CN1100097C - Process for preparing proanthocyandin - Google Patents
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- CN1100097C CN1100097C CN99116183A CN99116183A CN1100097C CN 1100097 C CN1100097 C CN 1100097C CN 99116183 A CN99116183 A CN 99116183A CN 99116183 A CN99116183 A CN 99116183A CN 1100097 C CN1100097 C CN 1100097C
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Abstract
The present invention relates to a preparation technology of proanthocyandin. The preparation technology comprises an extraction step and a refining step. Plant material which contains proanthocyanidin is lixiviated with ethanol water, and the proanthocyanidin is extracted. In the refining step, water soluble impurities are removed by a precipitating method with propanone, and a proanthocyanidin product which has high purity is obtained. The method of the technology is simple, and the price of obtained solvent is low. Grape pips and pine barks are used as raw material, and the yields of the proanthocyanidin are respectively equal to 5.0% and 12%. The content of the proanthocyanidin in a product is equal to 65% in general, the content of heavy metal, the microorganism index, the ash content of sulfide, etc. are much lower than those in standard of food sanitation, and the proanthocyandin can be safely used as additive agents of medicine, health products, food, cosmetics, etc.
Description
The present invention relates to a kind of is the production technique of feedstock production proanthocyanidin with the vegetable material.
Proanthocyanidin or pycnogenols (Proanthocyanidins, Procyanidins, Pycnogenols) belong to condensed tannin class material, be to link with C-C and the class polyphenolic substance (Polyphenols) that forms by hydroxyflavan compounds, its structural unit is flavan-3-alcohol (F1avan-3-ol), as (+)-catechin [(+)-Catechin] and (-)-l-Epicatechol [(-)-Epicatechin].This compounds itself is colourless, generates cyanidin(e) (Anthocyanidins) but add heat energy in acidic solution, so the name proanthocyanidin also claims leucoanthocyanidin (Leucoanthocyanidins).Contained proanthocyanidin mostly is the oligomer (Oligoproanthocyanidins) that 2～4 flavan-3-alcohols are polymerized greatly in the plant, so the commodity of proanthocyanidin " OPC " by name.Proanthocyanidin is to have antioxidant and the free-radical scavengers of pretending very much usefulness, can prevent and treat the various diseases that causes because of free radical.Therefore, proanthocyanidin become a kind ofly cure approximately, the important additives of the important source material of healthcare products and food, makeup.
Flat 3-200781), or with rare wine, rare acetone cold soaking extraction (Yao new life the existing preparation technology of proanthocyanidin is: (Japanese Patent: is extracted in water heating.Natural Medicine Chemistry.The People's Health Publisher.1988.253-257), extracting solution is at concentrating under reduced pressure, filtration or centrifugally obtain the aqueous solution after removing water-insoluble impurity, and this aqueous solution (if convection drying can obtain the crude extract of proanthocyanidin) needs to make with extra care because of containing a large amount of water-soluble impurities.The further refining general ethyl acetate that adopts extracts repeatedly, acetic acid ethyl acetate extract is convection drying (European patent: EP0 behind dehydration, concentrating under reduced pressure, 384,796A1) or earlier through the chloroform precipitation, with drying precipitate (United States Patent (USP): US4,698,360) obtain proanthocyanidin extract (being commodity OPC).Also have in the proanthocyanidin aqueous solution yeast powder of interpolation by fermentation remove get carbohydrate impurity (European patent: EP0,790,314A2).
In above-mentioned preparation technology, make with extra care and use ethyl acetate extraction, there is following shortcoming:
(1) because of the solubleness of proanthocyanidin in ethyl acetate is very low, so the yield of this process for purification is extremely low;
(2) because of consuming a large amount of organic solvents, the cost height;
(3) method more complicated, implementation process is higher to peopleware and equipment requirements.
Can't remove non-carbohydrate impurity with fermentation method is refining.
Purpose of the present invention is intended to address the above problem, and proposes a kind of extraction back and prepares high yield, highly purified proanthocyanidin novel process with the sedimentary method of branch.
The treating process of proanthocyanidin extract mainly is to remove water-soluble impurity, studies show that this impurity mainly be carbohydrate (comprising polysaccharide, oligosaccharides and small molecules carbohydrate) and a small amount of crude protein (comprising polypeptide, oligopeptides) etc. (European patent EP 790,314A2).These impurity are insoluble to acetone, and proanthocyanidin can be dissolved in acetone, and according to this character of proanthocyanidin and impurities thereof, we find to add amount of acetone in the aqueous solution of proanthocyanidin extract, can make above-mentioned these contamination precipitations and be removed, thereby reach the purified purpose.In this way, not only the yield height of proanthocyanidin, operation is simple, and cost is low, quality product is guaranteed.
The preparation technology of proanthocyanidin of the present invention, divide two operations to carry out: (1) abstraction process: with the plant is raw material, with solvent lixiviate vegetable material, separate remove concentrate after the water-insoluble matter the proanthocyanidin concentrated aqueous solution; (2) refining step: remove water-soluble impurity in the proanthocyanidin concentrated aqueous solution with solvent, concentrate then and remove solvent and the dry proanthocyanidin product that gets, it is characterized in that in the described refining step, make solvent with acetone, adopt sedimentary method to remove water-soluble impurity, the acetone add-on is 2～6 times (V/W) of described proanthocyanidin concentrated aqueous solution amount.
Vegetable material: any part of plant materials such as seed, bark, root, cauline leaf, as long as contain proanthocyanidin, the present invention can adopt and make raw material, has found that many vegetable materials contain proanthocyanidin, as Semen Vitis viniferae, Cortex Pini, Cortex Cinnamomi etc.Grape (Vitis vinifera) seed can be winery's brew waste residue vinous, but preferably unleavened Semen Vitis viniferae, otherwise yield will reduce greatly; Cortex Pini: be the endothelium of Pinus massoniana Lamb (Pinus massoniana).Vegetable material dries the back to be pulverized, and crosses 10～20 order scalpings.
Abstraction process: the present invention can adopt existing extracting method commonly used, for example can use water as the solvent heating extracts, but the water extract is difficult to filter, need high speed centrifugation equipment just can obtain settled solution, extract so preferably adopt aqueous ethanolic solution to make solvent soaking, alcohol concn is 50%～70% (volume ratio), and optimal concentration is 60%, for improving yield useable solvents lixiviate raw material repeatedly, general lixiviate 2～3 times.The amount that adds aqueous ethanolic solution is 2～8 times of used vegetable material quality.As being raw material with the Semen Vitis viniferae, extraction for the first time adds 4 times of vegetable material amounts (V/W), and second, third time adds 2～3 times of amounts; As being raw material with the Cortex Pini, add 8 times of vegetable material amounts (V/W) for the first time, second and add 4 times of amounts for the third time.Soak time: soak time is answered sufficiently long, is as the criterion so that proanthocyanidin can fully extract.In general, extracting for the first time to soak has 2～3 days, and second and respectively to have 1 day for the third time just passable substantially.Vat liquor is settled solution through filtering layer (as sand pocket, the filter cloth etc.) outflow of extractor or diafiltration pot bottom.No. three extracting solutions are merged, be evaporated to 1/3～2/3 (V/W) of vegetable material amount, add 2～3 times of water (V/V) that should concentrate liquid measure again.Place (general 10～24 hours) precipitation,, obtain the proanthocyanidin concentrated aqueous solution the supernatant liquor concentrating under reduced pressure.
Refining step: the proanthocyanidin concentrated aqueous solution under agitation adds acetone, and the amount that adds acetone is 2～6 times (V/W) of this proanthocyanidin concentrated aqueous solution weight, and optimal dose is 4～5 times.For saving acetone consumption, preferably 20～26 ° of the degree Beaume of proanthocyanidin concentrated aqueous solution (proportion 1.16～1.22).Leave standstill then 10～24 hours to precipitation fully, discard precipitation, supernatant liquor be evaporated under the lower temperature do not contain acetone till, this concentrated solution promptly obtains refining proanthocyanidin (commodity " OPC ") through concentrating under reduced pressure drying or spraying drying powder-forming.
The technique effect that the present invention reaches:
1. yield height, with the Semen Vitis viniferae be raw material generally about 5.0%, Cortex Pini is about 12%.
2. a step can finish refiningly, and method is simple; Implementation process is not high to personnel and equipment requirements.
3. the content height of proanthocyanidin in the extract that obtains is generally about 65%.
4. used organic solvent is cheap, and most of recyclable, and cost is low.
5. heavy metal content, microbiological indicator, sulfide ash grade far below " food hygienic standard " in the extract that obtains.
Below by embodiment preferred forms of the present invention and details are illustrated.
Use acidifying vanillin food grade,1000.000000ine mesh (Acidified Vanillin) method (Richard B.Broadhurst andWilliam T.Jones, 1978) to measure proanthocyanidin content in an embodiment.Concrete grammar is as follows:
1. prepare following solution earlier:
(1) 4% (W/V) vanillin food grade,1000.000000ine mesh methanol solution---vanillin food grade,1000.000000ine mesh solution.
(2) sample aqueous solution of 0.2-0.3mg/ml concentration---sample solution.
Catechin (purity the is 98%) aqueous solution---the standard solution of (3) 0.2 one 0.3mg/ml concentration.
2. measure:
(1) mensuration of sample: get the 0.5ml sample solution in the lucifuge test tube, add 3ml vanillin food grade,1000.000000ine mesh solution, mix
Even, add the 1.5ml concentrated hydrochloric acid again, under the temperature about 20 ℃, placed 15 minutes behind the mixing, measure
This solution is in the absorbancy (absorbance A) of 500nm wavelength.
(2) mensuration of standard substance: with above-mentioned (1) method bioassay standard product solution absorbency (absorbancy B).
(3) blank: replace sample solution with water, other method by (1) is carried out, and obtains absorbancy C.
(4) opaquing fluid: replace vanillin food grade,1000.000000ine mesh solution with methyl alcohol, other method by (1) is carried out, and obtains absorbancy D.
3. calculate: calculate by following formula:
Embodiment one:
400 gram Semen Vitis viniferae powder place tubualted bottle, with 60% ethanol cold soaking, add 1600 milliliters for the first time, soak 48 hours, and second, third time respectively adds 1200 milliliters, soaks 24 hours, emits and collect vat liquor.To be evaporated to 200 milliliters after three vat liquors merging, concentrated solution adds water to 800 milliliters, and mixing is placed 12 hours precipitations fully.Incline and supernatant liquor, supernatant liquor is evaporated to 80 grams (degree Beaume=25 °), this concentrated solution is divided into four parts (every part 20 grams) equally, under agitation add 40,60,80,100 milliliters of acetone respectively, place about 6 hours to precipitating fully, inclining supernatant liquor, concentrating under reduced pressure, be dried to powder, yield and proanthocyanidin content such as table 1.
Other get 100 the gram Semen Vitis viniferaes, fully by patent (European patent: EP0,384,796A1) the ethyl acetate extraction method is carried out, its yield and content are also listed in table 1.
Table 1: yield and the content of the refining OPC of the acetone precipitation of different ratios
| Process for purification | The inventive method (acetone precipitation) | Patented method (AcOEt extraction) | |||
| 2 times of amounts | 3 times of amounts | 4 times of amounts | 5 times of amounts | ||
| Yield (%) | 6.5 | 6.2 | 5.5 | 5.5 | 1.2 |
| Content (%) | 58.6 | 59.3 | 63.7 | 67.4 | 66.3 |
Embodiment two:
Pinus massoniana Lamb endothelium dry powder 100 grams add 800 milliliter of 60% alcohol immersion 48 hours, filter; Residue adds 300 milliliter of 60% alcohol immersion 24 hours, filters; Residue by the second time extracting method extract once again.Merge three times extract, be evaporated to 50 milliliters, add water to 200 milliliters, place 12 hours to precipitating fully, inclining supernatant liquor, is evaporated to about 20 grams, under agitation add 4.5 times of volume acetone in this concentrated solution, place 24 hours to precipitating fully, supernatant liquor becomes the light brown red powder through concentrating under reduced pressure, drying.Yield is 15%, and OPC content is 74%.
Embodiment three:
1500 kilograms of Semen Vitis viniferae powder place one 10 cubic metres extractor, add 6000 liter 60% ethanol, leach extracting solution; Residue extracts twice again, and second, third time extraction all adds 3000 liter of 60% alcohol immersion 24 hours.Merge No. three times extracting solution, be evaporated to the 500-700 liter, add water to 2000 liters, place 24 hours to precipitating fully, inclining supernatant liquor and is evaporated to 300 kilograms, under agitation add 1350 liters of acetone, place 24 hours to precipitation fully, with supernatant liquor reclaim under reduced pressure acetone, the aqueous solution spray-dried 81 kilograms of light brown red powder, yield is 5.4%, and OPC content is 67%.
Embodiment four:
1000 kilograms of Pinus massoniana Lamb endothelium dry powder place 10 cubic metres extractor, add 8000 liter 60% ethanol, leach extracting solution; Residue extracts twice again, and second, third time extraction all adds 4000 liter of 60% alcohol immersion 24 hours.Merge No. three times extracting solution, be evaporated to about 600 liters, add water to 2400 liters, place 24 hours to precipitating fully, inclining supernatant liquor and is evaporated to 500 kilograms, under agitation add 2250 liters of acetone, place 24 hours to precipitation fully, supernatant liquor reclaim under reduced pressure acetone, the aqueous solution that obtains spray-dried 123 kilograms of light brown red powder, yield is 12.3%, and OPC content is 71%.
Claims (6)
1. the preparation method of a proanthocyanidin, divide two operations to carry out: (1) abstraction process: with the plant is raw material, water or aqueous ethanolic solution lixiviate vegetable material, separate remove concentrate after the water-insoluble matter the proanthocyanidin concentrated aqueous solution; (2) refining step: remove water-soluble impurity in the proanthocyanidin concentrated aqueous solution with solvent, concentrate then and remove solvent and the dry proanthocyanidin product that gets, it is characterized in that in the described refining step, make solvent with acetone, adopt sedimentary method to remove water-soluble impurity, the acetone add-on is 2～6 times (V/W) of described proanthocyanidin concentrated aqueous solution amount.
2. the preparation method of proanthocyanidin according to claim 1, it is characterized in that in the described abstraction process, described Diluted Alcohol is that concentration is the aqueous ethanolic solution of 50%～70% (volume ratio), described aqueous ethanolic solution consumption is 2～8 times (V/W) of described vegetable material amount, described lixiviate is 3 times, the solution that the extracting solution of 3 lixiviate gained is removed respectively after the water-insoluble matter merges, be concentrated into 1/3～2/3 (V/W) of described vegetable material amount, the water (V/V) that adds 2～3 times of volumes again, remove once more concentrate behind the insoluble impurity that anhydrates the proanthocyanidin concentrated aqueous solution.
3. the preparation method of proanthocyanidin according to claim 1 is characterized in that described acetone add-on is 4～5 times (V/W) of described proanthocyanidin concentrated aqueous solution amount.
4. the preparation method of proanthocyanidin according to claim 1 and 2 is characterized in that in described abstraction process, and the degree Beaume of obtained proanthocyanidin concentrated aqueous solution is 20～26 °.
5. the preparation method of proanthocyanidin according to claim 1 and 2, the vegetable material that it is characterized in that being used to extracting proanthocyanidin is a Semen Vitis viniferae, described Diluted Alcohol is that concentration is the aqueous ethanolic solution of 60% (volume ratio), described lixiviate is 3 times, the consumption of aqueous ethanolic solution is 4 times (V/W) of described Semen Vitis viniferae amount for the first time, and second and third time lixiviate is 2～3 times (V/W) of described Semen Vitis viniferae amount.
6. the preparation method of proanthocyanidin according to claim 1 and 2, the vegetable material that it is characterized in that being used to extracting proanthocyanidin is a Cortex Pini, described Diluted Alcohol is that concentration is the aqueous ethanolic solution of 60% (volume ratio), described lixiviate is 3 times, the consumption of aqueous ethanolic solution is 8 times (V/W) of described Cortex Pini amount for the first time, and second and third time lixiviate is 4 times (V/W) of described Cortex Pini amount.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116183A CN1100097C (en) | 1999-05-17 | 1999-05-17 | Process for preparing proanthocyandin |
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| CN99116183A CN1100097C (en) | 1999-05-17 | 1999-05-17 | Process for preparing proanthocyandin |
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| CN1100097C true CN1100097C (en) | 2003-01-29 |
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| CN99116183A Expired - Fee Related CN1100097C (en) | 1999-05-17 | 1999-05-17 | Process for preparing proanthocyandin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086187A (en) * | 2011-01-28 | 2011-06-08 | 云南瑞升烟草技术（集团）有限公司 | Method for extracting and separating out oligomeric proanthocyanidins from Yunnan pine barks |
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| CN1303165C (en) * | 2004-01-12 | 2007-03-07 | 四川大学 | Extraction and separation of proto flower haematochrome and preparation method of its derivatives |
| CN1307315C (en) * | 2005-01-28 | 2007-03-28 | 朱寿民 | Extraction of anthocyanogen of black rice |
| CN102362876A (en) * | 2011-10-24 | 2012-02-29 | 浙江省医学科学院 | Chinese redwood bark extract, preparation method thereof and purpose thereof |
| CN102827861B (en) * | 2012-08-20 | 2014-04-30 | 湖南科技大学 | Method for increasing proanthocyanidin content in escherichia coli by cotransformation of brassica juncea gene ANS and brassica carinata BAN |
| CN102827849B (en) * | 2012-08-20 | 2013-10-16 | 湖南科技大学 | Method for increasing proanthocyanidin content in escherichia coli by cotransformation of brassica juncea gene BAN and DFR |
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| CN106810904B (en) * | 2017-01-11 | 2020-04-17 | 心颐和国际中医药投资控股（北京）有限公司 | Method for extracting anthocyanin components |
| CN107495202A (en) * | 2017-08-03 | 2017-12-22 | 宁夏天瑞产业集团现代农业有限公司 | A kind of proanthocyanidin health food and preparation method thereof |
| CN107722665A (en) * | 2017-11-13 | 2018-02-23 | 何会平 | The method that horseshoe skin extracts natural brown pigment |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4698360A (en) * | 1985-04-09 | 1987-10-06 | Societe Civile D'investigations Pharmacologiques D'aquitaine | Plant extract with a proanthocyanidins content as therapeutic agent having radical scavenger effect and use thereof |
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1999
- 1999-05-17 CN CN99116183A patent/CN1100097C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4698360A (en) * | 1985-04-09 | 1987-10-06 | Societe Civile D'investigations Pharmacologiques D'aquitaine | Plant extract with a proanthocyanidins content as therapeutic agent having radical scavenger effect and use thereof |
| US4698360B1 (en) * | 1985-04-09 | 1997-11-04 | D Investigations Pharmacologiq | Plant extract with a proanthocyanidins content as therapeutic agent having radical scavenger effect and use thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086187A (en) * | 2011-01-28 | 2011-06-08 | 云南瑞升烟草技术（集团）有限公司 | Method for extracting and separating out oligomeric proanthocyanidins from Yunnan pine barks |
| CN102086187B (en) * | 2011-01-28 | 2012-05-23 | 云南瑞升烟草技术（集团）有限公司 | Method for extracting and separating out oligomeric proanthocyanidins from Yunnan pine barks |
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