CN104277177B - The false template molecule imprinted polymer of a kind of gingerol and extract the method for gingerol with it from ginger - Google Patents
The false template molecule imprinted polymer of a kind of gingerol and extract the method for gingerol with it from ginger Download PDFInfo
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- CN104277177B CN104277177B CN201410589128.6A CN201410589128A CN104277177B CN 104277177 B CN104277177 B CN 104277177B CN 201410589128 A CN201410589128 A CN 201410589128A CN 104277177 B CN104277177 B CN 104277177B
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Abstract
The present invention relates to the false template molecule imprinted polymer of a kind of gingerol and from ginger, extract the method for gingerol with it, by false template, function monomer, linking agent, initiator, perforating agent mixing, ultrasonic degas, then nitrogen deoxygenation is filled, be polymerized 18 ~ 24 hours under 40 ~ 60 DEG C of conditions after sealing, obtain the polymkeric substance being with template molecule; Template molecule is removed by after the polymer abrasive obtained, screening; By the polymkeric substance of removing template molecule, after drying, obtain the false template molecule imprinted polymer of gingerol.False for gingerol template molecule imprinted polymer is done column chromatography filler dress post, and then use ginger extract upper prop, then go out decon with eluent solvent, last chromatography column methanol acetic acid eluant solution, effluent liquid is gingerol.Molecularly imprinted polymer selectivity of the present invention is strong, the purity of the gingerol obtained is improved greatly, and separation costs is lower.
Description
Technical field
The present invention relates to a kind of method extracting general gingerol from ginger, belong to Chinese drug preparation technique field.
Background technology
Ginger (ZingiberofficinaleRoscoe) belongs to zingiberaceous plant, originate in the torrid areas such as China and South East Asia, China's ginger cultivation history is long, records according to China's history records, just starts plantation, edible and medical ginger as far back as Zhou Qin China in period.The domestic and international research to the effective constituent of ginger and report are a lot, dietotherapeutic, have anti-oxidant, anti-inflammatory, anti-mutation, rheumatism, anti-kinetosis, antitumor, the multiple biological activity such as to dispel cold, its extract has been applied to the diseases such as Therapeutic cancer, disease for digest, cardiovascular disorder, ulcer, HIV-1.
Correlative study data shows, above-mentioned biological activity depends mainly on pungency component in ginger-ginger aldehydes matter, is the important compound colony with identity function, can be widely used in food and medicine field.The extraction purification of gingerol is the focus of field of deep processing of farm products in recent years.But ginger aldehydes matter is subject to the factor impacts such as acid, alkali, heat and destroys, these are all separated to it, Purification brings very large difficulty.The extracting method of current gingerol has organic solvent extraction, supercritical fluid extraction, high-speed counter-current extraction method etc.There is the shortcoming that extraction yield is low, have dissolvent residual in solvent extraction method; Although supercritical fluid extraction eliminates dissolvent residual, the purity of gained gingerol is high not enough.Above-mentioned separation in a word, purification process cost in production is higher, and operative technique requires high, to obtain highly purified gingerol, needs more to extract, crystallization, is a difficult problem for suitability for industrialized production.
Molecular imprinting (Molecularimprintingtechnology, MIT) be for obtaining the experiment technology of preparing of polymkeric substance of mating completely with certain a part (being commonly referred to template molecule) on space structure and binding sites, belonging to an interdisciplinary field between polymer chemistry, Materials science, biological chemistry, analytical chemistry etc.Molecularly imprinted polymer (Molecularimprintingpolymer, MIPs) refer to target molecule to be template molecule, the functionalized polymer monomer with complementary structure is combined with template molecule by mode covalently or non-covalently, add linking agent and carry out polyreaction, the class after having reacted, template molecule being extracted rear formation has fixed cavitation size and shape and has the cross-linked high polymer determining that arranging functional is rolled into a ball.Because the material of preparation has the molecular recognition performance of high selectivity and brilliance, to be widely used in Solid-Phase Extraction, artificial zymetology, chiral separation, biosensor, asymmetry catalysis etc. very soon.At natural active matter separation field, the molecular imprinting reported is used for the separation and purification of flavonoid, polyatomic phenol, alkaloids, steroid and coumarins.
Current gingerol molecularly imprinted polymer is obtained by Huang Xue pine (food and fermentation industries, 2009,35:84-86), Yan Fengchao (Food science, 2009,30:227-230) respectively.Tradition gingerol molecularly imprinted polymer is all Template preparation with 6-gingerol, and object is only for obtaining 6-gingerol monomer.As patent CN101255206A discloses a kind of preparation and application technology of 6-gingerol molecularly imprinted polymer of purifying.Its preparation method template 6-gingerol, function monomer, linking agent, initiator and solvent is added in reactor to mix, in isothermal reaction after degassed, obtain the molecularly imprinted polymer with template, being ground sieves obtains evenly with the molecularly imprinted polymer particle of template; Wash away template with organic solvent, dry and namely obtain the described molecularly imprinted polymer for 6-gingerol of purifying.Its application method is that preparation-obtained molecularly imprinted polymer is done column chromatography filler dress post, and by ginger juice upper prop, use spirituous solution wash-out, then concentrated also recovered alcohol, extraction, namely recycling design obtains 6-gingerol.
Have not yet to see the report utilizing the false template molecule engram technology of gingerol to extract the method for general gingerol from ginger.Mainly there is following reason: use general material to replace gingerol, by there will be, the selectivity of gingerol molecularly imprinted polymer to gingerol is poor, the purity of the gingerol obtained is very low, also there is no a kind of low-cost material so far to replace gingerol, and the molecularly imprinted polymer selectivity obtained is strong, can be used for orienting enriching gingerol.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide the false template molecule imprinted polymer of a kind of gingerol and from ginger, extract the method for gingerol with it.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for the false template molecule imprinted polymer of gingerol, comprises the following steps:
(1) be that 1 ~ 3:2 ~ 6:15 ~ 30:0.05 ~ 0.10:20 ~ 70 join in reactor and mix in mass ratio by false template, function monomer, linking agent, initiator, pore-creating agent; Described false template is N-(4-hydroxyl-3-methoxybenzy) pelargonamide; Function monomer is N-phenyl methyl alkene acid amides or N-(2-nitro-4-carboxyl phenyl) Methacrylamide;
(2) by the mixture ultrasonic degas (preferred 10-15 minute) of step (1), nitrogen deoxygenation (preferred 10-20 minute) is then filled;
(3) be polymerized 18 ~ 24 hours under 40 ~ 60 DEG C of conditions after sealing, obtain the polymkeric substance being with template molecule;
(4) template molecule is removed after polymer abrasive step (3) obtained, screening;
(5) by the polymkeric substance of removing template molecule, the false template molecule imprinted polymer of gingerol after drying, is obtained.
Function monomer described in above-mentioned preparation method is preferably N-(2-nitro-4-carboxyl phenyl) Methacrylamide; Described linking agent is N, N-dimethyl diacrylamine or Ethylene glycol dimethacrylate, is preferably N, N-dimethyl diacrylamine; Described pore-creating agent is glycol dimethyl ether, ethylene glycol monomethyl ether, is preferably ethylene glycol monomethyl ether.
The polymer abrasive that preferred above-mentioned steps (4) obtains crosses 150 ~ 200 mesh sieves, is the acetic acid methanol solution removing template molecule of 10% ~ 20% by the volume fraction of acetic acid.
Step (5) described drying is 50 ~ 65 DEG C of oven dry under vacuum.
The false template molecule imprinted polymer of the gingerol prepared by aforesaid method.
Utilize the false template molecule imprinted polymer of above-mentioned gingerol from ginger, extract the method for gingerol: false for gingerol template molecule imprinted polymer is done column chromatography filler dress post, then ginger extract upper prop is used, impurity is removed again with eluent solvent, last chromatography column methanol acetic acid eluant solution, effluent liquid is gingerol.
In the method for said extracted gingerol:
The solvent that described ginger extract uses is normal hexane, toluene, chloroform, tetrahydrofuran (THF) (THF), acetonitrile, the one in methyl alcohol, is preferably toluene.Described drip washing solvent is the mixing solutions of ethanol and normal hexane, and its ratio is the volume ratio of ethanol is 1%, 5%, 10%, 15%, and the one in 20%, be preferably 10%, volume is 2 ~ 8mL, is preferably 2mL.In described methanol acetic acid solution, methyl alcohol and acetic acid volume ratio are the one in 99:1,98:2,97:3, are preferably 97:3.
Beneficial effect of the present invention:
(1) gingerol analog N-(4-hydroxyl-3-methoxybenzy) pelargonamide is applied to the preparation of molecularly imprinted polymer as false template by the present invention first, introduce according to Shanghai Jing Chun biochemical technology limited-liability company (Aladdin reagent), commercial 6-gingerol price is 27 yuan/milligram, and N-(4-hydroxyl-3-methoxybenzy) pelargonamide price is 0.1 yuan/milligram, compared with conventional template molecule 6-gingerol, N-(4-methoxy-benzyl) pelargonamide can adopt chemical process to synthesize, with low cost, reliable raw material sources can be provided for preparing molecularly imprinted polymer on a large scale, cost is reduced greatly,
(2) first with N-phenyl methyl alkene acid amides or N-(2-nitro-4-carboxyl phenyl) Methacrylamide for function monomer, with false template reaction Synthesis of Molecular Imprinting Polymers;
(3) molecularly imprinted polymer selectivity of the present invention is strong, for purify gingerol time, only have gingerol molecule can enter in the middle of trace, and other impurity molecule can not enter trace, make this molecularly imprinted polymer primary attachment gingerol, other impurity absorption little, makes the purity of the gingerol obtained greatly improve, can reach more than 99%; The general gingerol that the present invention purifies and the 6-gingerol that patent CN101255206A purifies do not have difference in antioxidant activity tests, but greatly reduce in polymkeric substance preparation cost;
(4) the present invention is low for the molecularly imprinted polymer production cost of gingerol of purifying, and elutriant consumption is few;
(5) molecularly imprinted polymer for carrying gingerol of the present invention is also renewable after being applied to purification gingerol, and its renovation process is simple, feasible.
Accompanying drawing explanation
Fig. 1 is the schema of the Synthesis and applications of the false template molecule imprinted polymer of gingerol of the present invention;
Fig. 2 a is compound gingerol molecular structural formula involved in the present invention;
Fig. 2 b is the molecular structural formula of gingerol analog used in the present invention;
Fig. 3 a is obtained gingerol false template molecule imprinted polymer Electronic Speculum figure;
Fig. 3 b is obtained blank molecularly imprinted polymer Electronic Speculum figure;
Fig. 4 a is the structural formula of function monomer N-phenyl methacrylamide;
Fig. 4 b is the structural formula of function monomer N-(2-nitro-4-carboxyl phenyl) Methacrylamide.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, should be noted that following explanation is only to explain the present invention, not limiting its content.
Embodiment 1
The preparation of the false template molecule imprinted polymer of gingerol and extract from ginger gingerol method schema as shown in Figure 1, concrete steps are as follows:
The preparation of the false template molecule imprinted polymer of gingerol:
(1) get the raw materials ready
Each feed composition is by following consumption proportion batching: false template molecule N-(4-hydroxyl-3-methoxybenzy) pelargonamide 1.1736g, function monomer N-(2-nitro-4-carboxyl phenyl) Methacrylamide 3.3621g, linking agent N, N-dimethyl diacrylamine 7.9304g, initiator Diisopropyl azodicarboxylate 0.05g, pore-creating agent glycol dimethyl ether 30.0g;
(2) preparation is with the polymkeric substance of false template molecule
By above-mentioned N-(4-hydroxyl-3-methoxybenzy) pelargonamide, N-phenyl methacrylamide, the N that get ready, N-dimethyl diacrylamine, Diisopropyl azodicarboxylate, glycol dimethyl ether joins in reactor and mixes, ultrasonic degas 15min, then nitrogen deoxygenation is filled 15 minutes, be polymerized 24 hours in 60 DEG C of waters bath with thermostatic control after sealing, obtain the polymkeric substance with false template molecule;
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
By milled for the polymkeric substance of above-mentioned preparation 200 mesh sieves, namely obtain the polymer beads with false template molecule, be the methanol acetic acid eluant solution of 10% by acetic acid volume fraction, after 60 DEG C of vacuum-drying, obtain molecularly imprinted polymer 25.4g.
The method of extraction separation and purification gingerol from ginger:
Get the molecularly imprinted polymer dress post that 15 grams of the present embodiment are obtained, take 100g rhizoma zingiberis root and pulverize, add 500mL ethyl acetate supersound extraction, each 30min, after totally 3 times.Supernatant liquid filtering film, rotary evaporated to dryness is dry, redissolves with toluene.Toluene redissolution solution upper prop.After upper prop solution flows to end, carry out drip washing with hexanaphthene/ethanol (10:1, v/v), obtain leacheate.Chromatography column methanol acetic acid solution (97:3, v/v) wash-out, obtains elutriant.Obtain high purity gingerol, purity is 99.1%, and result illustrates the false template molecule trace-Solid-Phase Extraction of gingerol, has good effect to extraction separation and purification gingerol from ginger.
The regeneration of the false template molecule imprinted polymer of gingerol: by the above-mentioned molecularly imprinted polymer washing away the false template molecule of gingerol, use 95% ethanol elution, namely renewable for extracting use next time.
Embodiment 2
The preparation of the false template molecule imprinted polymer of gingerol:
(1) get the raw materials ready
Each feed composition is by following consumption proportion batching: false template molecule N-(4-hydroxyl-3-methoxybenzy) pelargonamide 1.1736g, function monomer N-phenyl methacrylamide 2.5792g, linking agent Ethylene glycol dimethacrylate 7.9304g, initiator Diisopropyl azodicarboxylate 0.05g, pore-creating agent ethylene glycol monomethyl ether 40.0g;
(2) preparation is with the polymkeric substance of false template molecule
By above-mentioned N-(4-hydroxyl-3-methoxybenzy) pelargonamide, N-phenyl methacrylamide, Ethylene glycol dimethacrylate, the Diisopropyl azodicarboxylate got ready, ethylene glycol monomethyl ether joins in reactor and mixes, ultrasonic degas 15min, then nitrogen deoxygenation is filled 15 minutes, be polymerized 24 hours in 60 DEG C of waters bath with thermostatic control after sealing, obtain the polymkeric substance with false template molecule;
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
By milled for the polymkeric substance of above-mentioned preparation 200 mesh sieves, namely obtain the polymer beads with false template molecule, be the methanol acetic acid eluant solution of 10% by acetic acid volume fraction, after 60 DEG C of vacuum-drying, obtain molecularly imprinted polymer 23.2g.
The method of extraction separation and purification gingerol from ginger:
Get the molecularly imprinted polymer dress post that 15 grams of the present embodiment are obtained, take 100g rhizoma zingiberis root and pulverize, add 500mL ethyl acetate supersound extraction, each 30min, after totally 3 times.Supernatant liquid filtering film, rotary evaporated to dryness is dry, redissolves with toluene.Toluene redissolution solution upper prop.After upper prop solution flows to end, carry out drip washing with hexanaphthene/ethanol (10:1, v/v), obtain leacheate.Chromatography column methanol acetic acid solution (97:3, v/v) wash-out, obtains elutriant.Obtain high purity gingerol, purity is 94.1%, and result illustrates the false template molecule trace-Solid-Phase Extraction of gingerol, has good effect to extraction separation and purification gingerol from ginger.
The regeneration of the false template molecule imprinted polymer of gingerol: by the above-mentioned molecularly imprinted polymer washing away the false template molecule of gingerol, use 95% ethanol elution, namely renewable for extracting use next time.
Embodiment 3
The preparation of the false template molecule imprinted polymer of gingerol:
(1) get the raw materials ready
Each feed composition is by following consumption proportion batching: false template molecule N-(4-hydroxyl-3-methoxybenzy) pelargonamide 1.1736g, function monomer N-phenyl methacrylamide 2.5792g, linking agent N, N-dimethyl diacrylamine 5.9478g, initiator Diisopropyl azodicarboxylate 0.06g, pore-creating agent glycol dimethyl ether 40.0g;
(2) preparation is with the polymkeric substance of template molecule
By above-mentioned N-(4-hydroxyl-3-methoxybenzy) pelargonamide, N-(2-nitro-4-carboxyl phenyl) Methacrylamide, the N that get ready, N-dimethyl diacrylamine, Diisopropyl azodicarboxylate, glycol dimethyl ether joins in reactor and mixes, ultrasonic degas 15min, then nitrogen deoxygenation is filled 15 minutes, be polymerized 24 hours in 60 DEG C of waters bath with thermostatic control after sealing, obtain the polymkeric substance with false template molecule;
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
By milled for the polymkeric substance of above-mentioned preparation 200 mesh sieves, namely obtain the polymer beads with false template molecule, be the methanol acetic acid eluant solution of 10% by acetic acid volume fraction, after 60 DEG C of vacuum-drying, obtain molecularly imprinted polymer 25.4g.
The method of extraction separation and purification gingerol from ginger:
Get the molecularly imprinted polymer dress post that 15 grams of the present embodiment are obtained, take 100g rhizoma zingiberis root and pulverize, add 500mL ethyl acetate supersound extraction, each 30min, after totally 3 times.Supernatant liquid filtering film, rotary evaporated to dryness is dry, redissolves with normal hexane.Normal hexane redissolution solution upper prop.After upper prop solution flows to end, carry out drip washing with hexanaphthene/ethanol (10:1, v/v), obtain leacheate.Chromatography column methanol acetic acid solution (97:3, v/v) wash-out, obtains elutriant.Obtain high purity gingerol, purity is 95.7%, and result illustrates the false template molecule trace-Solid-Phase Extraction of gingerol, has good effect to extraction separation and purification gingerol from ginger.
The regeneration of the false template molecule imprinted polymer of gingerol: by the above-mentioned molecularly imprinted polymer washing away the false template molecule of gingerol, use 95% ethanol elution, namely renewable for extracting use next time.
Embodiment 4
The preparation of the false template molecule imprinted polymer of gingerol:
(1) get the raw materials ready
Each feed composition is by following consumption proportion batching: false template molecule N-(4-hydroxyl-3-methoxybenzy) pelargonamide 1.1736g, function monomer N-(2-nitro-4-carboxyl phenyl) Methacrylamide 3.3621g, linking agent Ethylene glycol dimethacrylate 15.8572g, initiator Diisopropyl azodicarboxylate 0.07g, pore-creating agent glycol dimethyl ether 50.0g;
(2) preparation is with the polymkeric substance of false template molecule
By above-mentioned N-(4-hydroxyl-3-methoxybenzy) pelargonamide, N-(2-nitro-4-carboxyl phenyl) Methacrylamide, Ethylene glycol dimethacrylate, the Diisopropyl azodicarboxylate got ready, glycol dimethyl ether joins in reactor and mixes, ultrasonic degas 15min, then nitrogen deoxygenation is filled 15 minutes, be polymerized 24 hours in 60 DEG C of waters bath with thermostatic control after sealing, obtain the polymkeric substance with false template molecule;
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
By milled for the polymkeric substance of above-mentioned preparation 200 mesh sieves, namely obtain the polymer beads with false template molecule, be the methanol solution wash-out of 10% by acetic acid volume fraction, after 60 DEG C of vacuum-drying, obtain molecularly imprinted polymer 23.6g.
The method of extraction separation and purification gingerol from ginger:
Get the molecularly imprinted polymer dress post that 15 grams of the present embodiment are obtained, take 100g rhizoma zingiberis root and pulverize, add 500mL ethyl acetate supersound extraction, each 30min, after totally 3 times.Supernatant liquid filtering film, rotary evaporated to dryness is dry, redissolves with chloroform.Chloroform redissolution solution upper prop.After upper prop solution flows to end, carry out drip washing with hexanaphthene/ethanol (15:1, v/v), obtain leacheate.Chromatography column methanol acetic acid solution (97:3, v/v) wash-out, obtains elutriant.Obtain high purity gingerol, purity is 92.1%, and result illustrates the false template molecule trace-Solid-Phase Extraction of gingerol, has good effect to extraction separation and purification gingerol from ginger.
The regeneration of the false template molecule imprinted polymer of gingerol: by the above-mentioned molecularly imprinted polymer washing away the false template molecule of gingerol, use 95% ethanol elution, namely renewable for extracting use next time.
Embodiment 5
The preparation of the false template molecule imprinted polymer of gingerol:
(1) get the raw materials ready
Each feed composition is by following consumption proportion batching: false template molecule N-(4-hydroxyl-3-methoxybenzy) pelargonamide 1.1736g, function monomer N-(2-nitro-4-carboxyl phenyl) Methacrylamide 5.0432g, linking agent Ethylene glycol dimethacrylate 23.7859g, initiator Diisopropyl azodicarboxylate 0.02g, pore-creating agent ethylene glycol monomethyl ether 70.0g;
(2) preparation is with the polymkeric substance of false template molecule
By above-mentioned N-(4-hydroxyl-3-methoxybenzy) pelargonamide, N-(2-nitro-4-carboxyl phenyl) Methacrylamide, Ethylene glycol dimethacrylate, the Diisopropyl azodicarboxylate got ready, ethylene glycol monomethyl ether joins in reactor and mixes, ultrasonic degas 15min, then nitrogen deoxygenation is filled 15 minutes, be polymerized 24 hours in 60 DEG C of waters bath with thermostatic control after sealing, obtain the polymkeric substance with false template molecule;
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
By milled for the polymkeric substance of above-mentioned preparation 200 mesh sieves, namely obtain the polymer beads with false template molecule, be the methanol acetic acid eluant solution of 10% by acetic acid volume fraction, after 60 DEG C of vacuum-drying, obtain molecularly imprinted polymer 27.6g.
The method of extraction separation and purification gingerol from ginger:
Get the molecularly imprinted polymer dress post that 15 grams of the present embodiment are obtained, take 100g rhizoma zingiberis root and pulverize, add 500mL ethyl acetate supersound extraction, each 30min, after totally 3 times.Supernatant liquid filtering film, rotary evaporated to dryness is dry, redissolves with chloroform.Chloroform redissolution solution upper prop.After upper prop solution flows to end, carry out drip washing with hexanaphthene/ethanol (15:1, v/v), obtain leacheate.Chromatography column methanol acetic acid solution (98:2, v/v) wash-out, obtains elutriant.Obtain high purity gingerol, purity is 94.6%, and result illustrates the false template molecule trace-Solid-Phase Extraction of gingerol, has good effect to extraction separation and purification gingerol from ginger.
The regeneration of the false template molecule imprinted polymer of gingerol: by the above-mentioned molecularly imprinted polymer washing away the false template molecule of gingerol, use 95% ethanol elution, namely renewable for extracting use next time.
Embodiment 6
The preparation of the false template molecule imprinted polymer of gingerol:
(1) get the raw materials ready
Each feed composition is by following consumption proportion batching: false template molecule N-(4-hydroxyl-3-methoxybenzy) pelargonamide 1.1736g, function monomer N-phenyl methacrylamide 3.2240g, linking agent N, N-dimethyl diacrylamine 7.9304g, initiator Diisopropyl azodicarboxylate 0.06g, pore-creating agent glycol dimethyl ether 40.0g;
(2) preparation is with the polymkeric substance of false template molecule
By above-mentioned N-(4-hydroxyl-3-methoxybenzy) pelargonamide, N-phenyl methacrylamide, the N that get ready, N-dimethyl diacrylamine, Diisopropyl azodicarboxylate, glycol dimethyl ether joins in reactor and mixes, ultrasonic degas 15min, then nitrogen deoxygenation is filled 15 minutes, be polymerized 24 hours in 60 DEG C of waters bath with thermostatic control after sealing, obtain the polymkeric substance with false template molecule;
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
By milled for the polymkeric substance of above-mentioned preparation 200 mesh sieves, namely obtain the polymer beads with false template molecule, be the methanol acetic acid eluant solution of 10% by acetic acid volume fraction, after 60 DEG C of vacuum-drying, obtain molecularly imprinted polymer 19.6g.
The method of extraction separation and purification gingerol from ginger:
Get the molecularly imprinted polymer dress post that 15 grams of the present embodiment are obtained, take 100g rhizoma zingiberis root and pulverize, add 500mL ethyl acetate supersound extraction, each 30min, after totally 3 times.Supernatant liquid filtering film, rotary evaporated to dryness is dry, redissolves with normal hexane.Normal hexane redissolution solution upper prop.After upper prop solution flows to end, carry out drip washing with hexanaphthene/ethanol (95:5, v/v), obtain leacheate.Chromatography column methanol acetic acid solution (97:3, v/v) wash-out, obtains elutriant.Obtain high purity gingerol, purity is 94.1%, and result illustrates the false template molecule trace-Solid-Phase Extraction of gingerol, has good effect to extraction separation and purification gingerol from ginger.
The regeneration of the false template molecule imprinted polymer of gingerol: by the above-mentioned molecularly imprinted polymer washing away the false template molecule of gingerol, use 95% ethanol elution, namely renewable for extracting use next time.
Embodiment 7
The preparation of the false template molecule imprinted polymer of gingerol:
(1) get the raw materials ready
Each feed composition is by following consumption proportion batching: false template molecule N-(4-hydroxyl-3-methoxybenzy) pelargonamide 1.1736g, function monomer N-phenyl methacrylamide 3.2240g, linking agent Ethylene glycol dimethacrylate 11.8930g, initiator Diisopropyl azodicarboxylate 0.06g, pore-creating agent ethylene glycol monomethyl ether 30.0g;
(2) preparation is with the polymkeric substance of template molecule
By above-mentioned N-(4-hydroxyl-3-methoxybenzy) pelargonamide, N-phenyl methacrylamide, Ethylene glycol dimethacrylate, the Diisopropyl azodicarboxylate got ready, ethylene glycol monomethyl ether joins in reactor and mixes, ultrasonic degas 15min, then nitrogen deoxygenation is filled 15 minutes, be polymerized 24 hours in 60 DEG C of waters bath with thermostatic control after sealing, obtain the polymkeric substance with false template molecule;
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
By milled for the polymkeric substance of above-mentioned preparation 200 mesh sieves, namely obtain the polymer beads with false template molecule, be the methanol acetic acid eluant solution of 10% by acetic acid volume fraction, after 60 DEG C of vacuum-drying, obtain molecularly imprinted polymer 21.8g.
The method of extraction separation and purification gingerol from ginger:
Get the molecularly imprinted polymer dress post that 15 grams of the present embodiment are obtained, take 100g rhizoma zingiberis root and pulverize, add 500mL ethyl acetate supersound extraction, each 30min, after totally 3 times.Supernatant liquid filtering film, rotary evaporated to dryness is dry, redissolves with toluene.Toluene redissolution solution upper prop.After upper prop solution flows to end, carry out drip washing with hexanaphthene/ethanol (85:15, v/v), obtain leacheate.Chromatography column methanol acetic acid solution (98:2, v/v) wash-out, obtains elutriant.Obtain high purity gingerol, purity is 95.1%, and result illustrates the false template molecule trace-Solid-Phase Extraction of gingerol, has good effect to extraction separation and purification gingerol from ginger.
The regeneration of the false template molecule imprinted polymer of gingerol: by the above-mentioned molecularly imprinted polymer washing away the false template molecule of gingerol, use 95% ethanol elution, namely renewable for extracting use next time.
Embodiment 8
The preparation of the false template molecule imprinted polymer of gingerol:
(1) get the raw materials ready
Each feed composition is by following consumption proportion batching: false template molecule N-(4-hydroxyl-3-methoxybenzy) pelargonamide 1.1736g, function monomer N-(2-nitro-4-carboxyl phenyl) Methacrylamide 2.5216g, linking agent N, N-dimethyl diacrylamine 11.8929g, initiator Diisopropyl azodicarboxylate 0.05g, pore-creating agent glycol dimethyl ether 30.0g;
(2) preparation is with the polymkeric substance of false template molecule
By above-mentioned N-(4-hydroxyl-3-methoxybenzy) pelargonamide, N-(2-nitro-4-carboxyl phenyl) Methacrylamide, the N that get ready, N-dimethyl diacrylamine, Diisopropyl azodicarboxylate, glycol dimethyl ether joins in reactor and mixes, ultrasonic degas 15min, then nitrogen deoxygenation is filled 15 minutes, be polymerized 24 hours in 60 DEG C of waters bath with thermostatic control after sealing, obtain the polymkeric substance with false template molecule;
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
By milled for the polymkeric substance of above-mentioned preparation 200 mesh sieves, namely obtain the polymer beads with false template molecule, be the methanol acetic acid eluant solution of 10% by acetic acid volume fraction, after 60 DEG C of vacuum-drying, obtain molecularly imprinted polymer 21.6g.
The method of extraction separation and purification gingerol from ginger:
Get the molecularly imprinted polymer dress post that 15 grams of the present embodiment are obtained, take 100g rhizoma zingiberis root and pulverize, add 500mL ethyl acetate supersound extraction, each 30min, after totally 3 times.Supernatant liquid filtering film, rotary evaporated to dryness is dry, redissolves with normal hexane.Normal hexane redissolution solution upper prop.After upper prop solution flows to end, carry out drip washing with hexanaphthene/ethanol (80:20, v/v), obtain leacheate.Chromatography column methanol acetic acid solution (99:1, v/v) wash-out, obtains elutriant.Obtain high purity gingerol, purity is 93.1%, and result illustrates the false template molecule trace-Solid-Phase Extraction of gingerol, has good effect to extraction separation and purification gingerol from ginger.
The regeneration of the false template molecule imprinted polymer of gingerol: by the above-mentioned molecularly imprinted polymer washing away the false template molecule of gingerol, use 95% ethanol elution, namely renewable for extracting use next time.
Embodiment 9
The preparation of the false template molecule imprinted polymer of gingerol:
(1) get the raw materials ready
Each feed composition is by following consumption proportion batching: false template molecule N-(4-hydroxyl-3-methoxybenzy) pelargonamide 1.1736g, function monomer N-(2-nitro-4-carboxyl phenyl) Methacrylamide 1.6810g, linking agent Ethylene glycol dimethacrylate 11.8930g, initiator Diisopropyl azodicarboxylate 0.06g, pore-creating agent glycol dimethyl ether 30.0g;
(2) preparation is with the polymkeric substance of false template molecule
By above-mentioned N-(4-hydroxyl-3-methoxybenzy) pelargonamide, N-(2-nitro-4-carboxyl phenyl) Methacrylamide, Ethylene glycol dimethacrylate, the Diisopropyl azodicarboxylate got ready, glycol dimethyl ether joins in reactor and mixes, ultrasonic degas 15min, then nitrogen deoxygenation is filled 15 minutes, be polymerized 24 hours in 60 DEG C of waters bath with thermostatic control after sealing, obtain the polymkeric substance with false template molecule;
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
By milled for the polymkeric substance of above-mentioned preparation 200 mesh sieves, namely obtain the polymer beads with false template molecule, be the methanol acetic acid eluant solution of 10% by acetic acid volume fraction, after 60 DEG C of vacuum-drying, obtain molecularly imprinted polymer 23.4g.
The method of extraction separation and purification gingerol from ginger:
Get the molecularly imprinted polymer dress post that 15 grams of the present embodiment are obtained, take 100g rhizoma zingiberis root and pulverize, add 500mL ethyl acetate supersound extraction, each 30min, after totally 3 times.Supernatant liquid filtering film, rotary evaporated to dryness is dry, redissolves with normal hexane.Hexane solution upper prop.After upper prop solution flows to end, carry out drip washing with hexanaphthene/ethanol (80:20, v/v), obtain leacheate.Chromatography column methanol acetic acid solution (97:3, v/v) wash-out, obtains elutriant.Obtain high purity gingerol, purity is 96.1%, and result illustrates the false template molecule trace-Solid-Phase Extraction of gingerol, has good effect to extraction separation and purification gingerol from ginger.
The regeneration of the false template molecule imprinted polymer of gingerol: by the above-mentioned molecularly imprinted polymer washing away the false template molecule of gingerol, use 95% ethanol elution, namely renewable for extracting use next time.
Embodiment 10
(1) get the raw materials ready
Each feed composition is by following consumption proportion batching: false template molecule N-(4-hydroxyl-3-methoxybenzy) pelargonamide 1.1736g, function monomer N-(2-nitro-4-carboxyl phenyl) Methacrylamide 3.3621g, linking agent Ethylene glycol dimethacrylate 23.7859, initiator Diisopropyl azodicarboxylate 0.06g, pore-creating agent glycol dimethyl ether 40.0g;
(2) preparation is with the polymkeric substance of false template molecule
By above-mentioned N-(4-hydroxyl-3-methoxybenzy) pelargonamide, N-(2-nitro-4-carboxyl phenyl) Methacrylamide, Ethylene glycol dimethacrylate, the Diisopropyl azodicarboxylate got ready, glycol dimethyl ether joins in reactor and mixes, ultrasonic degas 15min, then nitrogen deoxygenation is filled 15 minutes, be polymerized 24 hours in 60 DEG C of waters bath with thermostatic control after sealing, obtain the polymkeric substance with false template molecule;
(3) molecularly imprinted polymer of template molecule is sloughed in preparation
By milled for the polymkeric substance of above-mentioned preparation 200 mesh sieves, namely obtain the polymer beads with false template molecule, be the methanol acetic acid eluant solution of 10% by acetic acid volume fraction, after 60 DEG C of vacuum-drying, obtain molecularly imprinted polymer 25.6g.
The method of extraction separation and purification gingerol from ginger:
Get the molecularly imprinted polymer dress post that 15 grams of the present embodiment are obtained, take 100g rhizoma zingiberis root and pulverize, add 500mL ethyl acetate supersound extraction, each 30min, after totally 3 times.Supernatant liquid filtering film, rotary evaporated to dryness is dry, redissolves with toluene.Toluene redissolution solution upper prop.After upper prop solution flows to end, carry out drip washing with hexanaphthene/ethanol (95:5, v/v), obtain leacheate.Chromatography column methanol acetic acid solution (99:1, v/v) wash-out, obtains elutriant.Obtain high purity gingerol, purity is 97.1%, and result illustrates the false template molecule trace-Solid-Phase Extraction of gingerol, has good effect to extraction separation and purification gingerol from ginger.
The regeneration of the false template molecule imprinted polymer of gingerol: by the above-mentioned molecularly imprinted polymer washing away the false template molecule of gingerol, use 95% ethanol elution, namely renewable for extracting use next time.
Anti-oxidant activity contrast experiment:
DPPH solution: take 0.1984gDPPH anhydrous alcohol solution, constant volume, in 50mL volumetric flask, shakes up, and is stored in refrigerator as storing solution, used time stepwise dilution.
6-gingerol solution: take 5.8mg6-gingerol, with anhydrous alcohol solution and constant volume in 50mL volumetric flask, shake up, for subsequent use;
General gingerol solution: take 5.8mg general gingerol, with anhydrous alcohol solution and constant volume in 50mL volumetric flask, shake up, for subsequent use;
The oxidation-resistance of various extracting solution is measured in DPPH system
Draw 1mLDPPH liquid storage, shake up to be measured in 100mL volumetric flask with dehydrated alcohol constant volume.Utilize the absorption that the feature red-purple of DPPH solution is rolled into a ball, the decline absorbed at wavelength 517nm place after adding oxidation inhibitor extracting solution by ultraviolet visible spectrophotometry mensuration represents that it eliminates ability to organic free radical, and calculates IC
50value, data are as shown in the table.
Found by Data Comparison, the general gingerol (embodiment 1-10) that the present invention purifies, anti-oxidant activity IC
50value is all better than 6-gingerol (CN101255206A), and beneficial effect is obvious.
Claims (10)
1. a preparation method for the false template molecule imprinted polymer of gingerol, is characterized in that, comprise the following steps:
(1) be that 1 ~ 3:2 ~ 6:15 ~ 30:0.05 ~ 0.10:20 ~ 70 join in reactor and mix in mass ratio by false template, function monomer, linking agent, initiator, pore-creating agent; Described false template is N-(4-hydroxyl-3-methoxybenzy) pelargonamide, and function monomer is N-phenyl methacrylamide or N-(2-nitro-4-carboxyl phenyl) Methacrylamide;
(2) by the mixture ultrasonic degas of step (1), nitrogen deoxygenation is then filled;
(3) be polymerized 18 ~ 24 hours under 40 ~ 60 DEG C of conditions after sealing, obtain the polymkeric substance with false template;
(4) the false template of removing after polymer abrasive step (3) obtained, screening;
(5) by the polymkeric substance of the false template of removing, the false template molecule imprinted polymer of gingerol after drying, is obtained.
2. the preparation method of the false template molecule imprinted polymer of a kind of gingerol according to claim 1, it is characterized in that, function monomer is N-(2-nitro-4-carboxyl phenyl) Methacrylamide.
3. the preparation method of the false template molecule imprinted polymer of a kind of gingerol according to claim 1, it is characterized in that, described linking agent is N, N-dimethyl diacrylamine or Ethylene glycol dimethacrylate.
4. the preparation method of the false template molecule imprinted polymer of a kind of gingerol according to claim 1, it is characterized in that, described pore-creating agent is glycol dimethyl ether or ethylene glycol monomethyl ether.
5. the preparation method of the false template molecule imprinted polymer of a kind of gingerol according to claim 1, it is characterized in that, the polymer abrasive that step (4) obtains crosses 150 ~ 200 mesh sieves, removes false template with the acetic acid methanol solution that the volume fraction of acetic acid is 10% ~ 20%.
6. the false template molecule imprinted polymer of the gingerol for preparing of method according to claim 1.
7. utilize the false template molecule imprinted polymer of the gingerol described in claim 6 from ginger, extract the method for gingerol, it is characterized in that, false for gingerol template molecule imprinted polymer is done column chromatography filler dress post, then ginger extract upper prop is used, again with drip washing eluent solvent removing impurity, last chromatography column methanol acetic acid eluant solution, effluent liquid is gingerol.
8. the method extracting gingerol from ginger according to claim 7, is characterized in that, the solvent that described ginger extract uses is normal hexane, one in toluene, chloroform, tetrahydrofuran (THF), acetonitrile, methyl alcohol.
9. the method extracting gingerol from ginger according to claim 7, is characterized in that, described drip washing solvent is the mixing solutions of ethanol and normal hexane, and wherein the volume ratio of ethanol is 1%, 5%, 10%, 15%, and the one in 20%.
10. the method extracting gingerol from ginger according to claim 7, is characterized in that, in described methanol acetic acid solution, methyl alcohol and acetic acid volume ratio are the one in 99:1,98:2,97:3.
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