CN1305869C - Tech. for preparing isoflavone of red clover from red clover - Google Patents
Tech. for preparing isoflavone of red clover from red clover Download PDFInfo
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- CN1305869C CN1305869C CNB2004100131894A CN200410013189A CN1305869C CN 1305869 C CN1305869 C CN 1305869C CN B2004100131894 A CNB2004100131894 A CN B2004100131894A CN 200410013189 A CN200410013189 A CN 200410013189A CN 1305869 C CN1305869 C CN 1305869C
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Abstract
The present invention relates to a technology for preparing the isoflavone of red clover from red clover, particularly to a method for preparing the isoflavone of red clover from red clover. The method has the following concrete technical process: firstly, red clover alcohol liquid extract is prepared by the hot reflux extraction of low-carbon alcohol; then, hydrolytic treatment is carried out by mineral acid; the pH value of filtering liquid with the hydrolytic treatment is regulated to be neutral; the neutral filtering liquid is depressurized and condensed; high-temperature activated silica gel powder or high-temperature activated active aluminum oxide is added for absorption; after the washing and the impurity removal of absorbed substances, the absorbed substances are eluted; eluent is filtered; solvent is recovered, and after condensation and drying, total isoflavone preparation objects of the red clover are obtained. After the present invention is adopted, onospin and sissotorin which have very high content in the red clover are previously hydrolyzed and conversed into formoononetin and Abiochanin A; four kinds of effective component isoflavone, such as the formoononetin, the Abiochanin A, genistein and daidzein can be easily and effectively prepared from the red clover; the total isoflavone content of preparation products surpasses 60%, and accordingly, the isoflavone of red clover from red clover has the favorable value of medicinal foods or functional foods.
Description
Technical field the present invention relates to a kind of preparation method who prepares the clinical medicinal or red clover isoflavones that functional food is used from red clover.
The background technology modern medicine study proved estrogen metabolism disorderly with climacterium syndrome, osteoporosis, cardiovascular disorder, senile dementia, estrogen-dependent tumour, closely related as uterus carcinoma, mammary cancer, prostate cancer, colorectal carcinoma etc., controversies in hormone replacement in the elderly has benifit to the control of climacterium syndrome, osteoporosis, cardiovascular disorder, senile dementia, prostate cancer, colorectal carcinoma, but may increase the sickness rate of uterus carcinoma, mammary cancer.Studies have shown that in a large number, phytoestrogen be supplemented with the control that helps above-mentioned disease, the disadvantage of the controversies in hormone replacement in the elderly of but having no talent.Therefore, the replacement therapy of phytoestrogen more and more is subjected to people's attention.
Red clover is a kind of herbage of extensive plantation, claims red clover, red clover again.The active substance that screw oil expeller axle isoflavones (Isoflavones) is that a class contains is similar to the human body estrin structure, the non-steroidal spline structure, human body oestrogenic hormon and gonad-stimulating hormone metabolism and expression are had the two-phase regulating effect.It mainly comprises " genistein ", " Daidezin ", " Biochanin A ", " Formononetin " and glucoside thereof, often is called as " phytoestrogen " (Phytoestrogens).Red clover is a kind of plant that contains four kinds of effective isoflavones rare the time, and west advanced country has recommended the red clover total isoflavones goods are applied to climacterium and menopausal women, sufferers of osteoporosis face as food supplement in recent years.
At present the preparation method who prepares screw oil expeller axle isoflavones from red clover has following several:
1. solvent method water, methyl alcohol, aqueous ethanol isopolarity solvent are done the heat extraction.Water with in, low-concentration ethanol is suitable for the extraction of flavonoid glycoside; Methyl alcohol and high concentration ethanol then are used for the extraction of glucoside unit.With the extract component complexity of solvent method gained, often need fluid extract opposed polarity solvent extraction and separation, and the extract isoflavone levels is low with water or alcohol, solvent consumption is big.
2. precipitator method water or ethanol-extracted, the flavones ingredient that extracting solution obtains flavonoid glycoside and has adjacent two phenolic hydroxyl groups or carboxyl structure with the plumbic acetate or the polyvinylpyrrolidone precipitator method.Though this method is easy, isoflavones is extracted not exclusively, and isoflavone levels is lower in the prepared product.
3. hydrolysis method thick daidzin that solvent method or the precipitator method are obtained is with the hydrochloric acid solution heating hydrolysis; Or polar solvent heat extracts solution and directly adds acid or enzymic hydrolysis, and glucoside unit is separated out in cooling.Though this method is easy, the foreign matter content of isoflavones is very high in the prepared product.
Column chromatography normal adopt polymeric amide, silica gel, aluminum oxide, dextrane gel, macroporous resin column chromatography method arranged.The solvent method or the precipitator method are obtained thing, and with above-mentioned weighting agent absorption, the back obtains various daidzin and glucoside unit with many groups multicomponent solvent system wash-out of opposed polarity gradient behind the concentrate drying.This method can obtain the quite high isoflavones goods of content, but separates different daidzins and glucoside unit operation more complicated, and the production cycle is long, and the cost height is difficult to large-scale industrial production.
5. preparative high performance liquid chromatography is thick isoflavones goods that column chromatography is obtained by preparative high performance liquid chromatography preparing the monomer of highly purified a certain isoflavones components, and is not suitable for the preparation of total isoflavone goods.
Isoflavones components is very complicated in the plant, and the physico-chemical property difference of various isoflavones components is very big, is difficult to adopt a logical method.At present, the production technique of red clover isoflavone formulation generally is to adopt solvent method to produce the lower thick product of isoflavone content---red clover medicinal extract; Adopting column chromatography is that the feedstock production isoflavone content is than higher goods with red clover medicinal extract.In addition, the isoflavones components that has estrogen-like effects in the plant generally includes isoflavone aglycones (element) and daidzin two big classes.It is generally acknowledged that reactive site is a glucoside unit, its glucoside is not only active low but also be difficult to absorb.Daidzin content is quite high in the plant, particularly at leaf with in spending.The content of daidzin surpasses 1/3 of its total isoflavone in the red clover, and pursuing target is high-load isoflavone aglycones in the red clover total isoflavones goods.
" method for preparing Herba Trifolii Pratentis extract " (number of patent application 03118845), this method comprise the following steps: with methyl alcohol or extraction using alcohol red clover herb; Filter this extracting solution and concentrated; With concentrated solution centrifuging and taking slag; With the dregs of a decoction with sherwood oil or normal hexane degreaser drying; After concentrating with the extraction of aliphatic ester class, crystallization obtains extract a; With extracting ethanol-extracted, the recovery alcohol of back slag, get concentrated solution with 50-90%; In mother liquor behind the gained crystallization and concentrated solution adjust pH=8-10, cross polystyrene skeleton macroporous adsorbent resin and separate, get extract b, extract a and b are merged, re-refine with alcohol, get the high-content extract.This application provides a kind of application Herba Epimedii, vitamins B ↓ [1], B ↓ [6] and has contained VITAMIN and has been combination and Herba Trifolii Pratentis extract compatibility, be used for kidney tonifying, replenish phytoestrogen, thus Breast Cancer Prevention, prostate cancer, colorectal carcinoma and prevent and treat osteoporosis, climacteric syndrome better.
Summary of the invention the objective of the invention is at above-mentioned present situation, aim to provide and a kind ofly can from red clover, produce four kinds of effective constituent isoflavones easier, expeditiously: Formononetin, Biochanin A, genistein, Daidezin, the total isoflavone content of prepared product surpasses 60%, has well medicinal or functional food is worth prepares the preparation technology of red clover isoflavones from red clover.
The implementation of the object of the invention is, a kind ofly prepares the preparation technology of red clover isoflavones from red clover, and its concrete technical process is:
1) will dry the storage medicinal material and cut into thin segment,
2) preparation red clover alcohol fluid extract: the red clover thin segment extracts with the thermal backflow of 6～12 times of amount low-carbon alcohol, and decompression and solvent recovery also concentrates and makes every milliliter of red clover fluid extract that contains crude drug 1 gram ± 0.2 gram,
3) hydrolysis treatment of pure red clover fluid extract: fluid extract is fully stirred redissolution with 2～5 times of amount 95% ethanol earlier, cross the elimination precipitation, it is 2～5% that filtrate adds ore deposit acid to final concentration, thermal backflow hydrolysis treatment 1.5～3 hours, and the hydrolyzed solution filter and remove residue,
4) filtrate of hydrolysis treatment is added saturated sodium hydroxide or potassium hydroxide solution and transfer pH to neutral, filter and remove residue,
5) after the neutral filtrate decompression is concentrated into 1/2 times of original volume, or increase temperature the activatory silica-gel powder and fully grind absorption, the silica gel consumption is 1/2-1 a times of solution amount, dry, carry out subsequent wash and wash-out again and handle, or increase temperature activatory activated alumina particle stirring 1/2～1 hour, the aluminum oxide consumption is 1/2～2 times of solution weight, suction filtration goes filtrate again
6) adsorptive washing impurity elimination: earlier with 2～5 times of amounts, temperature is lower than 15 ℃ cold petroleum ether and stirring washing, suction filtration removes ether, and the back is with 5～20 times of amounts, and temperature is lower than 15 ℃ cold water agitator treating suction filtration and anhydrates, slough the impurity in silica gel or the activated alumina adsorptive
7) silica gel or activated alumina adsorptive wash-out: the silica gel adsorption thing after the carrying out washing treatment with the water saturation vinyl acetic monomer at 50～60 ℃ of abundant wash-outs of heat agitated, water saturation vinyl acetic monomer consumption is 2～4 times of adsorptive weight, alumina adsorption, complex compound were with water saturation vinyl acetic monomer-Glacial acetic acid liquid thermal backflow wash-out of 1000: 1, water saturation vinyl acetic monomer consumption is 2～4 times of adsorptive weight, and elutriant filters, reclaims solvent, concentrates, is drying to obtain the red clover total isoflavones prepared product.
Adopt the present invention, the onospin that content in the red clover is quite high (Ononin) is converted into Formononetin and Biochanin A with sissotorin (Sissoirin) hydrolysis in advance, can produce four kinds of effective constituent isoflavones---Formononetin (Formonontin), Biochanin A (BiochaninA), genistein (Genistein), Daidezin (Daidzein) easier, expeditiously from red clover, the total isoflavone content of prepared product has well medicinal above 50% or functional food is worth.
Description of drawings
Red clover alcohol fluid extract efficient liquid phase chromatographic analysis spectrogram before Fig. 1 hydrolysis
Red clover alcohol fluid extract efficient liquid phase chromatographic analysis spectrogram after Fig. 2 hydrolysis
The cold petroleum ether liquid of Fig. 3 adsorptive high-efficient liquid phase chromatogram
Fig. 4 adsorptive cold water washing liquid high-efficient liquid phase chromatogram
Fig. 5 red clover alcohol medicinal extract-hydrolysis-silica gel adsorption-vinyl acetic monomer wash-out goods liquid chromatogram
Fig. 6 red clover alcohol medicinal extract-hydrolysis-alumina adsorption-acidifying vinyl acetic monomer wash-out goods liquid chromatogram
The concrete technical process of embodiment the present invention is:
1) will dry the storage medicinal material and cut into thin segment,
2) preparation red clover alcohol fluid extract: the red clover thin segment is with the repeatedly thermal backflow extraction 3 hours of 6～12 times of amount low-carbon alcohol, and 2～4 times, low-carbon alcohol is as 40～95% ethanol, methyl alcohol, water-saturated n-butanol.Decompression and solvent recovery also concentrates and makes every milliliter of red clover alcohol fluid extract that contains crude drug 1 gram ± 0.2 gram, be rich in Formononetin, Biochanin A, onospin, sissotorin in the red clover alcohol fluid extract, and contain a small amount of soybean isoflavones and genistein.Its efficient liquid phase chromatographic analysis spectrogram is seen Fig. 1
3) hydrolysis treatment of red clover alcohol fluid extract: red clover alcohol fluid extract is fully stirred redissolution with 2～5 times of amount 95% ethanol earlier, cross the elimination precipitation, be rich in Formononetin, Biochanin A, onospin, sissotorin in the filtrate, and containing a small amount of soybean isoflavones and genistein, its efficient liquid phase chromatographic analysis spectrogram is seen Fig. 1.It is 2～5% that filtrate adds ore deposit acid to final concentration, thermal backflow hydrolysis treatment 1.5～3 hours, and hydrolyzed solution filter and remove residue, methyl alcohol, water-saturated n-butanol thermal backflow extract and concentrate the fluid extract that makes and add 3～5 times of former stirring solvent dilutions of amount, the same filtration, go precipitation.。Filtrate adds ore deposit acid, as adds the concentrated hydrochloric acid hydrolysis processing.Filter and remove residue, the dry residue of filtrate sample detect with the dissolve with methanol high performance liquid chromatography and confirm that onospin, sissotorin become swarming to disappear substantially, be separately converted to and sting awns florigen and Biochanin A, this from Fig. 2 as seen,
4) filtrate of hydrolysis treatment is added saturated sodium hydroxide or potassium hydroxide solution and transfers pH to neutral, filter and remove residue, if do not add adjusting PH with base to neutral and directly concentrate, absorption will not cause the carbonization of part effective constituent to be lost efficacy,
5) silica white or activated alumina particle adsorption treatment: after neutral filtrate decompression is concentrated into original volume about 1/2; Or 100～200 order silica whites that increase temperature activation fully to grind absorption silica gel consumption be the 1/2-1 of amount of solution; Dry; Carrying out subsequent wash and wash-out processes again; Or the activated alumina particle that increases temperature activation stirred 1/2～1 hour; And leave standstill more than 2 hours; The aluminium oxide consumption is 1/2～2 times of solution weight; Fully after the absorption complexing again suction filtration go filtrate; The part isoflavones components will form complex compound with aluminium oxide when adopting alumina particle absorption
6) silica gel or activated alumina adsorptive washing impurity elimination: earlier with 2～5 times of amounts, temperature is lower than 15 ℃ cold petroleum ether and stirring washing 2 times, each 1/2～1 hour, suction filtration removes ether, the back is with 5～20 times of amounts, temperature is lower than 15 ℃ cold water agitator treating 2～5 times, each 1/2～1 hour, suction filtration anhydrates, cold petroleum ether and stirring washing can be dispeled nonpolar and low polar impurity, this susceptible of proof from Fig. 3 does not wherein contain 6 kinds of required isoflavones components substantially, if adopt hot petroleum ether and stirring washing with lost part significant part isoflavones components; The cold water agitator treating can be dispeled a large amount of high polar impurities, and the water washing liquor high performance liquid chromatography of Fig. 4 confirms wherein not contain substantially 6 kinds of required isoflavones components; If do not carry out the cold water agitator treating then prepared product be high gloss mud cream, moisture absorption is difficult to by force pulverize and obviously reduces goods total isoflavone content.
7) silica gel or activated alumina adsorptive wash-out: the silica gel adsorption thing after the carrying out washing treatment with the water saturation vinyl acetic monomer at 50～60 ℃ of abundant wash-outs of heat agitated, each elution time that stirs is no less than 1/2 hour, wash-out number of times 4～5 times, water saturation vinyl acetic monomer consumption is 2～4 times of adsorptive weight, alumina adsorption, complex compound is with water saturation vinyl acetic monomer-Glacial acetic acid liquid (1000: 1) thermal backflow wash-out, water saturation vinyl acetic monomer consumption is 2～4 times of adsorptive weight, each backflow elution time is no less than 2 hours, elutriant filters, wash-out number of times 2～4 times reclaims solvent again, concentrate, be drying to obtain the red clover total isoflavones prepared product.Elutriant contains a certain amount of acetic acid and helps to remove complexing, can obviously improve yield rate.
Ultraviolet spectrophotometry detects, the red clover total isoflavones content of the inventive method preparation, using in Formononetin will be above 60%, and the prepared product high performance liquid chromatography detects and confirms mainly to contain Formononetin and Biochanin A and contain a spot of soybean isoflavones and genistein.Wherein silica gel adsorption vinyl acetic monomer elution method finished product yield is higher than the activated alumina method; And activated alumina adsorbs, complexing, and the relative content of Biochanin A is higher in the acidifying vinyl acetic monomer elution method finished product.The total isoflavone content of two method resulting products is close, and this can find out from Fig. 5,6.
With the red clover total isoflavones goods of the inventive method preparation through with 14 climacterium at monthly age female Wistar kind rat, the surgical removal bilateral ovaries is divided into the red clover total isoflavones group of negative control group, stilboestrol group, large, medium and small 3 dosage at random after one week, every group 10,10 of sham operated rats.Every day, gastric infusion was 1 time, gave the red clover total isoflavones of solvent, stilboestrol and various dose respectively, and continuous 90 days, experimentation on animals the results are shown in Table 1:
Table 1 red clover total isoflavones to climacterium castrated rats estradiol, ovarian follicle generate plain, uterus exponential influence
| Group | Dosage | After testing before body weight (g) experiment | Uterus index (%) | Serum estradiol (pg/L) | The serum ovarian follicle generates plain (pg/L) |
| Sham operated rats | 268±11 288±25 | 0.19± 0.04 | 45.46± 9.10 | 3.97±0.95 | |
| Negative control group | 272±16 283±22 | 0.10± 0.04 | 23.16± 4.16 | 4.07±1.53 | |
| The stilboestrol group | 20μ g/kg | 276±9 276±17 | 0.14± 0.03 | 31.45± 8.50 | 5.66±1.37 |
| 1 group of this prepared product | 8mg/kg | 263±14 314±21 | 0.10± 0.05 | 28.67± 8.45 | 5.66±1.19 |
| 2 groups of this prepared products | 15mg/kg | 265±15 314±14 | 0.11± 0.02 | 30.71± 5.33 | 5.17±1.48 |
| 3 groups of this prepared products | 30mg/kg | 270±18 316±23 | 0.13± 0.03 | 31.54± 8.24 | 4.79±1.35 |
This prepared product has good phytoestrogen effect as seen from the table.
Claims (1)
1, a kind ofly prepare the preparation technology of red clover isoflavones, it is characterized in that its concrete technical process is from red clover:
1) will dry the storage medicinal material and cut into thin segment,
2) preparation red clover alcohol fluid extract: the red clover thin segment extracts with the thermal backflow of 6～12 times of amount low-carbon alcohol, and decompression and solvent recovery also concentrates and makes every milliliter of red clover fluid extract that contains crude drug 1 gram ± 0.2 gram,
3) hydrolysis treatment of pure red clover fluid extract: fluid extract is fully stirred redissolution with 2～5 times of amount 95% ethanol earlier, cross the elimination precipitation, it is 2～5% that filtrate adds ore deposit acid to final concentration, thermal backflow hydrolysis treatment 1.5～3 hours, and the hydrolyzed solution filter and remove residue,
4) filtrate of hydrolysis treatment is added saturated sodium hydroxide or potassium hydroxide solution and transfer pH to neutral, filter and remove residue,
5) after the neutral filtrate decompression is concentrated into 1/2 times of original volume, or increase temperature the activatory silica-gel powder and fully grind absorption, the silica gel consumption is 1/2-1 a times of solution amount, dry, carry out subsequent wash and wash-out again and handle, or increase temperature activatory activated alumina particle stirring 1/2～1 hour, the aluminum oxide consumption is 1/2～2 times of solution weight, suction filtration goes filtrate again
6) adsorptive washing impurity elimination: earlier with 2～5 times of amounts, temperature is lower than 15 ℃ cold petroleum ether and stirring washing, suction filtration removes ether, and the back is with 5～20 times of amounts, and temperature is lower than 15 ℃ cold water agitator treating suction filtration and anhydrates, slough the impurity in silica gel or the activated alumina adsorptive
7) silica gel or activated alumina adsorptive wash-out: the silica gel adsorption thing after the carrying out washing treatment with the water saturation vinyl acetic monomer at 50～60 ℃ of abundant wash-outs of heat agitated, water saturation vinyl acetic monomer consumption is 2～4 times of adsorptive weight, alumina adsorption, complex compound were with water saturation vinyl acetic monomer-Glacial acetic acid liquid thermal backflow wash-out of 1000: 1, water saturation vinyl acetic monomer consumption is 2～4 times of adsorptive weight, and elutriant filters, reclaims solvent, concentrates, is drying to obtain the red clover total isoflavones prepared product.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1981799B (en) * | 2006-05-25 | 2010-11-10 | 湖南省中药提取工程研究中心有限公司 | Preparing method for extracts of red clover |
| CN101386613B (en) * | 2007-09-11 | 2012-05-23 | 兰州大学 | Technique for extracting isoflavones materials from red clover |
| CN102373248A (en) * | 2010-08-26 | 2012-03-14 | 苏州宝泽堂医药科技有限公司 | Method for purifying biochanin A |
| CN103251050B (en) * | 2013-05-10 | 2016-04-27 | 龙岩学院 | A kind of preparation method of trifolium pretense oral liquid |
| CN110183541B (en) * | 2019-04-23 | 2021-07-20 | 湖南华诚生物资源股份有限公司 | Preparation method of red clover polysaccharide and total isoflavone |
| CN112972321B (en) * | 2019-12-16 | 2022-12-02 | 兰州大学 | Natural antioxidant for cosmetics and preparation method thereof |
| CN112142706A (en) * | 2020-10-19 | 2020-12-29 | 湖南朗林生物资源股份有限公司 | Method for extracting and purifying red clover isoflavone |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6391309B1 (en) * | 1996-03-13 | 2002-05-21 | Archer Daniesl Midland Company | Method of preparing and using isoflavones for the treatment of female symptoms |
| CN1439367A (en) * | 2003-03-27 | 2003-09-03 | 武汉健民中药工程有限责任公司 | Pratensein extraction and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6391309B1 (en) * | 1996-03-13 | 2002-05-21 | Archer Daniesl Midland Company | Method of preparing and using isoflavones for the treatment of female symptoms |
| CN1439367A (en) * | 2003-03-27 | 2003-09-03 | 武汉健民中药工程有限责任公司 | Pratensein extraction and preparation thereof |
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