CN102432580A - Method for degrading high polymer proanthocyanidin - Google Patents
Method for degrading high polymer proanthocyanidin Download PDFInfo
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- CN102432580A CN102432580A CN2011104380769A CN201110438076A CN102432580A CN 102432580 A CN102432580 A CN 102432580A CN 2011104380769 A CN2011104380769 A CN 2011104380769A CN 201110438076 A CN201110438076 A CN 201110438076A CN 102432580 A CN102432580 A CN 102432580A
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Abstract
The invention discloses a method degrading high polymer proanthocyanidin, which comprises the following steps: adding 5-10 times by volume of 0.5-5 wt% sulfite aqueous solution and/or bisulfite aqueous solution into the high polymer proanthocyanidin, and reacting while stirring at 40-80 DEG C for 0.5-2 hours; and separating, washing with alcohol to remove impurities, purifying, concentrating and drying. The method has the advantages of high oligomer proanthocyanidin content, low polymerization degree, higher product water solubility, lower turbidity and high recovery rate, can be used in food, medicine, cosmetics and other fields with higher requirements for water solubility, and widens the application range. The method has simple technical process, does not have high requirements for personnel and equipment in the implementation process, and is applicable to large-scale continuous production of oligomer proanthocyanidin; and the organic solvents are cheap and can be recycled, and thus, the cost is low.
Description
Technical field
The present invention relates to a kind of working method of oligomeric procyanidolics, especially a kind of sulphite or bisulfite salt brine solution of utilizing carries out the degradation method that height gathers pycnogenols.
Background technology
Pycnogenols is to be formed by the catechin of different quantities or l-Epicatechol condensation, forms dimer until ten aggressiveness compounds, and the size by the polymerization degree is called oligomer with the 2-4 aggressiveness, usually with the high polymer that is called more than 5 aggressiveness.
Research shows that the biological activity of pycnogenols is relevant with the connecting key and the polymerization degree between monomer composition, the monomer.Pycnogenols two, three, the tetramer shows good biological activity at aspects such as anti-oxidant, enzyme inhibition, mutation, wherein procyanidin dimers is active best.Oligomeric procyanidolics water-soluble better, can be used for water-soluble food of having relatively high expectations, medicine and cosmetic industry.Height gathers the pycnogenols poorly water-soluble, the utilization that is difficult to be absorbed by the body, and because sterically hindered influence, the activity of phenolic hydroxyl group is affected, and therefore major part can only be utilized as low value-added sub products such as natural pigments at present.Yet; Most pycnogenolss in the plant exist with the high polymer form; Height in the Semen Vitis viniferae extract gathers procyanidin content and accounts for more than 50% of total pycnogenols, for the biological activity that improves Semen Vitis viniferae extract and water-soluble, is necessary that height is gathered pycnogenols is degraded to oligomeric procyanidolics.
At present, the degradation method of the pycnogenols high polymer of putting down in writing in the document has following several kinds: 1, oxidation degradation method, and for example publication number is CN1654463 A, the one Chinese patent application of title " a kind of Procyanidcic Oligomers and preparation method and application "; 2, acid degradation method, publication number CN101012216 A for example, title " a kind of preparation method of Procyanidcic Oligomers " one Chinese patent application; 3, alkaline bleach liquor degradation method; 4, hydrogenation edman degradation Edman, publication number CN101239963 A for example, the one Chinese patent application of title " Chinese cassia tree pycnogenols superpolymer catalytic hydrogenolysis is the method for oligopolymer ".Wherein, oxidation degradation method adopts ydrogen peroxide 50 or Potcrate as oxygenant, use with storage in unstable, be prone to decomposition, thereby cause catalyst efficiency low, expend greatlyyer, and cause that easily phenolic hydroxyl group is oxidized to carboxyl and causes the product inactivation; Acid or the basic soln that acid degradation method and alkaline bleach liquor degradation method are used can cause corrosion to equipment, contaminate environment; The hydrogenation edman degradation Edman needs HTHP, and reaction requires than higher, inconvenient operation.
Summary of the invention
The degradation method that the technical problem that the present invention will solve provides that a kind of technology is simple, safety and the high height of the recovery gather pycnogenols.
For solving the problems of the technologies described above; The technical scheme that the present invention taked is: gathering the quality percentage composition that adds 5～10 times of volumes in the pycnogenols at height is 0.5%～5% sulfite solution and/or bisulfite salt brine solution, at 40～80 ℃ of following stirring reaction 0.5～2h; Separation then, assorted, the purifying of pure wash-out, concentrated at last, dry getting final product.
The preferred sulphite of the present invention is S-WAT; Preferred hydrosulphite is a sodium sulfite anhy 96.
Height of the present invention gathers pycnogenols and is preferably the height that from Semen Vitis viniferae, extracts and gathers pycnogenols.
Of the present inventionly be separated into spinning behind the reaction solution cool to room temperature.
Pure wash-out of the present invention is assorted to be: separate the supernatant that obtains and add alcoholic solution, the supernatant alcohol number of degrees are adjusted to 60～80%, stir, leave standstill the removal of impurities of 1～2h after-filtration, filtrating is reclaimed solvent.Preferred alcoholic solution is methanol solution or ethanolic soln.
Purifying of the present invention is: reclaim filtrating behind the solvent during pure wash-out is assorted through the AB-8 resin absorption, and the pure water washing, using volume percent then is that 50～70% ethanol carries out desorb.
Simmer down to of the present invention: the stripping liquid that purifying obtains arrives solids content 20～30wt% through concentrating under reduced pressure.
Drying of the present invention is a spraying drying.
Sulphite that the present invention is used or hydrosulphite are the nucleophilic reagents of using always, and height gathers the polymeric part C of pycnogenols
4-C
8Key can rupture under the attack of nucleophilic reagent, thereby reaches the purpose of degraded.If but reaction conditions control is bad, it is little to cause that mean polymerisation degree changes, and does not reach the degraded purpose or is degraded into catechin or epicatechin monomers fully, causes the pycnogenols recovery not high.Therefore screening and the control for reaction conditions is a thorny difficult problem.The contriver has solved an above-mentioned difficult problem after paying a large amount of creative works, thereby obtains technology of the present invention.
Adopt the beneficial effect that technique scheme produced to be:
1, product oligomeric procyanidolics content is high, generally accounts for more than 70% of total pycnogenols, and the pycnogenols mean polymerisation degree is reduced to 2～3 by 6～8; The water-soluble raising of product, the turbidity value of 1% aqueous solution is reduced to 30～50 by 600～700; The product oligomeric procyanidolics recovery is high, can reach more than 95%;
2, because the water-soluble improvement of product can be used for water-soluble requirement than fields such as higher food, medicine, makeup, expanded its range of application;
3, technological process is simple, and implementation process is not high to personnel and equipment requirements, is applicable to mass-producing, the serialization production of oligomeric procyanidolics;
4, used organic solvent is cheap, and recyclable, and cost is low.
Embodiment
Below in conjunction with specific embodiment the present invention is done further detailed explanation.
Embodiment 1: the degradation method that this height gathers pycnogenols adopts following process step:
1, extract: get 100kg Semen Vitis viniferae raw material extraction height and gather pycnogenols 12kg, the turbidity value of the 1wt% aqueous solution is 625.3, and mean polymerisation degree is 7.85;
2, degraded: gathering in the pycnogenols quality percentage composition that adds 100L at above-mentioned height is 5% sodium sulfite aqueous solution, and the volume ratio that height gathers pycnogenols and sodium sulfite aqueous solution is 1:8.33, at 65 ℃ of following stirring reaction 1.5h;
3, cooling: reaction solution is used the cold water cool to room temperature;
4, centrifugal: cooled reaction solution is centrifugal, obtains centrifuged supernatant 98.6L, and procyanidin content is 64.16g/L;
5, removal of impurities: with methanol solution the centrifugate alcohol number of degrees are adjusted to 75% (V/V), stir, leave standstill 1h after, filtering and impurity removing, filtrating is reclaimed solvent;
6, purifying: the filtrating behind the recovery solvent is through the AB-8 resin absorption, and the pure water washing uses the ethanol of 70% (V/V) to carry out desorb then, collects stripping liquid;
7, concentrate: stripping liquid arrives solids content 25wt% through concentrating under reduced pressure;
8, drying: the stripping liquid after concentrating obtains oligomeric procyanidolics product 6.6kg through spraying drying, and the turbidity value of the 1wt% aqueous solution is 35.2, and procyanidin content is 91.44wt%, pycnogenols mean polymerisation degree 2.06, oligomeric procyanidolics recovery 95.4wt%.
Embodiment 2: the degradation method that this height gathers pycnogenols adopts following process step.
1, extract: get 100kg Semen Vitis viniferae raw material extraction height and gather pycnogenols 14kg, the turbidity value of the 1wt% aqueous solution is 613.6, and mean polymerisation degree is 8.35;
2, degraded: gathering in the pycnogenols quality percentage composition that adds 100L at above-mentioned height is 3% aqueous solution of sodium bisulfite, and the volume ratio that height gathers pycnogenols and sodium sulfite aqueous solution is 1:7.14, at 50 ℃ of following stirring reaction 2h;
3, cooling: reaction solution is used the cold water cool to room temperature;
4, centrifugal: cooling afterreaction liquid is centrifugal, obtains centrifuged supernatant 97.8L, and procyanidin content is 66.95g/L;
5, removal of impurities: use ethanolic soln, the centrifugate alcohol number of degrees be adjusted to 80% (V/V), stir, leave standstill 1.5h after, filtering and impurity removing, filtrating is reclaimed solvent;
6, purifying: the filtrating behind the recovery solvent is through the AB-8 resin absorption, and the pure water washing uses the ethanol of 65% (V/V) to carry out desorb then, collects stripping liquid;
7, concentrate: stripping liquid arrives solids content 26.7wt% through concentrating under reduced pressure;
8, drying: the stripping liquid after concentrating obtains oligomeric procyanidolics product 6.7kg through spraying drying, and the turbidity value of the 1wt% aqueous solution is 30.8, and procyanidin content is 93.52wt%, pycnogenols mean polymerisation degree 2.11, oligomeric procyanidolics recovery 95.7wt%.
Embodiment 3: the degradation method that this height gathers pycnogenols adopts following process step:
1, extract: get 100kg Semen Vitis viniferae raw material extraction height and gather pycnogenols 13kg, the turbidity value of the 1wt% aqueous solution is 623.7, and mean polymerisation degree is 8.09;
2, degraded: gathering in the pycnogenols quality percentage composition that adds 5 times of volumes at above-mentioned height is 0.5% aqueous solution of sodium bisulfite, at 80 ℃ of following stirring reaction 0.5h;
3, cooling: reaction solution is used the cold water cool to room temperature;
4, centrifugal: cooling afterreaction liquid is centrifugal, obtains centrifuged supernatant 98.1L, and procyanidin content is 64.73g/L;
5, removal of impurities: use ethanolic soln, the centrifugate alcohol number of degrees be adjusted to 60% (V/V), stir, leave standstill 1.5h after, filtering and impurity removing, filtrating is reclaimed solvent;
6, purifying: the filtrating behind the recovery solvent is through the AB-8 resin absorption, and the pure water washing uses the ethanol of 50% (V/V) to carry out desorb then, collects stripping liquid;
7, concentrate: stripping liquid arrives solids content 30wt% through concentrating under reduced pressure;
8, drying: the stripping liquid after concentrating obtains oligomeric procyanidolics product 6.6kg through spraying drying, and the turbidity value of the 1wt% aqueous solution is 32.2, and procyanidin content is 92.38wt%, pycnogenols mean polymerisation degree 2.09, oligomeric procyanidolics recovery 96.0wt%.
Embodiment 4: the degradation method that this height gathers pycnogenols adopts following process step:
1, extract: get 100kg Semen Vitis viniferae raw material extraction height and gather pycnogenols 15kg, the turbidity value of the 1wt% aqueous solution is 617.5, and mean polymerisation degree is 7.98;
2, degraded: gathering in the pycnogenols quality percentage composition that adds 10 times of volumes at above-mentioned height is 1.0% bisulfite aqueous solutions of potassium, at 40 ℃ of following stirring reaction 1.0h;
3, cooling: reaction solution is used the cold water cool to room temperature;
4, centrifugal: cooling afterreaction liquid is centrifugal, obtains centrifuged supernatant 98.3L, and procyanidin content is 65.29g/L;
5, removal of impurities: use ethanolic soln, the centrifugate alcohol number of degrees be adjusted to 65% (V/V), stir, leave standstill 1.5h after, filtering and impurity removing, filtrating is reclaimed solvent;
6, purifying: the filtrating behind the recovery solvent is through the AB-8 resin absorption, and the pure water washing uses the ethanol of 60% (V/V) to carry out desorb then, collects stripping liquid;
7, concentrate: stripping liquid arrives solids content 20wt% through concentrating under reduced pressure;
8, drying: the stripping liquid after concentrating obtains oligomeric procyanidolics product 6.6kg through spraying drying, and the turbidity value of the 1wt% aqueous solution is 34.7, and procyanidin content is 92.66wt%, pycnogenols mean polymerisation degree 2.10, oligomeric procyanidolics recovery 95.5wt%.
Claims (10)
1. one kind high degradation method that gathers pycnogenols; It is characterized in that: it gathers the quality percentage composition that adds 5～10 times of volumes in the pycnogenols at height is 0.5%～5% sulfite solution and/or bisulfite salt brine solution, at 40～80 ℃ of following stirring reaction 0.5～2h; Separation then, assorted, the purifying of pure wash-out, concentrated at last, dry getting final product.
2. height according to claim 1 gathers the degradation method of pycnogenols, it is characterized in that: described sulphite is S-WAT.
3. height according to claim 1 gathers the degradation method of pycnogenols, it is characterized in that: described hydrosulphite is a sodium sulfite anhy 96.
4. height according to claim 1 gathers the degradation method of pycnogenols, it is characterized in that: described height gathers pycnogenols and gathers pycnogenols for the height that from Semen Vitis viniferae, extracts.
5. gather the degradation method of pycnogenols according to described any one height of claim 1-4, it is characterized in that: describedly be separated into spinning behind the reaction solution cool to room temperature.
6. the degradation method that gathers pycnogenols according to described any one height of claim 1-4; It is characterized in that; Described pure wash-out is assorted to be: separate the supernatant that obtains and add alcoholic solution, the supernatant alcohol number of degrees are adjusted to 60～80%, stir; Leave standstill the removal of impurities of 1～2h after-filtration, filtrating is reclaimed solvent.
7. height according to claim 6 gathers the degradation method of pycnogenols, it is characterized in that: described alcoholic solution is methanol solution or ethanolic soln.
8. the degradation method that gathers pycnogenols according to described any one height of claim 1-4; It is characterized in that; Described purifying is: reclaim filtrating behind the solvent during pure wash-out is assorted through the AB-8 resin absorption, and the pure water washing, using volume percent then is that 50～70% ethanol carries out desorb.
9. gather the degradation method of pycnogenols according to described any one height of claim 1-4, it is characterized in that described simmer down to: the stripping liquid that purifying obtains arrives solids content 20～30wt% through concentrating under reduced pressure.
10. gather the degradation method of pycnogenols according to described any one height of claim 1-4, it is characterized in that: described drying is a spraying drying.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796070A (en) * | 2012-08-29 | 2012-11-28 | 西南林业大学 | Preparation method of oligomeric proanthocyanidins |
| CN102924422A (en) * | 2012-09-10 | 2013-02-13 | 华南理工大学 | Method for preparing oligomeric proanthocyanidins by enhanced degradation under pulsed electric field |
| CN103910706A (en) * | 2014-03-26 | 2014-07-09 | 完美（中国）有限公司 | Method for preparing low-cost oligomeric proanthocyanidins |
| CN105837548A (en) * | 2016-04-28 | 2016-08-10 | 江苏师范大学 | Method for chemically degrading high polymerization proanthocyanidins by means of sulfurous acid |
| CN108003129A (en) * | 2018-01-18 | 2018-05-08 | 郑州大学 | A kind of method of high polymer procyanidine in acid degradation lotus pod using solid |
| CN108409702A (en) * | 2018-04-19 | 2018-08-17 | 哈尔滨工业大学（威海） | A method of with the high poly- procyanidine of lithium hydroxide chemical degradation |
| CN113173902A (en) * | 2021-04-27 | 2021-07-27 | 湖南华诚生物资源股份有限公司 | Continuous production method of oligomeric proanthocyanidins with uniform polymerization degree |
| CN116462987A (en) * | 2023-04-27 | 2023-07-21 | 陕西全奥之星生物科技有限公司 | Preparation method of acid-stable butterfly bean flower blue pigment |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796070A (en) * | 2012-08-29 | 2012-11-28 | 西南林业大学 | Preparation method of oligomeric proanthocyanidins |
| CN102924422A (en) * | 2012-09-10 | 2013-02-13 | 华南理工大学 | Method for preparing oligomeric proanthocyanidins by enhanced degradation under pulsed electric field |
| CN102924422B (en) * | 2012-09-10 | 2015-03-11 | 华南理工大学 | Method for preparing oligomeric proanthocyanidins by enhanced degradation under pulsed electric field |
| CN103910706A (en) * | 2014-03-26 | 2014-07-09 | 完美（中国）有限公司 | Method for preparing low-cost oligomeric proanthocyanidins |
| CN103910706B (en) * | 2014-03-26 | 2015-11-11 | 完美（中国）有限公司 | A kind of preparation method of oligomeric procyanidolics of low cost |
| CN105837548A (en) * | 2016-04-28 | 2016-08-10 | 江苏师范大学 | Method for chemically degrading high polymerization proanthocyanidins by means of sulfurous acid |
| CN108003129A (en) * | 2018-01-18 | 2018-05-08 | 郑州大学 | A kind of method of high polymer procyanidine in acid degradation lotus pod using solid |
| CN108409702A (en) * | 2018-04-19 | 2018-08-17 | 哈尔滨工业大学（威海） | A method of with the high poly- procyanidine of lithium hydroxide chemical degradation |
| CN113173902A (en) * | 2021-04-27 | 2021-07-27 | 湖南华诚生物资源股份有限公司 | Continuous production method of oligomeric proanthocyanidins with uniform polymerization degree |
| CN116462987A (en) * | 2023-04-27 | 2023-07-21 | 陕西全奥之星生物科技有限公司 | Preparation method of acid-stable butterfly bean flower blue pigment |
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