CN103755776A - Method for extracting saponin and rhamnose from yellow ginger - Google Patents
Method for extracting saponin and rhamnose from yellow ginger Download PDFInfo
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Abstract
The invention provides a method for producing diosgenin in a large scale from yellow ginger rootstock by utilizing an extraction, crystallization and recrystallization method aiming at the problems that the yellow ginger resources are insufficient at present, lots of wastes are produced, the long-term utilization and development prospects of the yellow ginger are severely influenced, lots of wastes are produced in the environment by adoption of a current extraction method. Moreover, the yield of yellow ginger saponin and rhamnose in the yellow ginger can be improved.
Description
Technical field
The invention belongs to natural product manufacture field, related to a kind of method of comprehensive utilization of turmeric extracted saponin, more particularly related to one and extracted saponin from yellow ginger, the method simultaneously again waste extracting after saponin being fully utilized.
Background technology
Yellow ginger has another name called Rhizome of Peltate Yam, is Dioscoreaceae Wild yam (Dioscrea.L) per nnial herb, is the highest kind of Determination of Diosgenin in the world.By < < Pharmacopoeia of People's Republic of China > > (2000 editions), recorded, the content of diosgenin in its rhizome (disogenin) (being commonly called as saponin) is 1.1 ﹪～16.15 ﹪, is the important medicine chemical material of synthesizing steroid hormones (steroid hormone) medicine and contraceptive steroid (steroid prophylactic).Herbaceous species.Rhizome grows wild.Stem is very thin, without hair, has vertical wrinkle or shallow slot, sometimes at the base portion both sides of branch or petiole dimpling, go out, or the short thorn of tool.Leaf alternate, peltate; Blade triangular shape is avette or long avette, and long 5～11 centimetres, wide 4～9 centimetres, edge is shallow wavy, and base portion is heart-shaped or be bordering on a section shape, and common 3 split, and central sliver tip is point gradually, both sides sliver circle ear shape; Petiole is shorter than blade.Flower unisexuality, dioecy; Male inflorescence spike, armpit is raw, branch sometimes; Flower stockless, normal 2～3 cluster, and only grow completely for 1～2; Bract is membranous, avette or triangular shape is avette; Tapel 6, avette, red-purple, stamen 6; Female inflorescence is spent 6～8, and flower has short handle, and perianth 6 splits, staminody; Ovary elongated cylindrical.Black-and-blue after capsule is dry, surface is with white meal, and the nearly lune of wing, is about 2.5 centimetres, wide approximately 1.5 centimetres, top nick, or be bordering on and cut a shape, and the narrow circle of base portion, the flat oval of seed, be the wing of film like around.5～August of florescence, really 9～October of phase.
China is the country of origin of Rhizome of Peltate Yam, just has the record of " Shaoze, its careless many Chinese yams are hoped in Jingshan mountain, north " in the < < the Classic of Mountains and Rivers > > before more than 2,000 year.Rhizome of Peltate Yam is Dioscoreaceae Wild yam (Dioscrea.L) per nnial herb, is the highest kind of Determination of Diosgenin in the world.By < < Pharmacopoeia of People's Republic of China > > (2000 editions), recorded, the content of diosgenin in its rhizome (disogenin) (being commonly called as saponin) is 1.1 ﹪～16.15 ﹪, is the important medicine chemical material of synthesizing steroid hormones (steroid hormone) medicine and contraceptive steroid (steroid prophylactic).With root stock, be used as medicine, traditional Chinese medicine thinks that its Xing Wei Gan ﹑ Ku ﹑ is cool, has removing heat from the lung to relieve cough, dampness removing is treating stranguria, removes obstruction in channels to relieve pain, and the function of detoxify and promote the subsdence of swelling, can control cough due to lung-heat, damp and hot pouring pain, lumbago due to pathogenic wind-dampness, the swollen sore of disliking of carbuncle, osteopatia sprain, honeybee bites insect bite, has the effects such as the infection for the treatment of skin acute festering type, soft tissue injury, reducing blood-fat simultaneously, also has the cholesterol of reduction, anti-inflammatory, the pharmacological action such as antitumor.
The root stock of Rhizome of Peltate Yam is containing chemical compositions such as the Mierocrystalline cellulose of the starch of the diosgenin of 1.1 ﹪～16.15 ﹪, 45 ﹪ left and right, 40 ﹪ and some water-soluble glycosides, alkaloids, flavonoid glycoside, cardiac glycoside, alkaloid, tannin, pigments.Liu builds this grade and has carried out extraction and the property research of pigment in Rhizome of Peltate Yam rhizome, result shows that Chinese yam pigment has ultraviolet ray is had to stronger sorption, heat-resisting, light fastness is good, Fe3+, Cu2+, Hg2+3 metal ion species all have certain hyperchromic effect to pigment, the character such as the impact of acid base pair pigment is larger, for comprehensive utilization provides a new way.
Dioscin comprises sugar and aglycon two portions.For saponin(e is positioned, Guo Yongbing etc. are divided into 5 sections by Rhizome of Peltate Yam rhizome, the distribution of its diosgenin is studied to discovery, the Determination of Diosgenin on tender stem top is the highest, the section of putting forth takes second place, then being tender stem section, is thereafter old stem section and bottom section, and the content of fibrous root and terrestrial stem base section is very low.Diosgenin has another name called saponin.It is the raw material that synthesizes in the world at present more than 300 kind of steroid hormone and contraceptive bian.
Liu Cheng comes, thin layer chromatography for Chen Yanyong etc. (different developping agent), Paper Chromatography has carried out separation and Extraction to Rhizome of Peltate Yam, result is isolated two kinds of water-insoluble trisaccharide saponin(es and two kinds of water-soluble tetrose saponin(es in root stock, with acetylize, acid hydrolysis, enzymolysis, the poor calculating of molecular rotation and infrared spectra, mass spectrum, hydrogen spectrum, the methods such as carbon spectrum are carried out Analysis and Identification, be respectively 1. and show-pull out chinaroot greenbrier sapogenin, 2. Trillium tschonoskii Maxim time glycosides, structure is 3-O-(β-D-glucopyanosyl)-diosgenin, 3. diosgenin-bis-glucosides, structure is 3-0-* β-D-glucopyanosyl (1 → 4)-β-D-glucopyanosyl]-diosgenin, 4. very thin saponin(e, structure is 3-O-, β-D-glucopyanosyl (1 → 3)-[a-L-sandlwood pyranose (1 → 2)+-β-D-glucopyanosyl } 4 steroidal compounds of-diosgenin, according to its chemical structure, be speculated as secondary saponin.
Rhizome of Peltate Yam sample is in order to study the protosaponin of Rhizome of Peltate Yam, explore its activity, within 1985, they separate and obtain 5. diosgenin cetylate through dry post method the methanol extract of fresh rhizome again, 6. β-sitosterol, very thin saponin(e, 7. former very thin saponin(e and 8. 5 kinds of steroid materials of former shield leaf saponin(e, its Central Plains shield leaf saponin(e is a newfound compound, the structure of identifying 2 kinds of former saponin(es is respectively 7. 3-O-, β-D-glucopyanosyl (1 → 3)-[a-L-sandlwood pyranose (1 → 2)+-β-D-glucopyanosyl }-26-O-, β-D-glucopyanosyl }-diosgenin and 8. 3-O-{a-L-sandlwood pyranose (1 → 3)-* β-D-glucopyanosyl (1 → 2)+-β-D-glucopyanosyl }-26-O-, β-D-glucopyanosyl }-diosgenin.
Tang Shirong, Wu Yufen etc. get two kinds of water-insoluble trisaccharide saponin(es (A and B) and two kinds of water-soluble tetrose saponin(es (C and D) from Rhizome of Peltate Yam root.9. A is new saponin(e, tentatively titled shield leaf saponin A, structure is diosgenin-3-O-* β-D-glucopyanosyl (1 → 2)+-O-[a-L-sandlwood pyranose (1 → 3)+-O-β-D-glucopyranoside, 10. B is very thin saponin(e isomer, (11) C is former shield leaf saponin A, (12) D is former shield leaf saponin(e B.Tang Shirong, Jiang Zhidong uses Aerial Part of Dioscorea Zingiberensis through extracting, decolouring, silica gel column chromatography and oppositely column chromatography for separation obtain shield leaf saponin A 1, A2, A3 and fork stamen saponin I V4 kind mainly contain the saponin(e of refined nurse sapogenin, first three is planted as new compound, be respectively (13) refined nurse sapogenin-3-O-[a-L-sandlwood pyranose (1 → 2)+-β-D-glucopyranoside, (14) hydroxyl refined nurse sapogenin-3-O-[a-L-sandlwood pyranose (1 → 2)+-β-D-glucopyranoside, (15) refined nurse sapogenin-3-O-{a-L-sandlwood pyranose (1 → 2)-* β-D-glucopyanosyl (1 → 4)+--β-D-glucopyranoside, wherein the aglycon of shield leaf saponin A 2 is a new steroid sapogenin, called after shield leaf sapogenin.The 4th kind for (16) refined nurse sapogenin-3-O-{a-L-sandlwood pyranose (1 → 2)-* β-D-glucopyanosyl (1 → 3)+--β-D-glucopyranoside.These are different from the saponin(e situation that underground part mainly contains diosgenin.
Jiang Chaohui etc. to Rhizome of Peltate Yam sapogenin breeding time content rule research think, it is to budding and full-bloom stage that saponin(e accumulates peak period in rhizome, after productive phase obviously decline; In root growth obvious 8～September, content improves, and during to October of withering period and November, declining appears again in content; Within 2 years, raw sapogenin content was apparently higher than life in 1 year; Should be buddingging flowering period of the withering period of the 2nd year or the 3rd year suitable collection period.The researchs such as Ding Zhizun think, Rhizome of Peltate Yam is generally higher to the Sheng phase saponin content of blooming in the budding period, wither the phase from productive phase to beginning, and saponin content declines gradually; Old rhizome saponin content is higher than new rhizome; The rhizome saponin content that moisture content is high is also high.
From yellow ginger, obtain at present diosgenin and have three kinds of methods.Directly acid-hydrolysis method: acid hydrolysis is to make glycosidic bond fracture generate aglycon and sugar.Pre-fermentation method: it is generally acknowledged that pre-fermentation method can improve the yield of diosgenin.Pre-fermentation method has aging process, enzymolysis process, microbe fermentation method.Partition method processing Chinese yam plant: first isolate vegetable fibre and starch from Rhizome of Peltate Yam, remainder extracts diosgenin through spontaneous fermentation again.
China starts to set up diosgenin production plant from the fifties in last century, adopt the direct acid-hydrolysis method of Rothrod invention to produce the technique of diosgenin, raw material soaking, pulverize after, acid adding heating hydrolysis, then use organic solvent extraction.The shortcoming of this technique is: the existence of and much starch hard due to Chinese yam rhizome quality, and facile hydrolysis is not thorough, and saponin yield is low; Owing to being hydrolyzed under the strong condition such as concentrated acid and high temperature, in Chinese yam, other composition, as starch etc. is destroyed, is unfavorable for the comprehensive utilization of resource.
Afterwards, all reported before vegetable material acid hydrolysis ferment in advance (claiming again spontaneous fermentation) both at home and abroad.China most of diosgenin factory all adopts this production technique at present, is about to after Chinese yam raw material pulverizing is soaked let alone spontaneous fermentation a couple of days, after plant materials is loose, adds strong acid heating hydrolysis, is washed to neutrality, and after filter residue oven dry, auspicious industrial naptha extracts saponin.The method improves saponin yield, but impurity increase, melting point depression.In addition, this technique is the same with production of saponin technique the earliest, public affairs have utilized content in yellow ginger only to account for 2% saponin, and account for the dry-matter compositions such as 98% starch, be not only used effectively completely, and produce a large amount of containing BOD, COD and acid high organic waste water, for follow-up water treatment causes very big difficulty.By this technique, one ton of fresh ginger of every processing produces 2.5 tons of above waste water.
If carry out process for cleanly preparing design from the angle of pollution treatment merely, not only pollution treatment cost is high, and with regard to current wastewater treating technology, is also difficult to realize.Therefore the key of turmeric extracted saponin clearer production technology is wherein to account for nearly 80% starch and processing and the utilization of cellulosic effective utilization and high density saponin waste water.Because starch has the glucose of nearly half destroyed after strong acid hydrolysis, no matter be that its utilising efficiency will reduce greatly for extracting glucose or zymamsis.Therefore to the utilization of Dioscorea. zingiberensis Wright Starch, to before acid hydrolysis, carry out, not only can maximally utilise starch resource, also will greatly reduce the required sour consumption of hydrolysis.
Existing Dioscorea. zingiberensis Wright Starch edible or the report brewing alcoholic beverages.Northwest Institute of Zoology has proposed " partition method is produced diosgenin novel process ": its key step is elder generation's separating starch slurry from yellow ginger, carry out again dilute acid hydrolysis and make mashing, after separation, obtain liquid glucose and sugared slag, sugared slag is used for extracting saponin, and liquid glucose is for inosine produced by fermentation.But according to the literature,, the disappearance of this technique in starch washing separates can affect saponin yield, and water treatment amount is large, does not obtain yet at present large-scale popularization.
Sugar degree in turmeric saponin wastewater is higher, have bibliographical information from high density saponin waste water, to extract glucose or utilize carbohydrate wherein to carry out zymamsis, but these methods has only been recycled the reducing sugar in waste water, still have secondary wastewater pollution problem.The employing waste saponin residues such as Miao Lihong directly absorb high density saponin waste water and produce organic fertilizer through compost fermentation, as the one improvement method of waste saponin residue and waste water.But this technology has only solved the governing problem of waste saponin residue and high density saponin waste water, do not relate to Dioscorea. zingiberensis Wright Starch utilization and in, the processing problem of lower concentration saponin waste water.
Summary of the invention
The object of the invention is to for current yellow ginger inadequate resource and produce a large amount of wastes; have a strong impact on yellow ginger and utilized for a long time development prospect; and adopt current extracting method all can cause a large amount of wastes to environment; the invention provides one and utilize extraction, crystallization and recrystallization method large-scale production turmeric saponin from yellow ginger rhizome, can improve again the yield of turmeric saponin and rhamnosyl in yellow ginger.
The microbial strains that the present invention adopts, yeast saccharomyces cerevisiae (Saccharomyces cerevisiae) derives from China Committee for Culture Collection of Microorganisms's common micro-organisms center, and numbering is respectively CGMCC No.2.558.
The preparation of S. cervisiae powder: cultivate by S. cervisiae CGMCC No.2.558 cultural method, centrifugation medium obtains yeast saccharomyces cerevisiae thalline, the dry S. cervisiae powder that is.
Therefore, the invention provides a kind of method of turmeric extracted saponin and rhamnosyl, its concrete steps are as follows:
(1) yellow ginger is cleaned, crushed after being dried crosses 20 mesh sieve >90%;
(2) add 80-90% methyl alcohol or ethanolic soln, extract three times, each 90min;
(3) by 3 yellow ginger extracting solution concentration and recovery methyl alcohol or ethanol to without alcohol taste;
(4) to adding hydrochloric acid soln to make its final concentration in concentrated solution, be 2.5mol/L, at 30 ℃, carry out acid hydrolysis 1.5 hours;
(5) acid hydrolysis solution is filtered, obtain thick saponin;
(6) thick saponin adopts sherwood oil to carry out crystallization and recrystallization, and then standing 8-12 hour filters, and recrystallization, until crystallization color is pure white, obtains turmeric saponin finished product by crystallisate vacuum-drying;
(7) in filtrate, add 1mol/L sodium hydroxide solution to neutralize, adopt AB-8 macroporous resin to adsorb at 45 ℃, filter, obtain the macroporous resin particle of adsorpting pigment, water carries out wash-out with 55% ethanol after rinsing again, elutriant is concentrated into the dry thing of dry acquisition and is yellow pigment sterling;
(8) (7) gained filtrate is added common bread yeast powder CGMCC No.2.558 at 28 ℃, stir insulation 3-5h at once;
(9) ceramic membrane filter removes yeast saccharomyces cerevisiae thalline, and filtrate carries out being evaporated to the 1/4-1/6 of original volume at 50 ℃, directly adds the kind crystalline substance of α-L-rhamnosyl, and at 4 ℃, crystallization and recrystallization method are prepared highly purified rhamnosyl.
In one embodiment, the consumption of methyl alcohol or ethanol described in step (2), its volume (L)/yellow ginger weight (kg)/ratio is 1:4-8.
In one embodiment, the consumption of sherwood oil described in step (6), its volume (L)/thick saponin weight (kg)/ratio is 1:2-5.
In one embodiment, the consumption of bread yeast powder described in step (8), its weight (kg)/filtrate volume (L) ratio=1:10-15.
In one embodiment, the add-on of rhamnosyl kind crystalline substance described in step (9), its weight (g)/filtrate volume (L) ratio=1:20-25.
Technique effect
1, in the inventive method, raw material, equipment used is common common raw material, equipment, has avoided in commercial process, for the dependence of expensive raw materials, instrument, having reduced widely production cost.
2, yellow ginger output is high, price is low, convenient sources, and follow-up resource is secure.
3, the inventive method is simple to operate; only use extraction, the filtration of resin chromatography, crystallization recrystallize technology, also do not need precision instrument or automatic equipment, greatly reduced the production cost of turmeric saponin; simplify production process, guaranteed large-scale production turmeric saponin.
4, the present invention can also obtain a large amount of rhamnosyls, is conducive to reduce the production cost of turmeric saponin, gets back simultaneously and can be used for the natural pigment that food adds.
Embodiment
With embodiment of the present invention, further illustrate essentiality content of the present invention below, but with this, do not limit the present invention.
Embodiment 1
After taking the dry yellow ginger of 100kg, pulverized 20 mesh sieve >90%, add 80% ethanol of 500kg, extract three times, each 1.5 hours, 3 yellow ginger extracting solutions are merged to concentration and recovery ethanol extremely without alcohol taste, to adding hydrochloric acid soln to make its final concentration in concentrated solution, be 2.5mol/L, at 30 ℃, carry out acid hydrolysis 90min; Acid hydrolysis solution is filtered, obtain thick saponin 4.34kg.Thick saponin adopts sherwood oil to carry out crystallization and recrystallization, and then standing 8-12 hour filters, recrystallization, until crystallization color is pure white, crystallisate vacuum-drying is obtained to turmeric saponin finished product 3.68kg, through HPLC method, carry out turmeric saponin content detection and reach 99.42%.Filtrate adopts the macroporous resin of AB-8 to adsorb at 45 ℃, filter, obtain the macroporous resin particle of adsorpting pigment, with after distilled water flushing again the ethanol with 55% carry out wash-out, elutriant is concentrated into the dry thing of dry acquisition and is yellow pigment sterling 1.45kg, through look valency, detect and reach 408; Add the common bread yeast powder of 10kg at 28 ℃, to stir insulation 3h gained filtrate 110L at once; Ceramic membrane filter removes yeast saccharomyces cerevisiae thalline, filtrate carries out being evaporated to 22L at 50 ℃, directly add the brilliant 1g of kind of α-L-rhamnosyl, at 4 ℃, crystallization and recrystallization method are prepared highly purified rhamnosyl, obtain rhamnosyl 0.67kg, through HPLC method, carry out rhamnosyl content detection and reach 98.55%.
Embodiment 2
After taking the dry yellow ginger of 200kg, pulverized 20 mesh sieve >90%, add 80% ethanol of 900kg, extract three times, each 1.5 hours, 3 yellow ginger extracting solutions are merged to concentration and recovery ethanol extremely without alcohol taste, to adding hydrochloric acid soln to make its final concentration in concentrated solution, be 2.5mol/L, at 30 ℃, carry out acid hydrolysis 90min; Acid hydrolysis solution is filtered, obtain thick saponin 8.85kg.Thick saponin adopts sherwood oil to carry out crystallization and recrystallization, and then standing 8-12 hour filters, recrystallization, until crystallization color is pure white, crystallisate vacuum-drying is obtained to turmeric saponin finished product 7.45kg, through HPLC method, carry out turmeric saponin content detection and reach 99.46%.Filtrate adopts the macroporous resin of AB-8 to adsorb at 45 ℃, filter, obtain the macroporous resin particle of adsorpting pigment, with after distilled water flushing again the ethanol with 55% carry out wash-out, elutriant is concentrated into the dry thing of dry acquisition and is yellow pigment sterling 3.03kg, through look valency, detect and reach 412; Add the common bread yeast powder of 22kg at 28 ℃, to stir insulation 4h gained filtrate 250L at once; Ceramic membrane filter removes yeast saccharomyces cerevisiae thalline, filtrate carries out being evaporated to 40L at 50 ℃, directly add the brilliant 2g of kind of α-L-rhamnosyl, at 4 ℃, crystallization and recrystallization method are prepared highly purified rhamnosyl, obtain rhamnosyl 1.35kg, through HPLC method, carry out rhamnosyl content detection and reach 98.67%.
Embodiment 3
After taking the dry yellow ginger of 400kg, pulverized 20 mesh sieve >90%, add 80% ethanol of 1800kg, extract three times, each 1.5 hours, 3 yellow ginger extracting solutions are merged to concentration and recovery ethanol extremely without alcohol taste, to adding hydrochloric acid soln to make its final concentration in concentrated solution, be 2.5mol/L, at 30 ℃, carry out acid hydrolysis 90min; Acid hydrolysis solution is filtered, obtain thick saponin 17.56kg.Thick saponin adopts sherwood oil to carry out crystallization and recrystallization, and then standing 8-12 hour filters, recrystallization, until crystallization color is pure white, crystallisate vacuum-drying is obtained to turmeric saponin finished product 13.55kg, through HPLC method, carry out turmeric saponin content detection and reach 99.63%.Filtrate adopts the macroporous resin of AB-8 to adsorb at 45 ℃, filter, obtain the macroporous resin particle of adsorpting pigment, with after distilled water flushing again the ethanol with 55% carry out wash-out, elutriant is concentrated into the dry thing of dry acquisition and is yellow pigment sterling 5.08kg, through look valency, detect and reach 421; Add the common bread yeast powder of 40kg at 28 ℃, to stir insulation 5h gained filtrate 450L at once; Ceramic membrane filter removes yeast saccharomyces cerevisiae thalline, filtrate carries out being evaporated to 90L at 50 ℃, directly add the brilliant 2g of kind of α-L-rhamnosyl, at 4 ℃, crystallization and recrystallization method are prepared highly purified rhamnosyl, obtain rhamnosyl 2.78kg, through HPLC method, carry out rhamnosyl content detection and reach 98.72%.
Claims (5)
1. the invention provides a kind of method of turmeric extracted saponin and rhamnosyl, its concrete steps are as follows:
(1) yellow ginger is cleaned, crushed after being dried crosses 20 mesh sieve >90%;
(2) add 80-90% methyl alcohol or ethanolic soln, extract three times, each 90min;
(3) by 3 yellow ginger extracting solution concentration and recovery methyl alcohol or ethanol to without alcohol taste;
(4) to adding hydrochloric acid soln to make its final concentration in concentrated solution, be 2.5mol/L, at 30 ℃, carry out acid hydrolysis 1.5 hours;
(5) acid hydrolysis solution is filtered, obtain thick saponin;
(6) thick saponin adopts sherwood oil to carry out crystallization and recrystallization, and then standing 8-12 hour filters, and recrystallization, until crystallization color is pure white, obtains turmeric saponin finished product by crystallisate vacuum-drying;
(7) in filtrate, add 1mol/L sodium hydroxide solution to neutralize, adopt AB-8 macroporous resin to adsorb at 45 ℃, filter, obtain the macroporous resin particle of adsorpting pigment, water carries out wash-out with 55% ethanol after rinsing again, elutriant is concentrated into the dry thing of dry acquisition and is yellow pigment sterling;
(8) (7) gained filtrate is added common bread yeast powder CGMCC No.2.558 at 28 ℃, stir insulation 3-5h at once;
(9) ceramic membrane filter removes yeast saccharomyces cerevisiae thalline, and filtrate carries out being evaporated to the 1/4-1/6 of original volume at 50 ℃, directly adds the kind crystalline substance of α-L-rhamnosyl, and at 4 ℃, crystallization and recrystallization method are prepared highly purified rhamnosyl.
2. according to the method for claim 1, the consumption of methyl alcohol or ethanol described in step (2), its volume (L)/yellow ginger weight (kg)/ratio=1:4-8.
3. according to the method for claim 1, the consumption of sherwood oil described in step (6), its volume (L)/thick saponin weight (kg)/ratio is 1:2-5.
4. according to the method for claim 1, the consumption of bread yeast powder described in step (8), its weight (kg)/filtrate volume (L) ratio=1:10-15.
5. according to the method for claim 1, the add-on of rhamnosyl kind crystalline substance described in step (9), its weight (g)/filtrate volume (L) ratio=1:20-25.
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| CN105733971A (en) * | 2014-12-09 | 2016-07-06 | 商南县时代生物科技有限公司 | Saccharomyces cerevisiae strain as well applications and culture method thereof |
| CN107384677A (en) * | 2017-07-17 | 2017-11-24 | 长沙爱扬医药科技有限公司 | The method that Chinese yam saponin and health liquor are produced using yellow ginger |
| CN107417763A (en) * | 2017-08-18 | 2017-12-01 | 刘玉通 | It is a kind of using production of saponin from turmeric and the technique of rhamnose |
| CN107417763B (en) * | 2017-08-18 | 2019-08-20 | 刘玉通 | A kind of technique using production of saponin from turmeric and rhamnose |
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