CN1115166C - Preparation of polyfucose sulfate with varible molecular weight - Google Patents
Preparation of polyfucose sulfate with varible molecular weight Download PDFInfo
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- CN1115166C CN1115166C CN 98110253 CN98110253A CN1115166C CN 1115166 C CN1115166 C CN 1115166C CN 98110253 CN98110253 CN 98110253 CN 98110253 A CN98110253 A CN 98110253A CN 1115166 C CN1115166 C CN 1115166C
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Abstract
The present invention relates to a preparation method for polyfucose sulfate sulfuric acid ester with variable molecular weight, which is used for extracting various kinds of polyfucose sulfate sulfuric acid ester having different molecular weight from sea tangles and other brown algaes. The present invention is characterized in that the method mainly comprises the processing steps of sea tangle water immersion, millipore filtration, ultrafiltration, concentration, first alcohol deposition, acid hydrolysis, H2O2 decoloration, salt removal by mixing anion and cation resins, secondary alcohol deposition, vacuum dryness, etc. The present invention having the advantages of simple technology, few steps, low cost, etc. is suitable for industrial production, and can be used for preparing products having different molecular weight according to different purposes, functions and effects.
Description
The preparation method of fucoidan, belong to the pharmaceutical product technical field that contains organic active ingredient, be mainly used in and from Thallus Laminariae (Thallus Eckloniae) or other Brown algaes, extract the fucoidan that contains various different molecular weights with multiple physiologically actives such as anticoagulation, blood fat reducing, antitumor, antiviral and enhancing human body immunity functions.
In the prior art, the comprehensive utilization of so-called Thallus Laminariae (Thallus Eckloniae), generally mean the industrialized extraction Algin of Thallus Laminariae (Thallus Eckloniae), mannitol and iodine, and, industrialized extractive technique is not arranged as yet for this important active component of other useful components in the Thallus Laminariae (Thallus Eckloniae) especially sulfated polysaccharide with one of rich seaweed resources.Because of sulfated polysaccharide contains fucose and sulfate radical, so be also referred to as fucoidan, fucosan, sulfated fucan.They are because all there is the significant difference between kind in the difference of Sargassum kind not only on the composition of sugar, and on the content and structure of of sugar.Find from the interrelated data that has retrieved, clear 46-2248 of Japan Patent and clear 50-5199 and Chinese invention patent application CN1129109A, relevant with the present invention.But Japan Patent mainly is a character of utilizing surfactant hexadecylpyridinium chloride (CPC) or hexadecane dimethyl ammonium bromide (CTAB) and fucoidan reaction to form quaternary ammonium compound to carry out isolatingly, and its preparation technology and the present invention have nothing to do.Chinese patent application " sulfated fucan is as medicine of renal failure and angiopathy and preparation method thereof ", wherein disclosed preparation method mainly is to adopt different pH value range of accommodation, the required component of variation extraction separation that cooperates concentration of alcohol again, flow process is long, complex process, processing step be nearly more than 23 steps, and can only prepare fixing high-molecular weight fucoidan, and can not prepare the fucoidan of different molecular weight.The molecular weight and the sulfate radical content that studies show that functions such as the anticoagulation that sulfated polysaccharide had, blood fat reducing, antitumor, antiviral and enhancing human body immunity in the Sargassum and component are closely related.
The object of the present invention is to provide a kind of preparation technology's flow process short, method is simple, step is few, cost is low, be suitable for suitability for industrialized production, it has not only solved concentrating and crystalline problem of a large amount of inorganic salts in the concentrating under reduced pressure process, and is easy to clean and disinfect, and can prepare the preparation method of molecular weight fucoidan of various different molecular weights in the 1000-110000 scope according to difference in functionality and needs.
According to the composition of Thallus Laminariae (Thallus Eckloniae) and the physicochemical characteristic of fucoidan, at existing questions in the prior art, basic design of the present invention is: be raw material with the Thallus Laminariae (Thallus Eckloniae), adopt acidic hydrolysis technology binding film to separate hyperfiltration technique, and reach the purpose of the fucoidan of short flow process extraction separation different molecular weight through microporous filter, chemical method decolouring; Wherein mainly be the control hydrolysising condition ultrafilter membrane (1000-50000) different to prepare the fucoidan that contains fucose 5-35%, organo-sulfate 0.5-45%, alduronic acid 0.6-20% that mean molecule quantity can be regulated according to purposes, function and effect in 1000-100000 with selecting molecular cut off for use; And molecular weight is at the fucoidan more than 100,000.
The preparation method of polyfucose sulfate with varible molecular weight of the present invention is characterized in that this preparation method comprises following process steps: (1) adds its weight 8-12 water logging bubble doubly 1-3 hour in dried Thallus Laminariae (Thallus Eckloniae), get the kelp soaking aqueous solution after the separation; (2) pH value of this kelp soaking aqueous solution is transferred to 5-6 and be the microfilter filtration of 0.5-5 μ m, make clear liquid with the aperture; (3) according to the ultra-filtration and separation concentration technique to above-mentioned clear liquid with the MW10000-50000 ultrafilter membrane with its ultrafiltration and concentration to the 1/5-1/10 of former state volume; (4) in above-mentioned concentrated solution, add the 25-30% that ethanol to this ethanol accounts for mixed liquor, staticly settle behind the mixing and remove Algin and impurity; (5) having continued toward above-mentioned removal to add ethanol to its concentration in the mixed liquor behind Algin and the impurity is 65-80%, behind the mixing, continues to precipitate again; (6) extract above-mentioned precipitate and carry out acidic hydrolysis, the PH of hydrolyzed solution is 1-3; (7) hold back with molecular weight and use H after holding back the 1/2-1/10 that is concentrated into original volume with the volume concentration technique with the MW1000-10000 ultrafilter membrane
2O
2(being hydrogen peroxide) decolouring and with cationic resin and resin anion (R.A.) mixing desalination; (8) add the 65-80% mixing precipitation that ethanol to this ethanol accounts for mixed liquor in the concentrated solution after the above-mentioned decolouring desalination; (9) the above-mentioned precipitate of centrifugalize gets filter cake and is dry under vacuum condition, contains fucose 5-35%, organo-sulfate 0.5-45%, the fucoidan of alduronic acid 0.6-20% through pulverizing promptly to make again.
Only using (1)-(5) in the above-mentioned processing step is fucoidan more than 100,000 through centrifugalize and the dry molecular weight that promptly makes again.
With the above-mentioned molecular weight that makes is that fucoidan more than 100,000 is that raw material is only used (6)-(9) in the above-mentioned processing step and controlled above-mentioned (6) described acidic hydrolysis condition 1-16 hour, can make its molecular weight adjustable fucoidan in the 1000-100000 scope.
With hydrogen peroxide decolouring, its consumption is the 0.5-5% of above-mentioned concentrated solution in the above-mentioned processing step (7).
Feature of the present invention is that also it is that fucoidan more than 100,000 is that raw material only utilizes above-mentioned processing step (6)-(9) and above-mentioned (6) the described acidic hydrolysis condition of controlling made its molecular weight adjustable fucoidan in the 1000-100000 scope in 1-16 hour that available BS by Thallus Laminariae (Thallus Eckloniae) processing and preparing mannitol replaces above-mentioned molecular weight.
Outstanding advantage of the present invention is: adopting ultrafilter membrane to separate and having solved has concentrating and crystalline problem of a large amount of inorganic salts in the concentrating under reduced pressure process; Technology for hydrolyzing under the acid condition specifically is applied in the preparation polyfucose sulfate with varible molecular weight technology key step, therefore can prepares the fucoidan that contains different molecular weight of various difference in functionalitys and result of use; Handling the traditional easier operation of plate-and-frame filtration of solid-liquid ratio with MF method also is more convenient for cleaning and sterilization; Adopt gentle chemical method decolouring than more superior with activated carbon decolorizing, employing anion and the desalination of cation exchange resin mixed column can be removed anion and the cation in the fucoidan, therefore this method sees that on the whole method is easy, flow process is short, processing step is few, cost is low, but also twice laid, pollution-free, be suitable for suitability for industrialized production, can finally make with this method and to contain the 5-35% fucose, the adjustable fucoidan of molecular weight that the organo-sulfate of 0.5-45% and 0.6-20% alduronic acid and physiologically active are stronger, thereby make its range of application wider.
One of most preferred embodiment of the present invention is: take by weighing dried Thallus Laminariae (Thallus Eckloniae) 5000g, add 50000ml water logging bubble 2 hours at ambient temperature, separate soak and regulate its pH value to 5-6 with diluted acid, carry out microporous filter with aperture 0.5-5 μ m microfilter and get 42000ml filtrate, it is 5000ml that the ultrafilter membrane of holding back with molecular weight 20000 carries out ultrafiltration and concentration to volume, add 1800ml concentration and be 95% ethanol, precipitation is removed Algin and other impurity, continue to add 95% ethanol 12000ml, continue precipitation, dry under vacuum condition after the centrifugalize, pulverize then and make 80g fucoidan crude product, be 115000 through measure its mean molecule quantity with viscosimetry.
Two of most preferred embodiment is: get molecular weight that the foregoing description one makes and be fucoidan crude product 50g more than 100,000 and be dissolved in the 2500ml diluted acid and transfer below its pH value to 2, hydrolysis 7 hours, microfilter with aperture 1 μ m after the viscosity of solution significantly reduces filters, get clear filtrate, the ultrafilter membrane classification of reuse MW3000 is concentrated into 500ml, add alkali and be adjusted to alkalescence (PH＞7.5), use H
2O
2Decolouring, with the desalination of zwitterion exchange column, adding 1000ml concentration is 95% ethanol precipitation, and centrifugalize gets filter cake, and is dry under vacuum condition, pulverizes and makes the 25g fucoidan, and measuring the product mean molecule quantity with viscosimetry is 7200.
Change as the embodiment of the invention:
1, available BS by Thallus Laminariae (Thallus Eckloniae) processing and preparing mannitol transfers PH below 2 with diluted acid, replace above-mentioned most preferred embodiment two in molecular weight be fucoidan more than 100,000, extracting molecular weight with the processing step identical with it is 6500 fucoidan;
2, Thallus Laminariae (Thallus Eckloniae) can replace by other Brown algae;
3, adding concentration of ethanol can suitably change.
Claims (4)
1, the preparation method of fucoidan is characterized in that with the Brown algae being raw material, with refining behind the water extraction, comprises the following steps: 1) in the Brown algae raw material, added its weight 8-12 water logging bubble doubly 1-3 hour, must soak aqueous solution after the separation; 2) should soak pH value of aqueous solution and be adjusted to 5-6, and be that the microfilter of 0.5-5 μ m filters, make clear liquid with the aperture; 3) adopt the MW10000-50000 ultrafilter membrane with the 1/5-1/10 of this clear liquid ultrafiltration and concentration to the former state volume; 4) in above-mentioned concentrated solution, add the 25-30% that ethanol to ethanol accounts for mixed liquor, staticly settle behind the mixing and remove Algin and impurity; 5) continuing to add ethanol to its concentration in above-mentioned mixed liquor after having removed Algin and impurity is 65-80%, behind the mixing, continues precipitation again.
2, preparation method according to claim 1 is characterized in that, also comprises the following steps: 6) precipitate in the step 5) carries out acidic hydrolysis, and the pH of hydrolyzed solution is less than 2, and the acidic hydrolysis time is 1-16 hour; 7) with the ultrafilter membrane of MW1000-10000 this hydrolyzed solution is held back concentratedly, making concentrated solution is with the hydrogen peroxide decolouring, and with anion and cation exchange resin mixing desalination behind the 1/2-1/10 of original volume; 8) add the 65-80% that ethanol to this ethanol accounts for mixed liquor, mix homogeneously in the concentrated solution after above-mentioned decolouring desalination; 9) precipitate is collected in centrifugalize, this precipitate of vacuum drying, and pulverize.
3, preparation method according to claim 2 is characterized in that, the hydrogen peroxide consumption that is used to decolour in the step 7) is the 0.5-5% of concentrated solution.
According to the described preparation method of claim 1-3, it is characterized in that 4, raw materials used is Thallus Laminariae (Thallus Eckloniae).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98110253 CN1115166C (en) | 1998-05-29 | 1998-05-29 | Preparation of polyfucose sulfate with varible molecular weight |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98110253 CN1115166C (en) | 1998-05-29 | 1998-05-29 | Preparation of polyfucose sulfate with varible molecular weight |
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| Publication Number | Publication Date |
|---|---|
| CN1197674A CN1197674A (en) | 1998-11-04 |
| CN1115166C true CN1115166C (en) | 2003-07-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 98110253 Expired - Fee Related CN1115166C (en) | 1998-05-29 | 1998-05-29 | Preparation of polyfucose sulfate with varible molecular weight |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305885C (en) * | 2004-12-31 | 2007-03-21 | 中国科学院海洋研究所 | Method for preparing L-fucoidan in sea tangle |
| CN100464756C (en) * | 2007-04-27 | 2009-03-04 | 山东大学 | Application of fucoidan in the preparation of medicine and health-care products for preventing and treating neurodegenerative diseases |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429318C (en) * | 2005-10-28 | 2008-10-29 | 大连水产学院 | Process for preparing fucoidan by enzymatic hydrolysis of brown algae |
| CN100428941C (en) * | 2006-01-13 | 2008-10-29 | 大连水产学院 | Sea-tangle oral liquid with low sugar and rich iodine and its preparation method |
| CN102532332B (en) * | 2011-09-09 | 2014-07-09 | 山东洁晶集团股份有限公司 | Method for extracting and preparing low molecular weight fucoidin from marine brown algae |
| FR2998894B1 (en) * | 2012-12-03 | 2015-07-31 | Seprosys | METHOD OF FRACTIONING ALGAE AND USING THE OBTAINED MOLECULES |
| CN107987179B (en) * | 2017-12-26 | 2020-07-07 | 中国科学院海洋研究所 | Application of low-sulfated fucan in preparation of immunopotentiator |
| CN108484788A (en) * | 2018-04-28 | 2018-09-04 | 唐山曹妃甸恒瑞海洋生物科技产业有限公司 | A kind of extraction and separation process of algal polysaccharide extract |
-
1998
- 1998-05-29 CN CN 98110253 patent/CN1115166C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305885C (en) * | 2004-12-31 | 2007-03-21 | 中国科学院海洋研究所 | Method for preparing L-fucoidan in sea tangle |
| CN100464756C (en) * | 2007-04-27 | 2009-03-04 | 山东大学 | Application of fucoidan in the preparation of medicine and health-care products for preventing and treating neurodegenerative diseases |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1197674A (en) | 1998-11-04 |
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| CB03 | Change of inventor or designer information |
Inventor after: Xue Changhu Inventor after: Li Zhaojie Inventor after: Xin Mei Inventor after: Cai Yuepiao Inventor after: Lin Hong Inventor after: Zhang Qunle Inventor after: Lin Hefeng Inventor before: Xue Changhu Inventor before: Li Zhaojie Inventor before: Xin Mei Inventor before: Cai Yuepiao Inventor before: Lin Hong Inventor before: Zhang Qunle |
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Free format text: CORRECT: INVENTOR; FROM: XUE ZHANGHU; LI ZHAOJIE; XIN MEI; CAI YUEPIAO; LIN HONG; ZHANG QUNYUE TO: XUE ZHANGHU; LI ZHAOJIE; XIN MEI; CAI YUEPIAO; LIN HONG; ZHANG QUNYUE; LIN HEFENG |
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