mix homogeneously in reactor, and ultrasonic degassing 15min, then nitrogen charging deoxygenation 15 minutes, in 60 DEG C of constant temperature after sealing
Water-bath is polymerized 24 hours, obtains the polymer with template molecule；
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
Milled 200 mesh sieves of polymer step (2) prepared, i.e. obtain the polymer beads with template molecule, use acetic acid
Volume fraction is 10% methanol solution eluting, after being vacuum dried in 60 DEG C, i.e. obtains molecularly imprinted polymer 30.4g.
Application in dencichine vacation template molecule imprinted polymer extraction dencichine:
Take the molecularly imprinted polymer dress post that 20 grams of the present embodiment prepare.Weigh 100g Radix Notoginseng to pulverize, add 500mL acetone
After heating and refluxing extraction 2h, filter, filtrate upper prop.After upper prop solution flows to end, molten with normal hexane/ethanol (10:1, v/v)
Liquid 300 milliliters carries out drip washing, obtains leacheate, chromatographic column isopropanol eluting, obtains eluent, and in eluent, dencichine purity is
98.8%.Result explanation molecular engram-Solid-Phase Extraction have preferable concentration effect to Radix Notoginseng.
The regeneration of dencichine vacation template molecule imprinted polymer: by the above-mentioned molecularly imprinted polymer washing away dencichine, use 95% second
Alcohol eluting, the most renewable extracts use for next time.
Embodiment 9
The preparation of dencichine vacation template molecule imprinted polymer:
(1) get the raw materials ready
The each component of the present embodiment is by following consumption proportion dispensing: template molecule phenylpyruvic acid 3.21g, function monomer 4-vinylpridine
6.63g, cross-linker divinylbenzene 35.76g, initiator azodiisobutyronitrile 0.10g, perforating agent chloroform 55.00g.
(2) preparation is with the polymer of template molecule
By the phenylpyruvic acid got ready in step (1), 4-vinylpridine, divinylbenzene, azodiisobutyronitrile, chloroform mixed
Bonding solvent adds mix homogeneously in reactor, and ultrasonic degassing 15min, then nitrogen charging deoxygenation 15 minutes, in 60 DEG C of constant temperature after sealing
Water-bath is polymerized 24 hours, obtains the polymer with template molecule；
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
Milled 200 mesh sieves of polymer step (2) prepared, i.e. obtain the polymer beads with template molecule, use acetic acid
Volume fraction is 10% methanol solution eluting, after being vacuum dried in 60 DEG C, i.e. obtains molecularly imprinted polymer 30.1g.
Application in dencichine vacation template molecule imprinted polymer extraction dencichine:
Take the molecularly imprinted polymer dress post that 20 grams of the present embodiment prepare.Weigh 100g Radix Notoginseng to pulverize, add 500mL acetone
After heating and refluxing extraction 2h, filter, filtrate upper prop.After upper prop solution flows to end, molten with normal hexane/ethanol (10:1, v/v)
Liquid 300 milliliters carries out drip washing, obtains leacheate, chromatographic column isopropanol eluting, obtains eluent, and in eluent, dencichine purity is
98.5%.Result explanation molecular engram-Solid-Phase Extraction have preferable concentration effect to Radix Notoginseng.
The regeneration of dencichine vacation template molecule imprinted polymer: by the above-mentioned molecularly imprinted polymer washing away dencichine, use 95% second
Alcohol eluting, the most renewable extracts use for next time.
Although the above-mentioned detailed description of the invention to the present invention is described, but not limiting the scope of the invention, affiliated
Skilled person should be understood that on the basis of technical scheme, and those skilled in the art need not pay creativeness
Various amendments that work can be made or deformation are still within protection scope of the present invention.
Claims (9)
1. the preparation method being used for extracting the imprinted polymer of dencichine, it is characterised in that comprise the steps:
1) it is that 1 ~ 3:2 ~ 6:15 ~ 30:0.05 ~ 0.10:20 ~ 70 are mixed and made into homogeneous system, ultrasonic degassing in mass ratio by vacation template molecule, function monomer, cross-linking agent, initiator, perforating agent, under nitrogen protection, is polymerized 18 ~ 24 hours in 40 ~ 60 DEG C；Obtain the polymer of band template molecule；
2) polymer prepared by step 1) is clayed into power,
Cross 150 ~ 200 mesh sieves, then carry out drip washing with the mixed solution of alcohol Yu organic acid, leacheate is carried out efficient Liquid Detection, till detecting without template material, be dried, obtain dencichine molecularly imprinted polymer;Described false template molecule is phenylpyruvic acid, DL-tyrosine or glycine-DL-LEUCINE.
2. the method for claim 1, it is characterised in that described function monomer is acrylamide, methacrylic acid or 4-vinylpridine.
3. the method for claim 1, it is characterised in that described cross-linking agent is N, N-dimethyl diacrylamine, Ethylene glycol dimethacrylate or divinylbenzene.
4. the method for claim 1, it is characterised in that described perforating agent is chloroform；Described initiator is azodiisobutyronitrile or AMBN.
5. the method for claim 1, it is characterised in that described alcohol is with the mixed solution of organic acid, and alcohol is 9:1 with the volume ratio of organic acid.
6. method as above-mentioned in claim 1, it is characterised in that the condition of described dried is 50 ~ 65 DEG C of drying under vacuum.
7. the molecularly imprinted polymer for extracting dencichine that prepared by the arbitrary described method of claim 1-6.
8. the application in extracting dencichine of the molecularly imprinted polymer described in claim 7, it is characterized in that, column chromatography filler dress post is made with the molecularly imprinted polymer described in claim 7, then with Radix Notoginseng extracting solution upper prop, again with the normal hexane that volume ratio is 10:1/mixed alkoxide solution drip washing, last chromatographic column alcohol eluting, effluent is dencichine.
Apply the most as claimed in claim 8, it is characterised in that described alcohol is ethanol, isopropanol, normal propyl alcohol or n-butyl alcohol.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775554A (en) * | 2012-07-06 | 2012-11-14 | 江南大学 | Preparation method for cinnamaldehyde surface molecularly imprinted polymer |
| CN103570870A (en) * | 2013-10-21 | 2014-02-12 | 南京医科大学 | Multi-template monodisperse active notoginsenoside molecular imprinted polymer and preparation method thereof |
| CN104004220A (en) * | 2014-06-10 | 2014-08-27 | 山东省分析测试中心 | Capsaicin fake-template molecularly-imprinted polymer, preparation method and applications thereof |
| CN104277177A (en) * | 2014-10-28 | 2015-01-14 | 山东省分析测试中心 | Gingerol pseudo-template molecularly imprinted polymer and method for extracting gingerol from fresh gingers by using same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775554A (en) * | 2012-07-06 | 2012-11-14 | 江南大学 | Preparation method for cinnamaldehyde surface molecularly imprinted polymer |
| CN103570870A (en) * | 2013-10-21 | 2014-02-12 | 南京医科大学 | Multi-template monodisperse active notoginsenoside molecular imprinted polymer and preparation method thereof |
| CN104004220A (en) * | 2014-06-10 | 2014-08-27 | 山东省分析测试中心 | Capsaicin fake-template molecularly-imprinted polymer, preparation method and applications thereof |
| CN104277177A (en) * | 2014-10-28 | 2015-01-14 | 山东省分析测试中心 | Gingerol pseudo-template molecularly imprinted polymer and method for extracting gingerol from fresh gingers by using same |
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