CN1660769A - Process for preparing chicoric acid from chicory - Google Patents
Process for preparing chicoric acid from chicory Download PDFInfo
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- CN1660769A CN1660769A CN 200410073388 CN200410073388A CN1660769A CN 1660769 A CN1660769 A CN 1660769A CN 200410073388 CN200410073388 CN 200410073388 CN 200410073388 A CN200410073388 A CN 200410073388A CN 1660769 A CN1660769 A CN 1660769A
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- chicoric acid
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- witloof
- chicoric
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- YDDGKXBLOXEEMN-IABMMNSOSA-L Chicoric acid Natural products C1=C(O)C(O)=CC=C1\C=C\C(=O)O[C@@H](C([O-])=O)[C@H](C([O-])=O)OC(=O)\C=C\C1=CC=C(O)C(O)=C1 YDDGKXBLOXEEMN-IABMMNSOSA-L 0.000 title claims abstract description 180
- YDDGKXBLOXEEMN-UHFFFAOYSA-N Di-E-caffeoyl-meso-tartaric acid Natural products C=1C=C(O)C(O)=CC=1C=CC(=O)OC(C(O)=O)C(C(=O)O)OC(=O)C=CC1=CC=C(O)C(O)=C1 YDDGKXBLOXEEMN-UHFFFAOYSA-N 0.000 title claims abstract description 180
- YDDGKXBLOXEEMN-IABMMNSOSA-N chicoric acid Chemical compound O([C@@H](C(=O)O)[C@@H](OC(=O)\C=C\C=1C=C(O)C(O)=CC=1)C(O)=O)C(=O)\C=C\C1=CC=C(O)C(O)=C1 YDDGKXBLOXEEMN-IABMMNSOSA-N 0.000 title claims abstract description 180
- 229930016920 cichoric acid Natural products 0.000 title claims abstract description 180
- YDDGKXBLOXEEMN-PMACEKPBSA-N dicaffeoyl-D-tartaric acid Natural products O([C@H](C(=O)O)[C@H](OC(=O)C=CC=1C=C(O)C(O)=CC=1)C(O)=O)C(=O)C=CC1=CC=C(O)C(O)=C1 YDDGKXBLOXEEMN-PMACEKPBSA-N 0.000 title claims abstract description 180
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
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- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 5
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 5
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- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 4
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
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- Preparation Of Fruits And Vegetables (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
The invention provides a preparation process for extracting a high-content and high-purity chicoric acid product from chicory, which comprises the following steps of carrying out postharvest treatment on chicory raw materials, improving the content of chicoric acid in the harvested chicory and greatly reducing the cost of the raw materials; preprocessing the processing raw materials, and maximally preserving chicoric acid in the plants from being decomposed; proper extraction solvent and separation technology are selected, so that active ingredients in the plants are extracted and separated to the maximum extent, and the production cost is reduced; scientific and advanced purification technology and equipment are selected, impurities of the non-chicoric acid are effectively removed, and the purity and the content of the chicoric acid are improved; selecting optimized separation carrier and filler to realize industrial production of pure chicoric acid; selecting proper commodity form to prolong the shelf life of chicoric acid. The method of the invention can produce various products and meet different requirements for the products.
Description
Technical field
The invention belongs to chemical industry and extract field, particularly a kind of technology of utilizing witloof to produce chicoric acid.
Background technology
Chicoric acid claims two coffee tartrate again, the genus coffea acid derivative.Be to be subjected at present a kind of immunopotentiating agent and the immunomodulator generally paid attention in the world; in addition; also having the collagen protein III that duplicates, protects that stimulates phagolysis, suppresses Unidasa and be not subjected to cause influence, anti-HIV, anticancer, the anti-ageing effect of waiting for a long time of the free radical of degrading, is the main component that is applied to pharmaceutical raw material and protective foods.
Chicoric acid is present in the feverfew usually, and what produce chicoric acid in the world at present mainly is to extract from echinacea purpurea, Echinacea purpurea Moench, white Echinacea purpurea Moench.Because chicoric acid has chemical instability, thereby from plant, extract and preserve chicoric acid and have very big challenge.Chinese patent application number is CN00813200, name is called " purple coneflower tonic and preparation method ", tonic of at least two kinds of components that comprise chicoric acid and preparation method thereof is provided, and the raw material of application is the Echinacea purpurea Moench platymiscium, and product is with the target that is extracted as of plurality of active ingredients.Yet in the medicinal plant of China, this composition mainly is present in the plant witloof.Witloof is a composite family Cichorium per nnial herb, originates in Europe, is widely used as feed, vegetables and sugaring raw material, and herb contains chicoric acid, introduces China the eighties, has become the most rising feed of China and cash crop new variety at present, widely cultivation.
Chicoric acid is more in the market is that form with liquid exists, and wherein contain a large amount of water, and water has increased the weight and volume of chicoric acid product, has increased the expense of unnecessary processing and transportation.Water in the bright witloof juice produces active environment for microorganism and yeast provide, make witloof juice easily fermentation go mouldy, chicoric acid is degraded easily.Therefore, chicoric acid is made Powdered, tablet, capsule becomes the focus that those skilled in the art pay close attention to overcome the problems referred to above.
Summary of the invention
The present invention aims to provide a kind of the extraction from witloof can sanatory biological activity coffic acid derivative---the technology of chicoric acid, and the present invention significantly reduces raw materials cost by adopting the content that aftertreatment improves chicoric acid in the witloof of results back.
The concrete technical scheme that realizes above-mentioned purpose is, 1. technology of utilizing witloof to prepare chicoric acid is raw material with root, stem, the leaf of witloof, it is characterized in that this technology comprises the following steps:
1) witloof is adopted aftertreatment
A. witloof is gathered: select the witloof of plantation 1-3, full-bloom stage selectively stem, the leaf on top is a raw material, treats that stem, the leaf of over-ground part excavate root after withered and make raw material;
B. pulverize: to the stem of the over-ground part of results, leaf raw material through in 4-10 ℃ cold house, pulverizing immediately after the removal of impurities; For the quick flush away silt of root raw material, foreign material and air-dry rapidly and section;
C. control relative humidity, adjust oxygen, subzero treatment: the root raw material after the stem after the pulverizing, leaf raw material and the section is put into a polyethylene bag or burlap bag or paper bag, make it keep opening-wide state, make raw material be exposed among the air fully, the opening that preferably also has several 2-3cm on the sack, then sack is put into freezing environment fast, and keep its relative humidity 40-85%, temperature between 0-10 ℃, 96 hours time.
Through the witloof raw material of above-mentioned processing, directly carry out the processing of next process, or adopt microwave vacuum drying, drying bu sublimation to carry out drying treatment, make in the raw material moisture content treat to use with post-treatment less than 10%;
2) extraction step
Stem, leaf raw material that extraction is divided into over-ground part extract and the extraction of root of Herba Cichorii raw material
A. the stem of over-ground part, leaf raw material extract:
The witloof raw material of drying treatment is added 40%-70% ethanol or methanol solution as extracting solvent, 1: 3 G/V～1: 20 G/V of solid-liquid ratio and to feed speed when stirring be that 500L/ hour nitrogen is to prevent the chicoric acid degraded; At room temperature placed 30 hours, the lixiviate chicoric acid obtains the chicoric acid extracting solution then;
Or add 40%-70% ethanol or methanol solution as extracting solvent at the witloof raw material, adopt supersound extraction 40min, 1: 3 G/V～1: 10G/V of solid-liquid ratio; Centrifugal or squeezing separation obtains the chicoric acid extracting solution, and slag repeats to extract once again, and extracting solution merges;
B. the root of Herba Cichorii raw material extracts:
The exsiccant root of Herba Cichorii material of freezing treatment is ground again, add boiling water, solid-liquid ratio 1: 2G/V～1: 20 G/V, lixiviate is 2～4.5 minutes in the water, be cooled to 60 ℃ and placed 4 hours in this temperature, squeeze the juice by the mechanical screw type squeezing machine, the solid residue that obtains repeats lixiviate twice again, merges the chicoric acid extracting solution;
3) the chicoric acid extracting solution for preparing in the said extracted step is prepared the different chicoric acid powder of content respectively according to the variant production content requirement.
The different chicoric acid powder of above-mentioned content comprises chicoric acid product A, chicoric acid product B, chicoric acid products C, and its preparation method is respectively:
A. prepare the chicoric acid product A
Stem, the leaf raw material of over-ground part are extracted the chicoric acid extracting solution that obtains, remove impurity such as deproteinize, tannin, polysaccharide and other macromolecule interfering components and microorganism, thalline, virus by hollow inorganic fiber micro-filtrate membrane filtration, the microfiltration membrane aperture is between 0.10 μ m～0.25 μ m, 40 ℃ of rotating thin film evaporimeters concentrate then, at 60 ℃, vacuum tightness is that oven dry obtains the chicoric acid powder under the 0.08MPa, and this chicoric acid content of powder is higher than 30%, is the chicoric acid product A;
B. prepare the chicoric acid product B
1. the chicoric acid extract refining of root of Herba Cichorii raw material:
To be concentrated into below 1/2 of former extracting solution in the root chicoric acid extracting solution, add 95% alcohol that 1-5 doubly measures then, unit: V/V, after adding alcohol, the pure content of solution is not less than 60%, unit: V/V, leave standstill 2-5h, polysaccharide and other sedimentable matter in the juice are removed in suction filtration or centrifugation, and centrifuging obtains containing the chicoric acid juice of higher concentration.Preferred aperture is removed thalline fully, is solidified and water-soluble protein, colloid, pigment and other insolubles at the inorganic ultra-filtration membrane of tubular fibre of 0.05-0.25 μ m, obtains the refining extracting solution of chicoric acid;
2. the preparation of chicoric acid product B:
The refining extracting solution of chicoric acid is carried out 40-50 ℃ of vacuum concentration, the content that is concentrated into solid substance in the extracting solution is between 20%-35%, be heated to 80 ℃ then, in concentrated solution, add maltose or Star Dri 5, tricalcium phosphate non-hygroscopic carrier, the ratio of add-on and soluble solids is 0.2: 1～1.2: 1, pass through vacuum-drying then, the spraying drying mode is carried out drying, its temperature in is controlled between 149 ℃-160 ℃ during spray-drying process, temperature out is controlled between 93 ℃～104 ℃, the product that obtains by 100 mesh sieve filterings, guarantees that it has at least 40% to pass through again; Perhaps at least 100% by 16 mesh sieves, finally obtain the chicoric acid powder of chicoric acid content more than 20%, are the chicoric acid product B.
C. prepare the chicoric acid products C
1. absorption with macroporous adsorbent resin separates:
With the refining extracting solution of the above-mentioned chicoric acid that from witloof over-ground part or root, obtains, concentrate and to remove alcohol, dissolve again with distilled water or deionized water, with the speed of 10ml/min with macroporous adsorptive resins on the sample, allow resin sufficient standing adsorption equilibrium more than 5 hours, washing is removed not by behind the impurity of resin absorption, uses 5%-10% methanol-water wash-out then, unit: V/V, collect elutriant, 40 ℃ of rotating thin film evaporimeters concentrate, and remove methyl alcohol, obtain chicoric acid;
2. the reverse silicagel column column chromatography of C-18:
With the chicoric acid medicinal extract that purification with macroreticular resin obtains, use dissolve with methanol solution, last C-18 silicagel column, the methanol solution wash-out with 50%, with toluene: ethyl acetate: it is developping agent that formic acid equals 5: 2: 0.7, silica gel G F
254Thin plate launches, and compares with witloof acidity scale product, detects and merges and collect the chicoric acid elutriant, concentrates, and removes methyl alcohol, the water recrystallization, and drying bu sublimation obtains the pure product chicoric acid of content more than 90%, is chicoric acid product c.
The chicoric acid of the inventive method preparation is to be extracting solution with water, alcohol-water, has reduced production cost, has improved extraction yield, avoids the decomposition of chicoric acid; Non-chicoric acid composition has effectively been removed in this invention, has prevented the interference of other composition to the chicoric acid active function; And to adopt the chicoric acid of method of the present invention preparation be Powdered, prevented that fermentation from going mouldy and degrade.
The present invention mainly utilize the second alcohol and water to mix according to a certain percentage or directly water extract more thorough as extracting the solvent extraction chicoric acid.Extract to stir process in feed nitrogen simultaneously to prevent the chicoric acid degraded, obtain containing the juice of chicoric acid.Can effectively remove impurity such as macromolecule interfering components such as deproteinize, tannin, polysaccharide and microorganism, thalline, virus by membrane filtration or alcohol precipitation caudacoria filtering technique, obtain purified chicoric acid extracting solution.Concentrate then, obtain the chicoric acid powder-product through following two kinds of different technologies after the drying.A kind of method is the juice of membrane filtration, removes impurity, and concentrate drying obtains humidity less than 8% chicoric acid powder.Another kind method is to utilize alcohol to precipitate the polysaccharide of removing in the juice earlier, concentrate after removing other impurity through the juice of membrane filtration then, and in concentration process, adding carriers such as maltose, tricalcium phosphate, drying obtains highly purified chicoric acid powder after sift out.At present, its content of effective of chicoric acid product of selling on the market is all lower, the highlyest is no more than 4%.By above-mentioned processing, chicoric acid content can be brought up to more than 20% in the product.
Chicoric acid easily decomposes, polarity is strong, and the pure product chicoric acid of suitability for industrialized production is difficulty very, and the present invention separates the above-mentioned purified chicoric acid extracting solution that obtains by absorption with macroporous adsorbent resin, obtain pure product chicoric acid by the reverse post column chromatographic isolation and purification of ODS again, purity is more than 90%.
Description of drawings
Fig. 1 is that technology of the present invention is extracted schema;
Fig. 2 be chicory leaf adopt the aftertreatment schema;
Fig. 3 is Powdered chicoric acid product A preparation flow figure;
Fig. 4 is chicoric acid product B preparation flow figure;
Fig. 5 is chicoric acid products C preparation flow figure.
Below in conjunction with drawings and Examples Technology of the present invention is described in further detail.
Embodiment
In the present invention, at first select each organ of witloof when its chicoric acid content is the highest, to gather, witloof after the results is pulverized immediately, control relative humidity then, carry out low tempertaure storage etc. at half oxygen supply state and adopt the aftertreatment measure, through adopting the witloof of aftertreatment like this, the content of its effective constituent chicoric acid has improved 1% at least with originally comparing.This is that the chicoric acid enzyme is proceeded physiological activity in the plant, and its secondary metabolism is proceeded because give appropriate condition, synthetic chicoric acid, but after 96 hours, chicoric acid katabolism dominate, chicoric acid content begins to descend, and need carry out next process immediately.This research greatly reduces planting cost.
Witloof through above-mentioned processing still contains a large amount of moisture; if allow plant be kept at high wet condition; chicoric acid is in significantly degraded of short period of time; produce all the year round for the ease of production and realization chicoric acid; need carry out drying treatment to witloof immediately through above-mentioned processing; the present invention adopts freeze-drying, microwave vacuum drying method or forced air drying method effectively to protect chicoric acid, avoids its degraded.
1, witloof is adopted aftertreatment:
The content of chicoric acid is influenced by floristics, growth year and growth conditions.For the chicoric acid of production high density, must consider many factors such as harvesting stage, production standard and extracting solution.
1) witloof is gathered: preferably select the witloof of plantation 1-3 in the witloof, plantation is more than 4 years, and content descends on the contrary to some extent; Full-bloom stage mainly selectively top be divided into raw material, approximately the flower of 10-25% is in the flower of flowering period to no more than 10% and withers the best in period; The withered back of over-ground part just can be excavated root and make raw material before being sprouted new over-ground part to next year.
2) pulverize: behind results over-ground part and the root, collect respectively in order to be beneficial to later processing.Overground part letter sorting is cut weeds and is waited foreign material, and foreign material such as the quick flush away silt of root are also air-dry rapidly, pulverizes (over-ground part), cut into slices (root) then immediately, make length between 1.4-5.1cm, the thickness of undercut sheet is preferably between the 0.5-1cm, and maximum is no more than 2cm, approaches excessively to be unfavorable for filtering.For the ease of utilizing, section should be big or small consistent; In order to prevent the decomposition of chicoric acid, pulverize in the cold house that is preferably in 4-10 ℃ and carry out, and the time between results and the pulverizing section should be minimized as far as possible, and fresh cut slice is stored fast.
3) control relative humidity, adjust oxygen, subzero treatment certain hour: fresh pulverizing, sliced materials can be placed in polyethylene bag or burlap bag, the paper bag.Preferably also have the opening of several 2-3cm on the sack, and make it keep opening-wide state, content is exposed among the air fully.Sack should be suitable for placing an amount of section, can not too push, to prevent the loss of rotten or chicoric acid.For example, the section of 10kg can be put into the polyethylene bag of load-bearing 10kg.Put into the freezing environment of one and half oxygen supplys then fast, keep between its relative humidity 40-85%, preferably 84%, temperature is between 0-10 ℃, preferably 3 ℃, approximately place that chicoric acid content begins to rise after 24 hours, and continue to raise up to 96 hours always, after this chicoric acid content is on a declining curve.So section is for further processing the broken raw material of witloof between should be at this moment.
2, drying treatment
Through adopting the witloof raw material of aftertreatment, can directly carry out the processing of next process, but need often, so that produce all the year round with most raw material temporary storage.In order to prevent the chicoric acid degraded in the plant, need carry out drying treatment to it, make in the raw material moisture content less than 10%.Microwave vacuum drying, drying bu sublimation and appropriate temperature are carried out forced air drying and can be reached the exsiccant purpose, can not cause decomposition to chicoric acid.The only temperature of forced air drying method is 40 ℃, dry with this understanding 55 hours effect even than the better effects if of microwave vacuum drying 47min.If 25 ℃ of forced air dryings, dry under 50%, 70 ℃ of condition of chicoric acid loss, the chicoric acid loss can be bigger, in a word, the rising above 40 ℃ along with drying temperature, reduce time of drying, and the chicoric acid loss increases gradually.
3. extract
1) witloof over-ground part ethanol extraction method: method one: will adopt aftertreatment and exsiccant witloof material add 40%-70% ethanol or methanol solution (v/v) as extracting solvent, solid-liquid ratio 1: 3-1: 20 (G/V) also feed nitrogen to prevent the chicoric acid degraded when stirring.At room temperature place 30 hours lixiviate chicoric acids.The too high meeting of alcohol concn increases the degree of degradation of chicoric acid; Alcohol concn is low excessively, can make to extract not exclusively, reduces output.The speed that nitrogen feeds is 500L/ hour.Method two: 40%-70% ethanol or methanol solution (v/v) are as extracting solvent, supersound extraction 40min, solid-liquid ratio 1: 3-1: 10 (G/V).Centrifugal or squeezing separation obtains the chicoric acid extracting solution, and slag repeats to extract once again, and extracting solution merges.
2) root of Herba Cichorii water extract method
The exsiccant root of Herba Cichorii material of freezing treatment is carefully ground again, add boiling water, solid-liquid ratio 1: 2-1: 20 (G/V), in the water lixiviate 2-4.5 minute, this flooding can improve output, and the flooding working method is compared with alcohol extracting can improve output 12%, even reaches 17%.Be cooled to 60 ℃, keep this temperature to place 4 hours, the content of chicoric acid can increase.Squeeze the juice by the mechanical screw type squeezing machine, the solid residue that obtains repeats lixiviate twice again, merges the chicoric acid extracting solution.
4. the preparation of chicoric acid product:
1) chicoric acid product A preparation
The chicoric acid extracting solution that the witloof over-ground part obtains, remove impurity such as deproteinize, tannin, polysaccharide and other macromolecule interfering components and microorganism, thalline, virus by hollow inorganic fiber micro-filtrate membrane filtration, preferred microfiltration membrane aperture is between 0.10-0.25 μ m, 40 ℃ of rotating thin film evaporimeters concentrate then, at 60 ℃, vacuum tightness is that oven dry obtains the chicoric acid finished product under the 0.08MPa, its humidity is less than 8%, preferably less than 5% chicoric acid powder, chicoric acid content is higher than 30%, i.e. the chicoric acid product A.
2) preparation of chicoric acid product B:
1. root chicoric acid extract refining: will be concentrated into below 1/2 of former extracting solution in the root chicoric acid extracting solution, add 95% alcohol (V/V) that 1-5 doubly measures then, after adding alcohol, the pure content of solution is not less than 60% (V/V), leave standstill 2-5h, polysaccharide and other sedimentable matter in the juice are removed in suction filtration or centrifugation, and centrifuging obtains containing the chicoric acid juice of higher concentration.Optional ethanol of alcohol and methyl alcohol, Virahol etc.The tubular fibre inorganic ultra-filtration membrane of aperture at 0.05-0.1 μ m preferably selected at 0.05-0.25 μ m in preferred aperture, removes thalline fully, solidifies and water-soluble protein, colloid, pigment and other insolubles, obtains the refining extracting solution of chicoric acid.
2. the preparation of chicoric acid product B: extracting solution carries out 40-50 ℃ of vacuum concentration, the content that is concentrated into solid substance in the extracting solution is between 20%-35%, preferably between the 25%-30%, be heated to 80 ℃ then, add maltose or non-hygroscopic carriers such as Star Dri 5, tricalcium phosphate in the concentrated solution, the add-on of carrier is decided according to the amount of soluble solids, and promptly the ratio of carrier and soluble solids is 0.2: 1-1.2: 1, and preferably 0.25: 1.Carry out drying through modes such as vacuum-drying, spraying dryings then.Preferably adopt spray-drying process, its temperature in is controlled between 149-160 ℃, and temperature out is controlled between 93-104 ℃.The product that obtains carries out filtering by 100 purpose sieves again, guarantees that it has at least 40% to pass through, and perhaps at least 100% can pass through 16 purpose sieves, finally obtains highly purified chicoric acid powder, and chicoric acid content is more than 20%, i.e. the chicoric acid product B.
This powder can be made capsule, tablet or be used in combination with other herbal medicine material.
5, the preparation of chicoric acid products C:
1. absorption with macroporous adsorbent resin separates: with the refining extracting solution of the above-mentioned chicoric acid that obtains from witloof over-ground part or root, concentrate and remove alcohol, again dissolve with distilled water or deionized water, with the sample upper prop, allow resin sufficient standing adsorption equilibrium more than 5 hours with the speed of 10ml/min.Washing is removed not by behind the impurity of resin absorption, uses 5%-10% (V/V) methanol-water wash-out then, and the most handy 7% (V/V) methanol-water wash-out is collected elutriant, and 40 ℃ of rotating thin film evaporimeters concentrate, and remove methyl alcohol, obtain purity chicoric acid preferably.Absorption with macroporous adsorbent resin separation and purification chicoric acid processing ease, easy, favorable reproducibility, consumption are few, and the resin activating and regenerating is easy, for next step preparation high pure chicoric acid provides raw material.Select nonpolar macroporous adsorption resin absorption such as HPD-100, D-101A, LSA-30, first-selected HPD-100.
2. the reverse silicagel column column chromatography of C-18: the purity that purification with macroreticular resin is obtained is chicoric acid medicinal extract preferably, use dissolve with methanol solution, last C-18 silica gel (40-60 order) post, methanol solution wash-out with 50%, with toluene-ethyl acetate-formic acid (5: 2: 0.7) is developping agent, the silica GF254 thin plate launches, compare with witloof acidity scale product, detect and merge and collect the chicoric acid elutriant, concentrate, remove methyl alcohol, the water recrystallization, drying bu sublimation obtains pure product chicoric acid, and its content is more than 90%.Cryogenic freezing is stored.
It below is the preferred embodiment that the contriver provides.
Embodiment 1: chicory leaf adopt aftertreatment:
Gather fresh witloof blade June, choose cut weeds, foreign material such as deadwood, pulverize the section that is cut into 1.5cm fast, humidity is about 73%, in 10 hours 10 kilograms pulverizing blade is positioned over unit weight and is in 10 kilograms the polyethylene bag, unlimited fully, and the long otch of 2 2.5cm is cut on both sides respectively, putting into temperature fast is 3 ℃ of freezers, keeping its relative humidity is 84%, and freezing treatment is after 24 hours, and HPLC measures chicoric acid content and begins to rise, reached maximum in 96 hours, its content has improved 1.03% than originally.40 ℃ of forced air dryings of witloof blade after will handling then 55 hours obtain exsiccant witloof blade, preserve 1 year, after measured the basic no change of chicoric acid content.
Embodiment 2: Powdered chicoric acid product A preparation:
What should full-bloom stage harvesting in July witloof over-ground part (specifically be? stem? leaf?), obtain chicoric acid content through the treatment process identical and bring up to 1.7% raw material with embodiment 1, get this raw material 100 grams, add the 500mL50% ethanolic soln, supersound extraction 40min, vacuum filtration obtains the chicoric acid extracting solution, slag repeats to extract once united extraction liquid again.Selecting the aperture is the microfiltration membrane removal of impurities of 0.25 μ m, obtains the refining extracting solution of chicoric acid, 40 ℃ of rotating thin film evaporation concentration, and it is 6% Powdered chicoric acid product A that 60 ℃ of vacuum-drying obtains moisture content, measuring chicoric acid content through HPLC is 21%.
Embodiment 3: the preparation of chicoric acid product B:
Gather in the crops root of Herba Cichorii September, obtain chicoric acid content through the treatment process identical and bring up to 0.9% raw material, get this raw material 100 grams, added in the 400mL boiling water lixiviate 3 minutes, be cooled to 60 ℃, keep this temperature to place 4 hours with embodiment 1.Squeeze the juice by expeller, obtain juice and slag.Slag is brought up again once, united extraction liquid is concentrated into 1/2 of extracting solution, adds 3 times of amount 95% ethanol, precipitation is removed throw outs such as polysaccharide, remove other interfering components by 0.1 μ m ultra-filtration membrane again, continuing to be concentrated into soluble solid content then is 20%, adds carrier tricalcium phosphate 0.315g in the time of 80 ℃, the powder that obtains of vacuum-drying is by 16 purposes sieve then, finally obtain highly purified chicoric acid powder, i.e. chicoric acid product B, its chicoric acid content is up to 34%.
Embodiment 4: the preparation of chicoric acid products C
Get the refining extracting solution 500mL of chicoric acid that embodiment 2 or embodiment 3 obtain, concentrate and remove alcohol, deionized water dissolves again, with HPD-100 type macroporous adsorptive resins on the sample, allows resin sufficient standing adsorption equilibrium 5 hours with the speed of 10ml/min, the 900mL water elution, remove not by behind the impurity of resin absorption, with 7% (V/V) methanol-water wash-out, TLC follows the tracks of detection, collect elutriant, 40 ℃ of rotating thin film evaporimeters concentrate, and obtain purity chicoric acid medicinal extract preferably, and chicoric acid medicinal extract dissolves with small amount of methanol solution, last C-18 silica gel (40-60 order) post, with 50% methanol solution wash-out, TLC follows the tracks of detection, merges to collect the chicoric acid elutriant, concentrate, remove methyl alcohol, water recrystallization, drying bu sublimation, obtain pure product chicoric acid, its content 92%.Cryogenic freezing is stored.It is developping agent that TLC detects with toluene-ethyl acetate-formic acid (5: 2: 0.7), and the silica GF254 thin plate launches, and compares with witloof acidity scale product.
Claims (3)
1. technology of utilizing witloof to prepare chicoric acid is raw material with root, stem, the leaf of witloof, it is characterized in that this technology comprises the following steps:
1) witloof is adopted aftertreatment
A. witloof is gathered: select the witloof of plantation 1-3, full-bloom stage selectively stem, the leaf on top is a raw material, treats that stem, the leaf of over-ground part excavate root after withered and make raw material;
B. pulverize: to the stem of the over-ground part of results, leaf raw material through in 4-10 ℃ cold house, pulverizing immediately after the removal of impurities; For the quick flush away silt of root raw material, foreign material and air-dry rapidly and section;
C. control relative humidity, adjust oxygen, subzero treatment: the root raw material after the stem after the pulverizing, leaf raw material and the section is put into polyethylene bag or the burlap bag or the paper bag of one and half oxygen supplys, make it keep opening-wide state, make raw material be exposed among the air fully, preferably also have the opening of several 2-3cm then sack to be put into freezing environment fast on the sack, and keep its relative humidity 40-85%, temperature between 0-10 ℃, 96 hours time.
Through the witloof raw material of above-mentioned processing, directly carry out the processing of next process, or adopt microwave vacuum drying, drying bu sublimation to carry out drying treatment, make in the raw material moisture content treat to use with post-treatment less than 10%.
2) extraction step
Stem, leaf raw material that extraction is divided into over-ground part extract and the extraction of root of Herba Cichorii raw material
A. the stem of over-ground part, leaf raw material extract:
The witloof raw material of drying treatment is added 40%-70% ethanol or methanol solution as extracting solvent, solid-liquid ratio 1: 3G/V～1: 20G/V and to feed speed when stirring be that 500L/ hour nitrogen is to prevent the chicoric acid degraded; At room temperature placed 30 hours, the lixiviate chicoric acid obtains the chicoric acid extracting solution then;
Or add 40%-70% ethanol or methanol solution as extracting solvent at the witloof raw material, adopt supersound extraction 40min, solid-liquid ratio 1: 3G/V～1: 10G/V; Centrifugal or squeezing separation obtains the chicoric acid extracting solution, and slag repeats to extract once again, and extracting solution merges;
B. the root of Herba Cichorii raw material extracts:
The exsiccant root of Herba Cichorii material of freezing treatment is ground again, add boiling water, solid-liquid ratio 1: 2G/V～1: 20G/V, lixiviate is 2～4.5 minutes in the water, be cooled to 60 ℃ and placed 4 hours in this temperature, squeeze the juice by the mechanical screw type squeezing machine, the solid residue that obtains repeats lixiviate twice again, merges the chicoric acid extracting solution;
3) the chicoric acid extracting solution for preparing in the said extracted step is prepared the different chicoric acid powder of content respectively according to the variant production content requirement.
2. the method for claim 1 is characterized in that, the different chicoric acid powder of described content comprises chicoric acid product A, chicoric acid product B, chicoric acid products C, and its preparation method is respectively:
A. prepare the chicoric acid product A
Stem, the leaf raw material of over-ground part are extracted the chicoric acid extracting solution that obtains, remove impurity such as deproteinize, tannin, polysaccharide and other macromolecule interfering components and microorganism, thalline, virus by hollow inorganic fiber micro-filtrate membrane filtration, the microfiltration membrane aperture is between 0.10 μ m～0.25 μ m, 40 ℃ of rotating thin film evaporimeters concentrate then, at 60 ℃, vacuum tightness is that oven dry obtains the chicoric acid powder under the 0.08MPa, and this chicoric acid content of powder is higher than 30%, is the chicoric acid product A;
B. prepare the chicoric acid product B
1. the chicoric acid extract refining of root of Herba Cichorii raw material:
To be concentrated into below 1/2 of former extracting solution in the root chicoric acid extracting solution, add 95% alcohol that 1-5 doubly measures then, unit: V/V, after adding alcohol, the pure content of solution is not less than 60%, unit: V/V, leave standstill 2-5h, polysaccharide and other sedimentable matter in the juice are removed in suction filtration or centrifugation, and centrifuging obtains containing the chicoric acid juice of higher concentration.Preferred aperture is removed thalline fully, is solidified and water-soluble protein, colloid, pigment and other insolubles at the inorganic ultra-filtration membrane of tubular fibre of 0.05-0.25 μ m, obtains the refining extracting solution of chicoric acid;
2. the preparation of chicoric acid product B:
The refining extracting solution of chicoric acid is carried out 40-50 ℃ of vacuum concentration, the content that is concentrated into solid substance in the extracting solution is between 20%-35%, be heated to 80 ℃ then, in concentrated solution, add maltose or Star Dri 5, tricalcium phosphate non-hygroscopic carrier, the ratio of add-on and soluble solids is 0.2: 1～1.2: 1, carry out drying through vacuum-drying, spraying drying mode then, the product that obtains after the drying by 100 mesh sieve filterings, guarantees that it has at least 40% to pass through again; Perhaps at least 100% by 16 mesh sieves, finally obtain the chicoric acid powder of chicoric acid content more than 20%, are the chicoric acid product B;
C. prepare the chicoric acid products C
1. absorption with macroporous adsorbent resin separates:
With the refining extracting solution of the above-mentioned chicoric acid that from witloof over-ground part or root, obtains, concentrate and to remove alcohol, dissolve again with distilled water or deionized water, with the speed of 10ml/min with macroporous adsorptive resins on the sample, allow resin sufficient standing adsorption equilibrium more than 5 hours, washing is removed not by behind the impurity of resin absorption, uses 5%-10% methanol-water wash-out then, unit: V/V, collect elutriant, 40 ℃ of rotating thin film evaporimeters concentrate, and remove methyl alcohol, obtain chicoric acid;
2. the reverse silicagel column column chromatography of C-18:
With the chicoric acid medicinal extract that purification with macroreticular resin obtains, use dissolve with methanol solution, last C-18 silicagel column, methanol solution wash-out with 50%, with toluene: ethyl acetate: it is developping agent that formic acid equals 5: 2: 0.7, the silica GF254 thin plate launches, compare with witloof acidity scale product, detect and merge and collect the chicoric acid elutriant, concentrate, remove methyl alcohol, the water recrystallization, drying bu sublimation obtains the pure product chicoric acid of content more than 90%, is chicoric acid product c.
3. the method for claim 1 is characterized in that, its temperature in was controlled between 149 ℃-160 ℃ when preparation chicoric acid product B adopted spray-drying process, and temperature out is controlled between 93 ℃～104 ℃.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101869348A (en) * | 2010-06-25 | 2010-10-27 | 王爱平 | Method for extracting antioxidation active substance from Cichorium endivia L. |
| CN102161620A (en) * | 2011-03-10 | 2011-08-24 | 湖南师范大学 | Method for non column chromatography separation and purification of witloof acid from Echinacea purpurea extractive |
| CN102249917A (en) * | 2011-05-20 | 2011-11-23 | 沈阳双鼎科技有限公司 | Chicoric acid and extraction and separation method and application thereof |
| CN103877071A (en) * | 2014-03-24 | 2014-06-25 | 中国科学院新疆理化技术研究所 | Medicinal application of chicoric acid |
| CN105294440A (en) * | 2015-09-30 | 2016-02-03 | 桂林三宝药业有限公司 | Method for extracting chicoric acid from echinacea purpurea moench |
| CN106380402A (en) * | 2016-08-29 | 2017-02-08 | 珀莱雅化妆品股份有限公司 | Preparation method for extracting high-purity chicoric acid from echinacea purpurea herb |
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| CN101869348A (en) * | 2010-06-25 | 2010-10-27 | 王爱平 | Method for extracting antioxidation active substance from Cichorium endivia L. |
| CN101869348B (en) * | 2010-06-25 | 2013-01-02 | 王爱平 | Method for extracting antioxidation active substance from Cichorium endivia L. |
| CN102161620A (en) * | 2011-03-10 | 2011-08-24 | 湖南师范大学 | Method for non column chromatography separation and purification of witloof acid from Echinacea purpurea extractive |
| CN102161620B (en) * | 2011-03-10 | 2013-01-30 | 湖南师范大学 | Method for non column chromatography separation and purification of witloof acid from Echinacea purpurea extractive |
| CN102249917A (en) * | 2011-05-20 | 2011-11-23 | 沈阳双鼎科技有限公司 | Chicoric acid and extraction and separation method and application thereof |
| CN103877071A (en) * | 2014-03-24 | 2014-06-25 | 中国科学院新疆理化技术研究所 | Medicinal application of chicoric acid |
| CN105294440A (en) * | 2015-09-30 | 2016-02-03 | 桂林三宝药业有限公司 | Method for extracting chicoric acid from echinacea purpurea moench |
| CN105294440B (en) * | 2015-09-30 | 2017-08-08 | 桂林三宝药业有限公司 | A kind of method that Cichoric acid is extracted from Echinacea |
| CN106380402A (en) * | 2016-08-29 | 2017-02-08 | 珀莱雅化妆品股份有限公司 | Preparation method for extracting high-purity chicoric acid from echinacea purpurea herb |
| CN106380402B (en) * | 2016-08-29 | 2018-09-21 | 珀莱雅化妆品股份有限公司 | A kind of preparation method for extracting high pure chicoric acid from Echinacea |
| CN107373747A (en) * | 2017-07-20 | 2017-11-24 | 云南中烟新材料科技有限公司 | The chicory root extract and preparation method and application of a kind of Microwave Pretreatment |
| CN107373747B (en) * | 2017-07-20 | 2020-03-31 | 云南中烟新材料科技有限公司 | Microwave-pretreated chicory root extract and preparation method and application thereof |
| CN110527001A (en) * | 2019-09-24 | 2019-12-03 | 武汉轻工大学 | A kind of witloof polysaccharide and its extraction process and application |
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