CN1199982C - Process for extracting saponins from white fleece-flower root - Google Patents
Process for extracting saponins from white fleece-flower root Download PDFInfo
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Abstract
The present invention relates to a method for extracting and producing saponins in cynanchum auriculatum, particularly to a method for extracting, refining and producing saponins in cynanchum auriculatum in water or alcohol containing water. The present invention is characterized in that water or alcohol containing water for leaching cynanchum auriculatum is adsorbed by adsorbing agents synthesized by methyl propylene series or aromatic series; then, the liquid is treated by desorption and elution by using alcohol containing 40% to 100% of water or alcohol or propanone; saponins in cynanchum auriculatum can be extracted after the solvent in eluent is removed, wherein the water for leaching cynanchum auriculatum is water leaching liquor which contains saponins of cynanchum auriculatum and is produced in quantity when refined powder of cynanchum auriculatum is produced, or the water can be saponin centrifugal separation liquor which is produced by putting fresh cynanchum auriculatum in water and then treating the cynanchum auriculatum by suspending, stirring, fully soaking and centrifugal separation; the leaching liquor of alcohol containing water which contains saponins of cynanchum auriculatum is extracted by leaching pieces or powder of fresh cynanchum auriculatum or dried cynanchum auriculatum in alcohol containing water. The alcohol containing water or alcohol comprises methanol, ethanol and propyl alcohol.
Description
Technical field
What the present invention extracted that the method for production relates to the saponin class that contains in the Root of Bunge Auriculate is the method for extracting, make with extra care, producing about to the saponin class that is present in the Root of Bunge Auriculate in water or the aqueous alcohol.
Background technology
Root of Bunge Auriculate is a kind of Chinese medicine that " Chinese medicinal herbal " (second, People's Health Publisher, 328 pages, 1979) once put down in writing.Former plant belongs to Asclepiadaceae, has Auriculoside A, mountain on the other way round cynanchum auriculatum Royle ex Wight, Bunge Swallowwort Root etc. several.Root of Bunge Auriculate is that the plant that extensively distributes is economized in Jiangsu, Hebei, Henan, Shandong, Shanxi, Liaoning, Jilin in China etc.The Root of Bunge Auriculate rhizome ate among the people being used in the past as far back as 100 years always, and particularly the Root of Bunge Auriculate kind in Jiangsu Province from its botanical character, belongs to the Auriculoside A class, existing cultivation history more than 100 years, also cultivation widely now.After this Root of Bunge Auriculate is processed into radix polygoni multiflori powder, for protective foods, edible widely all over China now through the ministry of Health of China authentication.
There is report to claim the pharmacologically active that Root of Bunge Auriculate has various excellences, anti-aging effects (Guo Qizheng etc. " Chinese Medicine journal " in February, 1987 for example, 32 phases), immunoregulation effect (Gu Ligang " Chinese medicine is closely reported " in November, 1986,50 phases), promote hair growth effect (Wu Bingqin etc. " Chinese Medicine journal " in February, 1987,29 phases) etc. all once to report.As the saponin class of one of effective constituent that contains in the Root of Bunge Auriculate, on the books in " Chinese medicinal herbal " (second, People's Health Publisher, 331 pages, 1979).These saponin classes are the mixtures with multiple compound of similar chemical structure.Wherein seven kinds have been verified its chemical structure (J.Chen, Z.Zhangand J.Zhou, Acta Bot.Yunnanica December nineteen ninety, 197 phases).They are C
21Steroid glycoside (C
21The steroid glucoside, the pregnane glycoside), called after Wilfoside C3N, C1N, C1G, K1N, Cynauricuricuoside A, B, C.As everyone knows, in the CynanchunWilfordi Hemsly that antasthenic uses, also contain Wilfoside (H.Mitsuhashi and K.Hayashi, Shoyakugakuzasshi, in January, 1985,39 phases) in the Korea peninsula.As everybody knows, these saponin classes are very important compound with excellent anti-tumor activity effect (Zhao Jin etc. " Chinese Medicine journal " in March, 1988,29 phases).And the multiple pregnane glycoside that excellent pharmacologically active effect is also arranged in other class plant of report Asclepiadaceae arranged once in recent years, new pregnane glycoside (the B.Ma et al. that for example has anti-obesic action in Hainan milk class, J.Nat.Prod., 1997 60 phases, 134-138 page or leaf), pregnane Pu grape glucoside (the R.Aquino et al that has the anti-tumor activity effect among the Leptadenia hastate Decne; J.Nat.Pord, 1996,59 phases, 555-564 page or leaf) etc.The importance of the saponin class that these are all contained in the hint Root of Bunge Auriculate shows especially just day by day.
The product form that Root of Bunge Auriculate is used as food, what sell on the market now is that its foundation partly remains untouched and is cut into flaky and to its rhizome portion processing, refining (powder, refined powder, the fast thawing product etc.) that form.That is to say to have only two kinds of products substantially.Also have water extract composite shampoo in addition, sale is also arranged on the market it.A spot of only so product is developed, and is astonishing in the history in hundreds of years of Root of Bunge Auriculate! It is from now on demands for development that the characteristics of performance Root of Bunge Auriculate are developed various products.Root of Bunge Auriculate has excellent pharmacological actions such as anti-aging effects, adjusting immunity, the effect of promotion hair growth, therefore compare with existing goods as protective foods, dose seldom can manifest the strong pharmacological action of its excellence, be very important, the direction that is from now on to be pursued.In addition, also be very important as the purposes of pharmaceuticals, there is as makeup a spot of interpolation can bring into play its good effect again, this also is the direction of pursuing from now on.Produce to develop at industrial operable extracting method and extract the saponin class that contains in the Root of Bunge Auriculate but successfully never in the past with protective foods, pharmaceuticals, the makeup that just can show on a small quantity its very excellent pharmacological action.Therefore, industrial operable easy, cheap, laborsaving, efficient and saponin class extracting method non-environmental-pollution is desired from now on.
Root of Bunge Auriculate has two kinds as the present finished product form of food, and a kind of is its rhizome portion to be remained untouched be cut into flaky Radix Polygoni Multiflori tablet, and another kind is the radix polygoni multiflori powder that its rhizome portion processing and refining is formed.The present manufacture method of radix polygoni multiflori powder is unprocessed rhizome portion to be added a large amount of cold water mix pulverize, and removes fiber, makes water and solid part separately again after centrifugation, solid part is collected carry out drying.This method is identical with the general manufacture method of utilizing its rhizome portion manufacturing starch, and basic skills is to use cold water flush, and end dissolving part in the cold water is made product.This is to utilize Root of Bunge Auriculate rhizome portion to contain the feature of a large amount of starch substances, develops the method for manufacturing.Therefore, produced like this product main component is a starch.A big problem points of this manufacture method is in centrifugal separation processes, discard the part of water, promptly discard owing to containing water section, Root of Bunge Auriculate water soluble components and be not dissolved in water or solubleness is very little, the one-tenth that proportion is lighter than water grades, after centrifugation, the composition that contains in water is just drained.This is not limited only to centrifugal separation, and the water flushing also is common problem when making.The most of water soluble of the effective constituent that contains in the Root of Bunge Auriculate has gone out of use along with the discarded of water.With the related important effective constituent saponin class of the present invention, though little to the solvability of water, have the character of interfacial agent as glycoside, so with water Combination is arranged, owing to water section goes out of use, thereby saponin class major part goes out of use.Therefore, present manufacture method has been thought thousand and one way to the usage quantity of water, using method etc., manages to make to make it contain the product of a large amount of plurality of active ingredients as far as possible.But reduce the effusive methods of its effective constituent of control such as usage quantity of water, final quality product is reduced, also become a very big problem.One of effective ways that address these problems are exactly: simply extract the saponin class that wherein contains by technical scale in a large amount of depleted water, if extract feasible, utilizing again of these saponin classes also is feasible, after for example and now the product on the market mixes, produce than the product innovation of product better effects if in the past or produce new protective foods and also have aspect purposes such as pharmaceuticals, makeup, the product form that can extract from Root of Bunge Auriculate will be extremely extensive.Therefore, press for a kind of easy, cheap, efficient and realize the extracting method that can extract the saponin class of industrialization from water section.
Summary of the invention
The present invention is directed to above-mentioned weak point a kind of method of the saponin class that contains in the Root of Bunge Auriculate being extracted production is provided, invented saponin class in the Root of Bunge Auriculate, at water or suitably in the aqueous alcohol of determining alcohol, being adsorbed on methacrylic is synthetic adsorbent, or aromatic series (SDVB) is on the synthetic adsorbent, then use the aqueous alcohol of higher proper concn, perhaps acetone carries out the method for desorb, thereby finishes the present invention.
Produced like this saponin class contains the multiple saponin that contains in the Root of Bunge Auriculate.Record and narrate as the front, now identified the saponin class chemical structure of 7 kinds of Root of Bunge Auriculate.But, also contain more saponin class in the Root of Bunge Auriculate.We think that they are the still undetermined novel cpds of chemical structure.That is to say that the present invention has can be with the produced outstanding feature of novel saponin class of useful Root of Bunge Auriculate.
Because of extracting to (for example liking solid state or liquid state, the leacgate of water or aqueous alcohol etc.) and different, during solid state, comprise and make pharmaceuticals, makeup etc., use various solvents generally speaking, for example chloroform, ethanol, methyl alcohol, water and their mixed solvent etc. extract after the saponin class is dissolved.In food mfg, preferably use ethanol, water and their mixing solutions from the security viewpoint.Solvent in these extracts is removed, and remaining extract can be used as product.In general, these extracts are because contain multiple a large amount of foreign matter, so generally will further carry out various precision work, for example profound extraction solvent, distribute according to different solvents, utilize operations such as ion exchange resin is made with extra care, activated carbon treatment, activated alumina processing.Need carry out for example various chromatographys such as silica gel, gel, ion exchange resin toward contact when making the goods can reach pharmaceutical purity, and the high-speed liquid chromatography method that is further purified usefulness, operations such as avidity chromatography.Extraction to as if special extracting method such as supercritical extraction also arranged during liquid state, but in general, saponin class dissolving under the water leacgate situation, use organic solution with water sepn, for example extract the saponin class, remove after the solvent, adopt above-mentioned object with hexane, trichloromethane, acetate, N-butanols etc., various process for purification when solid state are purified it, reach its required purity.When purifying, under pure content can reach state with its solvent separation degree, with taking identical method with aqueous extract with aqueous alcohol.These manufacture method, at pharmaceuticals, the occasion of makeup is feasible.But, often use hexane when making edible oil, but under most of occasion,, do not wish to use these organic solvents from the viewpoint of security with soybean in the occasion of food.In addition, in the occasion of pharmaceuticals, makeup, when handling a large amount of Root of Bunge Auriculate water leacgates, also need large-scale extraction element, solution retrieving arrangement, use a large amount of organic solvents, manufacture method is very complicated, and manufacturing cost is very high.Thereby, industrial press for easy, cheap laborsaving, efficiently, help the extracting method of environment protection.
The saponin class that contains in the Root of Bunge Auriculate is extracted the method for production, it is characterized in that water or aqueous alcohol leacgate with Root of Bunge Auriculate are synthetic adsorbent or the absorption of fragrant family synthetic adsorbent by methacrylic, use moisture 40%～100% aqueous alcohol or alcohol or acetone desorb elution process more in addition, solvent in the eluant is removed, just can be extracted the saponin class in the Root of Bunge Auriculate.Fragrance family synthetic adsorbent adopts vinylbenzene, Vinylstyrene.
The method of the saponin class that contains in the Root of Bunge Auriculate being extracted production can be lower than 40% aqueous alcohol leacgate with water or the water ratio of Root of Bunge Auriculate, being adsorbed on methacrylic is on the synthetic adsorbent, the desorb elution in addition of alcohol with moisture 40%～100% or alcohol, remove solvent, from Root of Bunge Auriculate, obtain the saponin class.
The method of the saponin class that contains in the Root of Bunge Auriculate being extracted production can be lower than 20% aqueous alcohol leacgate with water or the water ratio of Root of Bunge Auriculate, being adsorbed on methacrylic is on the synthetic adsorbent, the desorb elution in addition of alcohol with moisture 80%～100% or alcohol, remove solvent, from Root of Bunge Auriculate, obtain the saponin class.
The method of the saponin class that contains in the Root of Bunge Auriculate being extracted production can be lower than 20% aqueous alcohol leacgate with water or the water ratio of Root of Bunge Auriculate, after the desalting treatment, being adsorbed on methacrylic is on the synthetic adsorbent, the desorb elution in addition of alcohol with moisture 80%～100% or alcohol, remove solvent, from Root of Bunge Auriculate, obtain the saponin class.
The method of the saponin class that contains in the Root of Bunge Auriculate being extracted production can be lower than 20% aqueous alcohol leacgate with water or the water ratio of Root of Bunge Auriculate, being adsorbed on aromatic series (vinylbenzene, Vinylstyrene) is on the synthetic adsorbent, with acetone to its desorb elution, remove solvent, from Root of Bunge Auriculate, obtain the saponin class.
Produce the saponin class water leacgate that contains Root of Bunge Auriculate in a large number when the water of described Root of Bunge Auriculate is meant the refined powder of making Root of Bunge Auriculate, perhaps fresh Root of Bunge Auriculate is placed on outstanding turbid, the saponin class centrate that contains the tuber of multiflower knotweed that carries out the centrifugation generation after stirring, fully soaking in the water.
The leacgate of described aqueous alcohol is meant that adopting aqueous alcohol that fresh Root of Bunge Auriculate or exsiccant Root of Bunge Auriculate sheet, powder are carried out leaching handles, and extracts the saponin class aqueous alcohol leacgate that contains Root of Bunge Auriculate.
Above-mentioned aqueous alcohol or alcohol comprise methyl alcohol, ethanol, propyl alcohol.
The representative resin that uses in the chemical fields such as food, medical treatment, catalyst, water treatment is an ion exchange resin.In the ion exchange resin, strongly-acid, slightly acidic, strong basicity, weakly alkaline, inner complex resin etc. are arranged.The representative polymer carrier of these ion exchange resin is the copolymer of vinylbenzene and Vinylstyrene, according to the difference of degree of crosslinking the very many ion exchange resin of kind is arranged, and uses widely industrial.And according to special polymerization, what also have makes porousness to polymer carrier.Among the present invention, ion exchange resin also can be used as complementary use, but the key resin of relevant invention is not an ion exchange resin.
Synthetic adsorbent used in the present invention is according to the chemical structure of different polymer carriers, and being divided into methacrylic system and aromatic series (SDVB) is two kinds.The basic structure of these synthetic adsorbents is the macromolecular compounds with insoluble three-dimensional crosslinking structure, in general, has porousness.Though do not have ion-exchange group, have very big surface area, have the character of mainly adsorbing various organic compound by van der waals forces.Its fragrant family sorbent material is generally X=H, but in order to strengthen hydrophobicity, also has to add Br etc. and become the aromatic series based compound.Methacrylic is a synthetic adsorbent, does not contain the aromatic series based compound, compares with fragrant family synthetic adsorbent, and the polarity of its polymer carrier is very high, and its character is fit to the higher organic compound of absorption relative polarity.The chemical structure that its structural formula is synthetic adsorbent diaion HP2MG for its representative methacrylic.Propylene is that synthetic adsorbent is the nearly edge compound of methacrylic system, and also being referred to as methacrylic sometimes is synthetic adsorbent.Fragrance family synthetic adsorbent has or not according to the substituent of aromatic nucleus, is to increase the special processing that surface-area carries out, and pore distributes, particle dia not equal.Methacrylic is a synthetic adsorbent.Distribute according to pore, not degree of crosslinking not equal, the synthetic adsorbent that numerous species is arranged on the market is used by industrial widely selling, and these commodity are not quite similar according to different manufacturing firms, and various trade name is arranged.The existing several trade(brand)names of illustration are for reference.The synthetic adsorbent that Mitsubishi KCC produces is commodity as methacrylic, and diaion HP10, HP2MG are arranged; As fragrant family commodity, diaion HP10, HP20, HP21, HP30, HP40, HP50 are arranged, add the commodity of hydrophobic group as fragrant family, there are amino grain soap SP205, SP206, SP207 to come the commodity of handling through high surface area as aromatic series, amino grain soap SP800, SP825, SP850, SP875 are arranged, as the less precision separation product of particle dia, products such as the amino grain of diaion HP20SS soap SP20SS are arranged, and SD300, the SD301 that Chinese Zhengguang Resin Co., Ltd. produces, SD302 etc. are fragrant family synthetic adsorbent.HZ802, HZ803 etc. that Yadong, Shanghai nuclear grade resins company limited produces are fragrant family synthetic adsorbent.
Utilize these synthetic adsorbents to extract, make with extra care, make saponin time-like in the Root of Bunge Auriculate, the absorption of the saponin class of the determining alcohol of aqueous alcohol and Root of Bunge Auriculate and the relation of desorb are extremely important.Absorption and desorb are subjected to influence of various factors.For example the ionic kind of the difference of the product of the different manufacturing companies of the kind of synthetic adsorbent, quality discrepancy that each is made batch, temperature, use solvent amount, adsorption method, adsorption time, desorption method, parsing time, coexistence and concentration etc.The result that present inventors inquire into keen determination, clearly in water, the saponin class of Root of Bunge Auriculate can be by methacrylic and fragrant family synthetic adsorbent adsorbed.
In addition, done elaboration in [problem that traditional technology and invention plan to solve] one, but made the occasion of the refined powder of Root of Bunge Auriculate, according to present manufacture method, the saponin of Root of Bunge Auriculate contains under the state in a large amount of water and goes out of use.Extracting the saponin class from this a large amount of water leacgate is one of main achievement of the present invention.Therefore, the absorption of water leacgate is crucial, this occasion, and it is adsorbed that the saponin class of Root of Bunge Auriculate is synthesized sorbent material.But from fresh Root of Bunge Auriculate or exsiccant Root of Bunge Auriculate sheet, powder, extract the saponin class sometimes.Under this occasion, because the saponin class is low to the solubleness of water, use aqueous alcohol etc. to extract in order to improve solubleness, can reduce the solvent amount, improved extraction efficiency.To further make clear with high concentration aqueous alcohol and adsorb condition with desorb, just mean and will get water clear or low determining alcohol adsorbs the extraction conditions of saponin class, this in Root of Bunge Auriculate, extract, refining, to make the saponin class be very important.Certainly as us from knowing the document, extracting with the mixed solvent of chloroform and methyl alcohol is general method.But it is not to be ideal that these solvents use aspect food.At medicine, aspect the makeup, the problem of remaining solvent also often appears, and in order to remove residual solvent fully, and, need some equipment, thereby need various types of large-scale devices cause industrial unfavorable factor in order not produce public hazards (environmental pollution).Thereby use aqueous alcohol, and particularly aqueous ethanol extracts, and is the most favourable from the viewpoint of environment, consider from aspects such as security, economy in addition, and aspect industrialization, be ideal.
Using methacrylic is the occasion of synthetic adsorbent, with moisture 40% alcohol, though absorption is not thoroughly but have a considerable amount of saponin classes to be adsorbed, so, would rather adsorb not thoroughly, but get rid of impurity, improve purity, when primary viewing is conceived to this point, formed the adsorption conditions that we recommended.Under this condition, the saponin class that is adsorbed in the aqueous alcohol or alcohol of 40～100% higher determining alcohols, is carried out desorb from synthetic adsorbent, and these eluants are collected, and solvent is removed, and can produce the saponin class of Root of Bunge Auriculate.Here be expressed as with 100% alcohol carry out elution be for narrate convenient for the purpose of.In other words, the alcohol that uses under this occasion is absolute alcohol, but in fact, in the synthetic adsorbent of absorption saponin class, more or less can contain moisture content, so and 100% described in non-legible.The expression of 100% methyl alcohol in this specification sheets, propyl alcohol etc. also is same.
Using aromatic series (SDVB) is the occasion of synthetic adsorbent, and the saponin analogy of Root of Bunge Auriculate is that the stronger adsorptive power of synthetic adsorbent is adsorbed on the synthetic adsorbent with methacrylic.When elution, need the higher alcohol of concentration, promptly allow water ratio be lower than the leacgate of 20% aqueous alcohol, be adsorbed on the fragrant family synthetic adsorbent, to carry out elution to it with moisture 80～100% alcohol or alcohol, these eluants are collected, remove after the solvent, can produce the saponin class of Root of Bunge Auriculate.The a large amount of minimizing of solvent amount of using these high concentration aqueous alcohol that the saponin class in the Root of Bunge Auriculate is used when extracting also is industrial one to greatly enhance the place and exist.
The result that present inventors discuss with fragrant family synthetic adsorbent the time, has distinguished that the absorption of the saponin class of Root of Bunge Auriculate has been subjected to the ionic influence of coexistence.Promptly to be adsorbed on the synthetic adsorbent more thoroughly for the saponin class that makes Root of Bunge Auriculate, just in order more effectively extracting industrial, to remove under the ionic state of coexistence, it is more favourable that it is adsorbed on the synthetic adsorbent.Can adopt ion exchange resin treatment during desalination.Industrial method commonly used such as electrodialysis.
The result that present inventors study in the occasion of utilizing fragrant family synthetic adsorbent, has distinguished with aqueous alcohol or alcohol, and the meeting of the saponin class of desorb Root of Bunge Auriculate produces very strong afterbody prolongation effect.Promptly from synthetic adsorbent, desorb time expand at leisure, this situation will make the rate of recovery of saponin class lower, the solvent amount of using increases (its result must use more massive various device), make the lost of life of synthetic adsorbent etc., derive many problems that are unfavorable for suitability for industrialized production.For addressing these problems, the effect of acetone is significantly, promptly by using acetone to make it can desorb from synthetic adsorbent rapidly, thereby have solved an industrial problem points.The acetone that use this moment in not having the scope of obstacle, is allowed certainly and is contained water, ethanol etc.
Methacrylic is synthetic adsorbent and fragrant family synthetic adsorbent, to the saponin class of Root of Bunge Auriculate adsorb, the effect of desorb, and the compound beyond the saponin class of Root of Bunge Auriculate adsorbed and the effect of desorb, very big difference is arranged between the two.Thereby the two synthetic adsorbent is used in combination, just can extract, make with extra care, make more highly purified saponin class, this point is conspicuous.
As described above, using methyl-prop rare is synthetic adsorbent or fragrant same clan synthetic adsorbent, from the leacgate of the water of Root of Bunge Auriculate or aqueous alcohol, extract, refining, make the saponin class of Root of Bunge Auriculate, the novel manufacturing process that this did not report before being fully.
Embodiment
Below list embodiment, the present invention will be described in further detail, and the present invention has more than and is limited to these examples.
[quantitative method of the saponin class that contains in the Root of Bunge Auriculate] following embodiment records and narrates the quantitative method that the saponin class is adopted.
1. sample
According to the method in the document (J.Chen, Z.Zhang and J.Zhou, Acta Bot, Yunnanica 12,197,1990), from fresh Root of Bunge Auriculate, isolate Wilfoside C1N, C3N, C1G, K1N separately.In the following example, mainly Wilfoside C1N is used as the mark product and uses.
2. quantitative method
Use high efficiency liquid chromatography (HPLC, high performance liquid chromatography; Waters company, 2487 types) carry out quantitatively.Adsorption tower is that (3.9 * 150mm) chromatographic analysis solvents are that (methyl alcohol: water=82.5: 17.5), flow velocity is 1mL/min to 82.5% methyl alcohol, measures and uses UV, and inspection-free thing injection rate is 5mL, analyzes to Nova-Pack C18.With Wilfoside C1N, K1N mark product, made the typical curve of mark product concentration and area.The typical curve of two kinds of saponins does not have too big-difference.Though therefore Root of Bunge Auriculate contains multiple saponin, supposes that these typical curves are identical, calculates the total content of saponin class.Each embodiment has carried out the modification of typical curve.
Embodiment 1: the fresh white tuber of multiflower knotweed (25g) after will removing the peel be placed in the water in (250mL) outstanding turbid, stir, fully soak after, carry out centrifugation (3000rpm).With the supernatant liquor (230mL) of centrifugation be divided into 6,50,85, four parts of 85mL.6mL former state concentrate drying is analyzed soluble portions with the ethanol of 2mL.When measuring its weight behind the 50mL concentrate drying, be 310mg.85mL intactly washes by the adsorption tower of diaion HP2MG (methacrylic is synthetic adsorbent, Mitsubishi chemical Co., Ltd's system, 10mL), become 120mL, again 6mL is wherein carried out concentrate drying, use the ethanol of 2mL that soluble portions is carried out the HPLC analysis.Use 30mL ethanol elution 2 times then.Intactly carrying out HPLC respectively analyzes.Other 85mL intactly fully washes by diaion HP2MG (10mL) adsorption tower.To merge by liquid and water lotion, carry out dry overnight with drying machine behind the concentrate drying.Its weight is 490mg, uses 0.1m Nacl then, and 30mL tries elution.Fully washing then continues to carry out elution with ethanol (30mL), the ethanol elution is divided carry out the HPLC analysis, extrapolates 0.1m, the elution rate of Nacl.The result of embodiment 1 is as follows.The saponin class is that benchmark calculates according to the result that HPLC analyzes with Wilfoside C1N.
The about 37mg of water leaching of Root of Bunge Auriculate (is adsorbed onto on the diaion HP2MG (10mL).
The saponin class that calculates Root of Bunge Auriculate is adsorbed on the adsorption rate on the HP2MG.Its result is: containing Wilfoside C1N among the 85mL is that 2.1mg almost 100% is adsorbed.The amount of ethanol elution for the first time is 2.0mg.The elution rate is about 100%, and the rate of ethanol elution for the second time is about 3%.
Use 0.1M, during Nacl almost not elution go out.
In the material of diaion HP2MG absorption, the content of Wilfoside C1N is about 5.7%.In the material of diaion HP2MG absorption, total saponin amount is calculated and is resin absorption thing about 15.9%.
With Wilfoside C1N is that benchmark has been calculated with after the diaion HP2MG processing concentration rate of saponin class, the clearance of material beyond the saponin class.Concentrated about 250 times from fresh white tuber of multiflower knotweed dry weight, concentrated about 14 times from fresh white tuber of multiflower knotweed water sample extract.Material about 93% beyond the saponin class of fresh white tuber of multiflower knotweed water sample extract is removed.
Embodiment 2:
With the fresh white tuber of multiflower knotweed (15g) after the peeling be placed in the water (150mL) outstanding turbid, stir, fully soak after, carry out centrifugation (3000rpm), the supernatant liquor (134mL) of centrifugation is divided into two parts of 6mL, 128mL.6mL former state concentrate drying carries out HPLC with the ethanol of 2mL to soluble portions and analyzes.After the 128mL former state is fully washed by diaion HP2MG (10mL) adsorption tower, use moisture 50%, 70%, 90% ethanol and 100% ethanol (each 30mL) to carry out elution, and carry out HPLC respectively and analyze.The result of embodiment 2 is as following note.The elution rate of saponin class is a benchmark with Wilfoside C1N, calculates according to the HPLC analytical results, and be 37% with moisture 50% alcoholic acid elution rate, with moisture 70% ethanol elution rate is 46%, with moisture 90% ethanol elution rate is 15%, is 4% with 100% ethanol elution rate, adds up to 102%.
Embodiment 3:
Carried out elution with embodiment 2 the same moisture 50%, 70%, 90% ethanol and 100% ethanol of using, its result, aqueous ethanol does not have much difference during with ethanol.Can adopt methyl alcohol, propyl alcohol to carry out elution equally, with eluant concentrate, dry, remove solvent, promptly can from Root of Bunge Auriculate, obtain the saponin class.
Embodiment 4:
To remove the peel the fresh white tuber of multiflower knotweed (10g) be placed in the water (100mL) outstanding turbid, stir, fully soak after, carry out centrifugation (3000rpm).The supernatant liquor (88mL) of centrifugation is passed through strong basic ion exchange resin (the system diaion SA-11A of Mitsubishi chemical Co., Ltd, OH
-Type 10mL) adsorption tower will merge by liquid and water lotion with the water flushing of 20mL, again by strong-acid ion exchange resin (the system diaion SK=104H of Mitsubishi chemical Co., Ltd
-Type 10mL) adsorption tower is with the water flushing of 20mL.To wash by HP20 (fragrant family synthetic adsorbent, Mitsubishi Denki K.K., 20mL) adsorption tower by overflowing and the water lotion merging again.To merge by liquid and water lotion (200mL), get wherein the 6mL concentrate drying after, with the ethanol of 2mL soluble portions has been carried out the HPLC analysis.Again 50% ethanol (60mL) being carried out HPLC by diaion HP20 adsorption tower former state analyzes.Next use ethanol (60mL) to carry out elution, former state is carried out HPLC and is analyzed.Next use acetone (40mL) elution, remove solvent after, with the ethanol of 2mL soluble portions is carried out HPLC and analyzes.The HPLC analytical results of embodiment 4 can be summarized as:
The passing through of formaldehyde resin HP20 adsorption tower do not detect the saponin class in liquid and the water lotion, and the saponin class is almost all adsorbed by HP20.
In 50% the ethanol eluant, do not detect the saponin class, do not gone out by elution.
In the alcoholic acid eluant,, there is 50% saponin class to be reclaimed approximately by elution if be that benchmark calculates with Wilfoside C1N.
With acetone the saponin class is all reclaimed.
Embodiment 5:
With the fresh white tuber of multiflower knotweed (30g) of peeling be placed in the water (300mL) outstanding turbid, stir, fully soak after, carry out centrifugation (3000rpm).Reach 300mL after in the supernatant liquor of centrifugation, adding less water.Respectively get 100mL, respectively by the amino grain of diaion HP20 (4mL) soap SP825 fragrance family synthetic adsorbent (the system 4mL of Mitsubishi chemical Co., Ltd), diaion HP2MG (4mL).Passing through separately got 6mL behind concentrate drying in the liquid (about 100mL), with 2mL ethanol soluble portions is carried out HPLC and analyze.Then, carry out elution with ethanol 50mL, remain untouched and carry out HPLC and analyze at separately adsorption tower.The result of embodiment 5 is as follows: the saponin class is that benchmark is calculated as follows according to the result that HPLC analyzes with WilfosideC1N:
The adsorption rate of saponin class on various resins of Root of Bunge Auriculate is respectively diaion HP2MG (about 93%), diaion HP20 (about 75%), amino grain soap SP825 (about 60%), the order of adsorptive power is respectively diaion HP2MG) diaion HP20), amino grain soap SP825.
Alcoholic acid elution graphic presentation diaion HP2MG does not almost have afterbody to prolong, and afterbody prolongs and diaion HP20 (about 75%), amino grain soap SP825 find to have significantly.
Embodiment 6:
With the fresh white tuber of multiflower knotweed (22g) of peeling be placed in the water (220mL) outstanding turbid, stir, fully soak after, carry out centrifugation (3000rpm).With the supernatant liquor (205mL) of centrifugation be divided into 25,90, three parts of 90mL.25mL former state concentrate drying carries out the HPLC analysis with 2mL ethanol to soluble portions after becoming 6mL.The 90mL former state becomes 150mL by after diaion HP20 (fragrant family synthetic adsorbent, Mitsubishi chemical Co., Ltd's system, 10L) the adsorption tower washing, with 10mL concentrate drying wherein, with the ethanol of 2mL soluble portions is carried out the HPLC analysis.Other 90mL is by strong basic ion exchange resin (Mitsubishi chemical Co., Ltd's system, diaion SA-11A, OH
-Type, 10mL) adsorption tower washes with the water of 90mL.To merge by liquid and water lotion, by strong-acid ion exchange resin (the system diaion SK-104 of Mitsubishi chemical Co., Ltd, H
+Type, 10mL), adsorption tower and water flushing.To merge by liquid and water lotion and become 200mL, to wherein 13mL concentrate drying, ethanol with 2mL, soluble portions is carried out HPLC to be analyzed, the elution operation is as follows: the occasion that spent ion exchange resin is handled, carry out elution with 1M Nacl (30mL), and fully water flushing (whole liquid measures, 200mL) then, (30mL) carries out elution with ethanol.HPLC is carried out in ethanol elution division analyze, extrapolate the elution rate of 1M Nacl.Do not carry out the occasion of ion exchange resin treatment,, carry out HPLC and analyze with ethanol (30mL) elution 2 times.The result of embodiment 6 is as follows.The saponin class is that benchmark is calculated as follows according to the result that HPLC analyzes with Wilfoside C1N:
The untreated occasion of ion exchange resin: the adsorption rate of alkaline methanol resin HP20 is 81.2%, and the rate of ethanol elution for the first time is 75.3%, and ethanol elution rate is 4.2% for the second time, adds up to 79.5%.
The occasion of ion exchange resin treatment: the adsorption rate of diaion HP20 is almost 100%, 1M, and Nacl elution rate is about 32% (reckoning), and alcoholic acid elution rate is 48%.
Embodiment 7:
With the fresh Root of Bunge Auriculate (40g) in peeling back be placed in the water (400mL) outstanding turbid, stir, fully soak after, carry out centrifugation (3000rpm).The supernatant liquor (350mL) of centrifugation is divided into 6mL, 86mL * 4 part, 6mL former state concentrate drying, with 2mL ethanol soluble portions being carried out HPLC analyzes, after 86mL * 4 are fully washed by diaion HP2MG (10mL) adsorption tower respectively, also carry out elution with moisture each 30mL of 20%, 30%, 40%, 50% ethanol, concentrate drying respectively then carries out the HPLG analysis with the ethanol of 2mL to soluble portions.The result of embodiment 7 is as follows, and the saponin class is that benchmark calculates according to the HPLC analytical results with Wilfoside C1N.During moisture 20% ethanol, almost do not gone out by elution; There is percentum elution to go out during moisture 30% ethanol; Carry approximately during moisture 40% ethanol and wash out 18%; During moisture 50% ethanol approximately elution go out 40%.
Embodiment 8:
To remove the peel the back fresh white tuber of multiflower knotweed (50g) be placed in the water (500mL) outstanding turbid, stir, fully soak after, carry out centrifugation (3000rpm), with the supernatant liquor (430MI) of centrifugation by strong basic ion exchange resin (the diaion SA-11A of Mitsubishi chemical Co., Ltd, OH
-Type, 50mL) the adsorption tower water flushing of 100mL.To merge by liquid and water lotion, by strong-acid ion exchange resin (the diaion SK-104 of Mitsubishi chemical Co., Ltd, H
+Type, 50mL) adsorption tower is with the flushing of the water of 100mL, will merge by liquid and water lotion, add water to 700mL, is divided into 6mL, about 139mL * 4 part.Ethanol with 2mL behind the 6mL former state concentrate drying carries out the HPLC analysis to soluble portions; About 139mL * 4, by diaion HP20 (10mL) adsorption tower, fully, carry out elution respectively with moisture 50%, 70%, 80%, 90% ethanol and each 30mL of 100% ethanol through after the washing, carry out concentrate drying respectively, with 2mL ethanol soluble portions is carried out HPLC and analyze.The result of embodiment 8 such as following, saponin class are that benchmark calculates according to the result that HPLC analyzes with Wilfoside C1N.Do not find that almost elution goes out during moisture 50%, 70% ethanol.Find during moisture 80% ethanol that about 33% is gone out by elution, during moisture 90% ethanol approximately elution go out 75%, during moisture 100% ethanol approximately elution go out 90%.
Embodiment 9:
Identical with embodiment 8, carry out elution with moisture 70%, 90% ethanol and 100% ethanol, its result, the elution rate when aqueous ethanol and ethanol does not have much difference.
Embodiment 10:
To remove the peel the back fresh white tuber of multiflower knotweed (10g) be placed on hang in moisture 70% ethanol (100mL) turbid, stir fully immersion after, carry out centrifugation (3000rpm).Supernatant liquor after the centrifugation (90mL) is passed through strong basic ion exchange resin (the Diaion SA-11A of Mitsubishi chemical Co., Ltd, OH
-Type, 10mL) adsorption tower with the flushing of 20mL water, will merge by liquid and water lotion, by strong-acid ion exchange resin (the Diaion SK-104 of Mitsubishi chemical Co., Ltd, H
+Type, 10mL) adsorption tower 20mL water flushing, will merge by liquid and water lotion, add water to 200mL, be divided into 6mL and 140mL two minutes, 6mL former state concentrate drying 2mL ethanol carries out HPLC to soluble portions and analyzes.About 140mL is by diaion HP20 (10mL) adsorption tower, fully washing, with the elution of 30mL ethanol, the ethanol of concentrate doing respectively admittedly with 2mL carries out elution, soluble portions is carried out HPLC to be analyzed, the saponin class is calculated with the Wilfoside C1N result that to be benchmark analyze according to HPLC, has 78% saponin to be extracted out approximately.
Embodiment 11:
To remove the peel the back fresh white tuber of multiflower knotweed (100g) be placed on hang in the water (1000mL) turbid, stir and fully after the immersion, carry out centrifugation (3000rpm), the supernatant liquor after the centrifugation (900mL) is divided into two parts of 6mL and 894mL.With 2mL ethanol soluble portions has been carried out the HPLC analysis behind the 6mL former state concentrate drying; 894mL, fully washes with moisture 20% ethanol fully through after the washing by diaion HP2MG (methacrylic is synthetic adsorbent, Mitsubishi chemical Co., Ltd's system, 30mL) adsorption tower again.Then, carry out elution, eluant is concentrated, just produce insoluble substance with moisture 90% ethanol.This insolubles is filtered with flushing limit, a large amount of watersides, is collected, after the water flushing, carry out dry overnight with drying machine after, obtain 237.6mg, this product has been carried out the HPLC analysis.The saponin class is that benchmark calculates according to the result that HPLC analyzes with Wilfoside C1N.As a result, the saponin class content of this product is 85.3%.
Embodiment 12:
The saponin class water leacgate (water of Root of Bunge Auriculate) that contains Root of Bunge Auriculate in a large number that produces during with the refined powder of making Root of Bunge Auriculate is that synthetic adsorbent or aromatic series (vinylbenzene, Vinylstyrene) are the absorption of synthetic adsorbent adsorption tower by methacrylic is housed, again with moisture 40%～100% aqueous alcohol or acetone desorb flushing adsorption tower in addition, eluant is removed solvent through concentrate drying, can from the water of Root of Bunge Auriculate, extract the saponin class.
Embodiment 13:
Adopt aqueous alcohol that fresh Root of Bunge Auriculate or exsiccant Root of Bunge Auriculate sheet, powder are carried out leaching and handle, extract the saponin class aqueous alcohol leacgate that contains Root of Bunge Auriculate, is that synthetic adsorbent or aromatic series (vinylbenzene, Vinylstyrene) are the absorption of synthetic adsorbent adsorption tower with the above-mentioned saponin class aqueous alcohol leacgate that contains Root of Bunge Auriculate by methacrylic is housed, again with moisture 40%～100% aqueous alcohol or acetone desorb flushing adsorption tower in addition, eluant is removed solvent through concentrate drying, can from the water of Root of Bunge Auriculate, extract the saponin class.
The effect of invention: in sum, the saponin class of extracting Root of Bunge Auriculate according to the present invention from the leacgate of the water of Root of Bunge Auriculate or aqueous alcohol can easy, cheap, laborsaving, high-level efficiency, and can extract and make with extra care in environmentally safe ground, can be provided at the manufacture method of industrial only Root of Bunge Auriculate saponin class.
Conform to into the chemical constitution formula of the basic structure of sorbent material, that is: synthetic adsorbent is the macromolecular compound that three-dimensional crosslinking structure is arranged with basic structure as follows.
The synthetic adsorbent chemical structure is as follows:
1, fragrant family synthetic adsorbent
X=H, Br etc.
2, methacrylic is a synthetic adsorbent
N=2; First
Aldehyde is resin HP2MG
Claims (8)
1, a kind of method of the saponin class that contains in the Root of Bunge Auriculate being extracted production, it is characterized in that it is synthetic adsorbent or the absorption of fragrant family synthetic adsorbent by methacrylic that the water of Root of Bunge Auriculate or water ratio are lower than 40% aqueous alcohol leacgate, use moisture 40%～100% aqueous alcohol or alcohol or acetone desorb elution process more in addition, solvent in the eluant is removed, just can be extracted the saponin class in the Root of Bunge Auriculate.
2, the method for the saponin class that contains in the Root of Bunge Auriculate being extracted production according to claim 1, it is characterized in that water or the water ratio of Root of Bunge Auriculate are lower than 20% aqueous alcohol leacgate, being adsorbed on methacrylic is on the synthetic adsorbent, the desorb elution in addition of alcohol with moisture 80%～100% or alcohol, remove solvent, from Root of Bunge Auriculate, obtain the saponin class.
3, the method for the saponin class that contains in the Root of Bunge Auriculate being extracted production according to claim 1, it is characterized in that water or the water ratio of Root of Bunge Auriculate are lower than 20% aqueous alcohol leacgate, after the desalting treatment, being adsorbed on methacrylic is on the synthetic adsorbent, the desorb elution in addition of alcohol with moisture 80%～100% or alcohol, remove solvent, from Root of Bunge Auriculate, obtain the saponin class.
4, the method for the saponin class that contains in the Root of Bunge Auriculate being extracted production according to claim 1, it is characterized in that water or the water ratio of Root of Bunge Auriculate are lower than 20% aqueous alcohol leacgate, be adsorbed on the fragrant family synthetic adsorbent, with acetone to its desorb elution, remove solvent, from Root of Bunge Auriculate, obtain the saponin class.
5, the method for the saponin class that contains in the Root of Bunge Auriculate being extracted production according to claim 1, produce the saponin class water leacgate that contains Root of Bunge Auriculate in a large number when the water that it is characterized in that described Root of Bunge Auriculate is meant the refined powder of making Root of Bunge Auriculate, perhaps fresh Root of Bunge Auriculate is placed on outstanding turbid, the saponin class centrate that contains the tuber of multiflower knotweed that carries out the centrifugation generation after stirring, fully soaking in the water.
6, according to claim 1 the saponin class that contains in the Root of Bunge Auriculate is extracted the method for production, it is characterized in that fragrant family synthetic adsorbent adopts vinylbenzene, Vinylstyrene.
7, the method for the saponin class that contains in the Root of Bunge Auriculate being extracted production according to claim 1, the leacgate that it is characterized in that described aqueous alcohol is meant that adopting aqueous alcohol that fresh Root of Bunge Auriculate or exsiccant Root of Bunge Auriculate sheet, powder are carried out leaching handles, and extracts the saponin class aqueous alcohol leacgate that contains Root of Bunge Auriculate.
8, according to claim 1 the saponin class that contains in the Root of Bunge Auriculate is extracted the method for production, it is characterized in that aqueous alcohol or alcohol comprise methyl alcohol, ethanol, propyl alcohol.
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| CN1313085C (en) * | 2005-06-23 | 2007-05-02 | 中国人民解放军第二军医大学 | Application of total hypone of radix cynanchi bungei and hypnone for preparing medicine for treating gastrointestinal tract diseases |
| CN101125154B (en) * | 2007-08-14 | 2010-04-21 | 山东轻工业学院 | Raidx cynanchum bungei decne glycoside of mountain Tai and preparation method thereof |
| CN113817614B (en) * | 2021-11-02 | 2023-06-27 | 盐城师范学院 | High-efficiency synthesis C 21 Alternaria alternata Z-44 of steroid glycoside and application thereof |
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