CN1218952C - Preparing method for kutkin II crystal - Google Patents
Preparing method for kutkin II crystal Download PDFInfo
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- CN1218952C CN1218952C CN 02149356 CN02149356A CN1218952C CN 1218952 C CN1218952 C CN 1218952C CN 02149356 CN02149356 CN 02149356 CN 02149356 A CN02149356 A CN 02149356A CN 1218952 C CN1218952 C CN 1218952C
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- rhizoma picrorhizae
- picrorhizae glucoside
- acid
- described method
- glucoside
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Abstract
The present invention relates to a method for extracting, separating and purifying natural compound picroside II with a medicinal application, which provides production technology for extracting, separating and purifying the picroside II by using the roots and stems of Tibet picrorhiza (picrorhiza scrophulariiflora Pennell) and India picrorhiza (picrorhiza kurroa Royleex Benth). The present invention provides a new separation method of adsorbing alkali washing and re-adsorption and a purification method for crystallization and recrystallization by using ethyl acetate-anhydrous alcohol composite solvents.
Description
Rhizoma Picrorhizae glucoside II (Picroside II is a kind of iridoid glycoside analog derivative Amphicoside), have protect the liver, physiologically active (medicinal use patent applied for, application number 02125544.X) such as anti-inflammatory, antianaphylaxis, anti-asthma.S.K.Kapoor in 1971 etc. separate from plant Amphicome emodi Lindl first and obtain Rhizoma Picrorhizae glucoside II, separate obtaining Rhizoma Picrorhizae glucoside II later in succession from India's Rhizoma Picrorhizae (picrorhiza kurroaRoyle ex Benth) rhizome and Tibet picrorhiza rhizome (picrorhiza scrophulariifloraPennell) rhizome.Used method is that the plumbic acetate precipitator method, silica gel column chromatography and reverse silica gel column chromatography separate, but does not all obtain Rhizoma Picrorhizae glucoside II crystallization product.
The chemical structural formula of Rhizoma Picrorhizae glucoside II is as follows:
Molecular formula: C
23H
28O
13
Molecular weight: 512.1530
Fusing point: 214-215 ℃
Solvability: water, methyl alcohol, ethanol are easily molten, acetone solution, and ethyl acetate is molten slightly.
The invention provides the preparation method of Rhizoma Picrorhizae glucoside II with industrial value.Its separation method and crystallization method are quick, and be simple, practicality.Compare with technology in the past, the method novelty has tangible novelty.
A kind ofly prepare the method for Rhizoma Picrorhizae glucoside II with Tibet picrorhiza rhizome (picrorhiza scrophulariiflora Pennell) and India's Rhizoma Picrorhizae (picrorhiza kurroa Royle ex Benth) rhizome, it is characterized in that, Tibet picrorhiza rhizome (or India's Rhizoma Picrorhizae) is through water, methyl alcohol, ethanol, acetone or its mixed solvent extract, compositions such as Rhizoma Picrorhizae glucoside II after extracting solution concentrates in the aqueous solution of the extract of gained are after adsorbents adsorb is handled, separate Rhizoma Picrorhizae glucoside II with the basic solution wash-out, alkaline eluant neutralizes with acid, but basic solvent wash-out compositions such as the Rhizoma Picrorhizae glucoside II in the neutralizer are once more after handling with adsorbents adsorb, use methyl alcohol, ethanol, acetone or its mixed solvent, the perhaps mixed solvent wash-out of they and water, after elutriant is concentrated into and does, residue anhydrous solvent such as methyl alcohol, ethanol, acetone, ethyl acetate extraction, extracting solution is concentrated into dried, promptly get the Rhizoma Picrorhizae glucoside II crude product, the Rhizoma Picrorhizae glucoside II crude product mixed solvent crystallization and the recrystallization of ethyl acetate-dehydrated alcohol.
The invention provides the extraction of Rhizoma Picrorhizae glucoside II, separate, the method of purifying is, get Tibet picrorhiza rhizome (picrorhiza scrophulariiflora Pennell) and India's Rhizoma Picrorhizae (picrorhizakurroa Royle ex Benth) rhizome or its pulverizing product, water, methyl alcohol, ethanol, acetone equal solvent or its two kinds, multiple mixed solvent extracts, extracting solution vacuum concentration below 70 ℃ is to doing (or organic solvent-free), add water to suitable volume, remove precipitation (if any precipitation), the adsorption column A that last conventional processing is good, wash decon with water, to closely colourless, and sugared reaction test should be negative (molish reaction negative), again with buck or contain lower concentration methyl alcohol, ethanol, the buck wash-out Rhizoma Picrorhizae glucoside II of acetone, elutriant is immediately with the acid neutralization, neutralizer is gone up the good adsorption column B of conventional processing once more, wash with water to closely colourless, use the pure water desalination, use methyl alcohol at last, ethanol, acetone and other organic solvent or their water-containing solvent wash-out, elutriant is concentrated into dried, residue ethanol, the mixed solution of the organic solvent that the acetone isopolarity is bigger or they and ethyl acetate extracts, extracting solution vacuum concentration below 70 ℃ is to doing, get the Rhizoma Picrorhizae glucoside II crude product, with ethyl acetate-dehydrated alcohol mixed solvent crystallization and recrystallization, promptly get Rhizoma Picrorhizae glucoside II.
1, above-mentioned to extract the used solvent of composition contain Rhizoma Picrorhizae glucoside II from crude drug can be water, ethanol, methyl alcohol, acetone, both can use separately, also can two or more solvent merges to use.
2, the above-mentioned extraction from crude drug contained recklessly the composition of xanthosine II and can use refluxing extraction, also can extract with the diacolation extraction or with apparatus,Soxhlet's.
3, the used filler of above-mentioned filling adsorption column can be the resin of nonpolar or low-pole, for example, and styrene type (comprising vinyl toluene type, ethyl styrene type) or vinyl cyanide type interpolymer resin.It also can be activated carbon.
4, above-mentioned can be the aqueous solution of sodium hydroxide, potassium hydroxide, ammonia from the used buck of adsorption column A wash-out Rhizoma Picrorhizae glucoside II, and these aqueous solution can be to contain concentration to be not more than 20% methyl alcohol, ethanol and acetone.
5, the used acid of above-mentioned neutralization bases elutriant can be organic acid, as formic acid, acetate, propionic acid etc.Also can be the mineral acid and their aqueous solution, example hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid etc.
6, if the alkali lye that wash-out is used in above-mentioned 4 is when containing methyl alcohol, ethanol, acetone and other organic solvent, must thin up after the neutralization makes it contain the alcohol amount and is not more than 10%, goes up the macroporous resin column enrichment again, and wash the decolouring desalination with water.
7, above-mentioned can be methyl alcohol, ethanol, acetone, ethyl acetate or their mixture from the used solvent of adsorption column B wash-out Rhizoma Picrorhizae glucoside II, or the mixture of they and water.
8, extracting the used solvent of Rhizoma Picrorhizae glucoside II from above-mentioned residue can be methyl alcohol, dehydrated alcohol, acetone or mixed solution, or the mixed solution of they and ethyl acetate.
Embodiment
With following embodiment the present invention is specified, but the present invention is not limited to the content that the following example comprises.
[embodiment one]
Get the meal 500g of Tibet picrorhiza rhizome (picrorhiza scrophulariiflora Pennell) rhizome, use 50% ethanol percolate extraction, get percolate 5000ml, be evaporated to about 400ml and remove residual ethanol, the water that adds equivalent, on the D101 type macroporous resin column A (3kgD101 type macroporous resin places in the glass column of Φ=10cm) that handled well, the conventional flush away impurity of water, to closely colourless, and sugared reaction test be negative (molish reaction negative), with the sodium hydroxide solution 5000ml wash-out Rhizoma Picrorhizae glucoside II that contains 15% alcoholic acid 2%, elutriant is neutralized to pH value 6 with acetate immediately, neutralizer adds the ordinary water of equivalent, on the D101 type macroporous resin column B (2kgD101 type macroporous resin places in the glass column of Φ=8cm) that handled well, wash with water to closely colourless, use the pure water desalination, with 85% ethanol 3000ml wash-out, elutriant is concentrated into dried, residue extracts three (500ml with ethyl acetate-dehydrated alcohol (3: 2) mixed-liquor return, 400ml, 400m1), extracting solution is extremely placed crystallization behind about 300ml in vacuum concentration below 70 ℃, with promptly getting Rhizoma Picrorhizae glucoside II 21.7g behind ethyl acetate-dehydrated alcohol (3: 2) recrystallization.
[embodiment two]
Get the meal 500g of Tibet picrorhiza rhizome (picrorhiza scrophulariiflora Pennell) rhizome, use 50% ethanol percolate extraction, get percolate 5000ml, be evaporated to about 400ml and remove residual ethanol, the water that adds equivalent, on the macroporous resin column A (3kgD101 type macroporous resin places in the glass column of Φ=10cm) that handled well, the conventional flush away impurity of water, to closely colourless, and sugared reaction test feminine gender (molish reaction negative), with the sodium hydroxide solution 5000ml wash-out Rhizoma Picrorhizae glucoside II that contains 2%, elutriant is neutralized to pH value 6.5 with acetate immediately, (3kgD101 type gac places in the glass column of Φ=10cm the activated carbon column B that has handled well on the neutralizer, before the dress post, used gac was 140 ℃ of bakings 4.5 hours), wash with water to nearly colourless and potential of hydrogen when neutral, with using 75% ethanol 3000ml wash-out after the pure water desalination again, elutriant is concentrated into dried, residue extracts three (500ml with ethyl acetate-dehydrated alcohol (3: 1) mixed-liquor return, 400ml, 400ml), extracting solution is concentrated into about 300ml and places crystallization, with promptly getting Rhizoma Picrorhizae glucoside II 17.5g behind ethyl acetate-dehydrated alcohol (3: 1) recrystallization.
[embodiment three]
Get Tibet picrorhiza rhizome (picrorhiza scrophulariiflora Pennell) rhizome 500g, be added in the 4000ml80 ℃ of water, constantly stirring down, slow fire is heated to the maintenance 10 minutes of boiling, the leaching decoction liquor, the dregs of a decoction add water 3000ml and decoct boiling 20 minutes, the leaching decoction liquor, the dregs of a decoction add water 3000ml and decoct boiling 30 minutes, the leaching decoction liquor, the decoction liquor that merges all leachings, on the D101 type macroporous resin column A (3kgD101 type macroporous resin places in the glass column of Φ=10cm) that handled well, the conventional flush away impurity of water, to closely colourless, and sugared reaction test be negative (molish reaction negative), with the sodium hydroxide solution 5000ml wash-out Rhizoma Picrorhizae glucoside II that contains 2%, elutriant is neutralized to pH value 7 with acetate immediately, the D101 type macroporous resin column B that has handled well on the neutralizer (2kgD101 type macroporous resin column places in the glass column of Φ=8cm), wash with water to nearly colourless and potential of hydrogen when neutral, use the pure water desalination, with 65% ethanol 3000ml wash-out, elutriant is concentrated into dried, residue extracts three (500ml with ethyl acetate-dehydrated alcohol (65: 35) mixed-liquor return, 400ml, 400ml), extracting solution is concentrated into about 300ml for 70 ℃ and places crystallization, with promptly getting Rhizoma Picrorhizae glucoside II 22.6g behind ethyl acetate-dehydrated alcohol (65: 35) recrystallization.
[embodiment four]
Get the meal 500g of Tibet picrorhiza rhizome (picrorhiza scrophulariiflora Pennell) rhizome, use 50% ethanol percolate extraction, get percolate 5000ml, be evaporated to about 400ml and remove residual ethanol, the water that adds equivalent, on the activated carbon column A that handled well (3kgD101 type gac places in the glass column of Φ=12cm, before the dress post, used gac was 140 ℃ of bakings 4.5 hours), the conventional flush away impurity of water, to closely colourless, and sugared reaction test be negative (molish reaction negative), with the sodium hydroxide solution 5000ml wash-out Rhizoma Picrorhizae glucoside II that contains 10% alcoholic acid 2%, elutriant is neutralized to pH value 7 with acetate immediately, neutralizer adds the ordinary water of equivalent, on the macroporous resin column B (2kgD101 type macroporous resin places in the glass column of Φ=8cm) that handled well, wash with water to nearly colourless and potential of hydrogen when neutral, use the pure water desalination, use 45% ethanol, 3000 wash-outs again, elutriant is concentrated into dried, residue extracts three (500ml with ethyl acetate-dehydrated alcohol (1: 1) mixed-liquor return, 400ml, 400ml), extracting solution is concentrated into about 300ml and places crystallization, with promptly getting Rhizoma Picrorhizae glucoside II 19.6g behind ethyl acetate-dehydrated alcohol (1: 1) 300ml recrystallization.
[embodiment five]
Get the meal 500g of India's Rhizoma Picrorhizae (picrorhiza kurroa Royle ex Benth) rhizome, use 50% ethanol percolate extraction, get percolate 5000ml, be evaporated to about 400ml and remove residual ethanol, the water that adds equivalent, on the activated carbon column A that handled well (3kgD101 type gac places in the glass column of Φ=12cm, before the dress post, used gac was 140 ℃ of bakings 4.5 hours), the conventional flush away impurity of water, to closely colourless, and sugared reaction test be negative (molish reaction negative), with the sodium hydroxide solution 5000ml wash-out Rhizoma Picrorhizae glucoside II that contains 10% alcoholic acid 2%, elutriant is neutralized to pH value 7 with acetate immediately, neutralizer adds the ordinary water of equivalent, on the macroporous resin column B (2kgD101 type macroporous resin places in the glass column of Φ=8cm) that handled well, wash with water to nearly colourless and potential of hydrogen when neutral, use the pure water desalination, with 45% ethanol, 3000 wash-outs, elutriant is concentrated into dried, residue extracts three (500ml with ethyl acetate-dehydrated alcohol (1: 1) mixed-liquor return, 400ml, 400ml), extracting solution is concentrated into about 300ml and places crystallization, with promptly getting Rhizoma Picrorhizae glucoside II 9.6g behind ethyl acetate-dehydrated alcohol (1: 1) 300ml recrystallization.
[embodiment six]
Get the meal 500g of India's Rhizoma Picrorhizae (picrorhiza kurroa Royle ex Benth) rhizome, use 50% ethanol percolate extraction, get percolate 5000ml, be evaporated to about 400ml and remove residual ethanol, the water that adds equivalent, on the activated carbon column A (3kgDM that handled well
2The type gac places in the glass column of Φ=12cm, before the dress post, used gac was 140 ℃ of bakings 4.5 hours), the conventional flush away impurity of water, to closely colourless, and sugared reaction test be negative (molish reaction negative), with the sodium hydroxide solution 5000ml wash-out Rhizoma Picrorhizae glucoside II that contains 10% alcoholic acid 2%, elutriant is neutralized to pH value 7 with acetate immediately, and neutralizer adds the ordinary water of equivalent, on the macroporous resin column B (2kgDM that handled well
2The type macroporous resin places in the glass column of Φ=8cm), wash with water to nearly colourless and potential of hydrogen when neutral, use the pure water desalination, with 45% ethanol, 3000 wash-outs, elutriant is concentrated into dried, and residue extracts three (500ml with ethyl acetate-dehydrated alcohol (1: 1) mixed-liquor return, 400ml, 400ml), extracting solution is concentrated into about 300ml and places crystallization, with promptly getting Rhizoma Picrorhizae glucoside II 9.0g behind ethyl acetate-dehydrated alcohol (1: 1) 300ml recrystallization.
[embodiment seven]
Get Tibet picrorhiza rhizome (picrorhiza scrophulariiflora Pennell) rhizome 500g, be added in the 4000ml80 ℃ of water, constantly stirring down, slow fire is heated to the maintenance 10 minutes of boiling, leaching decoction liquor, the dregs of a decoction add water 3000ml and decoct boiling 20 minutes, leaching decoction liquor, the dregs of a decoction add water 3000ml and decoct boiling 30 minutes, the leaching decoction liquor merges the decoction liquor of all leachings, on the activated carbon column A (3kgD that handled well
2The type gac places in the glass column of Φ=12cm, before the dress post, used gac was 140 ℃ of bakings 4.5 hours), the conventional flush away impurity of water, to closely colourless, and sugared reaction test be negative (molish reaction negative), with the sodium hydroxide solution 5000ml wash-out Rhizoma Picrorhizae glucoside II that contains 10% alcoholic acid 2%, elutriant is neutralized to pH value 7 with acetate immediately, and neutralizer adds the ordinary water of equivalent, on the macroporous resin column B (2kgD that handled well
2The type macroporous resin places in the glass column of Φ=8cm), wash with water to nearly colourless and potential of hydrogen when neutral, use the pure water desalination, use 45% ethanol, 3000 wash-outs again, elutriant is concentrated into dried, and residue extracts three (500ml with ethyl acetate-dehydrated alcohol (1: 1) mixed-liquor return, 400ml, 400ml), extracting solution is concentrated into about 300ml and places crystallization, with promptly getting Rhizoma Picrorhizae glucoside II 19.6g behind ethyl acetate-dehydrated alcohol (1: 1) 300ml recrystallization.
Claims (10)
1, a kind of method for preparing Rhizoma Picrorhizae glucoside II with the Tibet picrorhiza rhizome rhizome, it is characterized in that the Tibet picrorhiza rhizome water, methyl alcohol, ethanol, acetone, or extract with its mixed solvent, extracting solution concentrates the extracting solution of back gained after adsorbents adsorb is handled, separate Rhizoma Picrorhizae glucoside II with the basic solution wash-out, alkaline eluant neutralizes with acid, after but the basic solvent wash-out composition in the neutralizer is handled with adsorbents adsorb once more, use methyl alcohol, ethanol, acetone, or use its mixed solvent, perhaps use the mixed solvent wash-out of they and water, after elutriant is concentrated into and does, residue extracts with anhydrous solvent, extracting solution is concentrated into dried, promptly get the Rhizoma Picrorhizae glucoside II crude product, the Rhizoma Picrorhizae glucoside II crude product mixed solvent crystallization and the recrystallization of ethyl acetate-dehydrated alcohol.
2, according to the described method for preparing Rhizoma Picrorhizae glucoside II of claim 1, wherein ethyl acetate is 65 to 35 with the ratio of dehydrated alcohol.
3, according to the described method for preparing Rhizoma Picrorhizae glucoside II of claim 1, wherein sorbent material is a non-polar resin, or the low-pole resin, or activated carbon.
4, according to the described method for preparing Rhizoma Picrorhizae glucoside II of claim 3, wherein non-polar resin is the styrene type resin.
5, according to the described method for preparing Rhizoma Picrorhizae glucoside II of claim 3, wherein the low-pole resin is a vinyl cyanide type resin.
6, according to the described method for preparing Rhizoma Picrorhizae glucoside II of claim 1, wherein basic solution is the aqueous solution that sodium hydroxide, potassium hydroxide or ammonia are made into.
7, according to the described method for preparing Rhizoma Picrorhizae glucoside II of claim 1, wherein used acid is organic acid, or mineral acid.
8, according to the described method for preparing Rhizoma Picrorhizae glucoside II of claim 7, wherein used organic acid or formic acid, or acetate, or propionic acid, or their aqueous solution that is made into.
9, according to the described method for preparing Rhizoma Picrorhizae glucoside II of claim 7, wherein used mineral acid or hydrochloric acid, or sulfuric acid, or nitric acid, or phosphoric acid, or the aqueous solution that they were made into.
10, according to the described method for preparing Rhizoma Picrorhizae glucoside II of claim 1, wherein anhydrous solvent or methyl alcohol, or ethanol, or acetone, or ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02149356 CN1218952C (en) | 2002-11-13 | 2002-11-13 | Preparing method for kutkin II crystal |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02149356 CN1218952C (en) | 2002-11-13 | 2002-11-13 | Preparing method for kutkin II crystal |
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| CN1500798A CN1500798A (en) | 2004-06-02 |
| CN1218952C true CN1218952C (en) | 2005-09-14 |
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| CN 02149356 Expired - Fee Related CN1218952C (en) | 2002-11-13 | 2002-11-13 | Preparing method for kutkin II crystal |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371340C (en) * | 2004-11-26 | 2008-02-27 | 周亚伟 | Production of Rhizoma Picrorhizae glucoside II monomer and its drug form for treating hepatitis B |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013042131A1 (en) | 2011-09-23 | 2013-03-28 | M KUMAR, Anil | A process for preparation of synergistic herbal preparation of extracts picrorhiza kurroa and glycyrrhiza glabra having medicinal value |
| CN103936804B (en) * | 2014-03-31 | 2016-05-11 | 扬子江药业集团有限公司 | A kind of kutkin Ⅱcrystal preparation technology |
| CN104592325A (en) * | 2015-01-30 | 2015-05-06 | 济南东源生物医药技术有限公司 | Method for recycling picroside II from mother liquor after hydrothermal recrystallization of picroside II |
-
2002
- 2002-11-13 CN CN 02149356 patent/CN1218952C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371340C (en) * | 2004-11-26 | 2008-02-27 | 周亚伟 | Production of Rhizoma Picrorhizae glucoside II monomer and its drug form for treating hepatitis B |
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| Publication number | Publication date |
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| CN1500798A (en) | 2004-06-02 |
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