CN1380342A - Method for preparing algin oligosaccharide - Google Patents
Method for preparing algin oligosaccharide Download PDFInfo
- Publication number
- CN1380342A CN1380342A CN 01107952 CN01107952A CN1380342A CN 1380342 A CN1380342 A CN 1380342A CN 01107952 CN01107952 CN 01107952 CN 01107952 A CN01107952 A CN 01107952A CN 1380342 A CN1380342 A CN 1380342A
- Authority
- CN
- China
- Prior art keywords
- oligosaccharides
- algin
- oxidizing agent
- manufacture method
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001542 oligosaccharide Polymers 0.000 title claims abstract description 23
- 150000002482 oligosaccharides Chemical class 0.000 title claims abstract description 21
- 235000010443 alginic acid Nutrition 0.000 title claims abstract description 16
- 229920000615 alginic acid Polymers 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 7
- 235000010408 potassium alginate Nutrition 0.000 abstract description 3
- 239000000737 potassium alginate Substances 0.000 abstract description 3
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 abstract description 3
- 239000005708 Sodium hypochlorite Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229940072056 alginate Drugs 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- -1 oligosaccharide calcium salt Chemical class 0.000 description 2
- 108010004131 poly(beta-D-mannuronate) lyase Proteins 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WFIYPADYPQQLNN-UHFFFAOYSA-N 2-[2-(4-bromopyrazol-1-yl)ethyl]isoindole-1,3-dione Chemical compound C1=C(Br)C=NN1CCN1C(=O)C2=CC=CC=C2C1=O WFIYPADYPQQLNN-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
一种褐藻胶寡糖的制造方法,包括将褐藻胶分解成寡糖,并分离不同聚合度的寡糖,其特征是所述的分解为在氧化剂存在下的酸水解。所述的氧化剂为过氧化氢或次氯酸钠,其用量为褐藻酸钾水溶液的1－10%。所述的分离采用Bio－Gel－P6或Superdex30柱进行分离。本发明使用的氧化剂和酸的价格低廉,便于大规模生产,并且生产的速度快。A method for producing algin oligosaccharides, comprising decomposing algin into oligosaccharides and separating oligosaccharides with different degrees of polymerization, characterized in that the decomposition is acid hydrolysis in the presence of an oxidizing agent. The oxidizing agent is hydrogen peroxide or sodium hypochlorite, and its dosage is 1-10% of the potassium alginate aqueous solution. Said separation adopts Bio-Gel-P6 or Superdex30 column for separation. The oxidizing agent and acid used in the invention are cheap, convenient for large-scale production, and the production speed is fast.
Description
本发明涉及一种褐藻胶寡糖的制造方法。The invention relates to a method for producing algin oligosaccharides.
褐藻胶无毒，在食品和医药中得到了广泛应用，但由于高分子量褐藻胶不容易被人体消化吸收，如降低其分子量得到相应寡糖，就可以极大地提高其生物利用度，充分发挥其生物学作用。在褐藻胶寡糖的制备与应用方面，有一日本专利(专利号JP05304974)披露了一种采用褐藻胶酶制备褐藻胶寡糖的方法，先在20℃下预培养褐藻胶降解菌，再在25℃下培养24小时，再从中提取褐藻胶酶，然后在40℃下用此酶水解褐藻酸钾，得到寡糖混合物，采用Dowex50w离子交换树脂处理用氢氧化钙中和，并用BioGel P-GDG柱色谱分离后得到寡糖钙盐。该专利将寡糖钙盐应用于降低血压。但用该法制备褐藻胶寡糖所需酶解时间(24小时)长，所用试剂价格高，因而不易商业化。Alginate is non-toxic and has been widely used in food and medicine. However, since high-molecular-weight alginate is not easily digested and absorbed by the human body, if its molecular weight is reduced to obtain corresponding oligosaccharides, its bioavailability can be greatly improved and its potential can be fully utilized. biological effect. In terms of the preparation and application of algin oligosaccharides, there is a Japanese patent (Patent No. JP05304974) which discloses a method for preparing algin oligosaccharides using alginase. First, pre-cultivate algin-degrading bacteria at 20°C, and then at 25 Cultivate at ℃ for 24 hours, extract alginase from it, then use this enzyme to hydrolyze potassium alginate at 40℃ to obtain oligosaccharide mixture, treat with Dowex50w ion exchange resin, neutralize with calcium hydroxide, and use BioGel P-GDG column The oligosaccharide calcium salt is obtained after chromatographic separation. This patent applies oligosaccharide calcium salt to lower blood pressure. However, the enzymatic hydrolysis time (24 hours) required for the preparation of alginic oligosaccharides by this method is long, and the cost of the reagents used is high, so it is not easy to commercialize.
本发明的目的是提供一种氧化酸水解制备褐藻胶寡糖的方法，用它可大量生产褐藻胶寡糖，能弥补现有技术的上述不足。The object of the present invention is to provide a method for preparing algin oligosaccharides by oxidative acid hydrolysis, which can be used to produce algin oligosaccharides in large quantities, and can make up for the above-mentioned shortcomings of the prior art.
一种褐藻胶寡糖的制造方法，包括将褐藻胶水解成寡糖，并分离不同聚合度的寡糖，其特征是所述的水解为在氧化剂存在下的酸水解。A method for producing algin oligosaccharides, comprising hydrolyzing algin into oligosaccharides and separating oligosaccharides with different degrees of polymerization, characterized in that the hydrolysis is acid hydrolysis in the presence of an oxidizing agent.
本发明使用的氧化剂和酸的价格低廉，便于大规模生产，并且生产的速度快。The oxidizing agent and acid used in the invention are cheap, convenient for large-scale production, and the production speed is fast.
下面通过实施例说明本发明。The present invention is illustrated by the following examples.
将低聚褐藻酸钾(平均分子量10000)配成重量百分浓度为3的水溶液，然后用浓度为2mol/L的盐酸调节至pH4，加入氧化剂进行氧化，使其重量百分浓度为2，在高压反应釜中在105℃进行水解3小时，冷却后用氢氧化钾调节至pH7，经0.45μm膜过滤后，旋转蒸发浓缩，采用Bio-Gel-P6或Superdex30柱进行分离，用0.1mol/L(pH7)磷酸缓冲液进行洗脱，得到聚合度为2-12的寡糖，经Sephadex G10脱盐后，冷冻干燥得到白色粉末即为本发明的寡糖产品。Potassium oligomeric alginate (average molecular weight 10,000) is made into an aqueous solution with a weight percent concentration of 3, then adjusted to pH 4 with hydrochloric acid with a concentration of 2 mol/L, and an oxidizing agent is added for oxidation to make the weight percent concentration 2. Hydrolyze at 105°C for 3 hours in a high-pressure reactor, adjust the pH to 7 with potassium hydroxide after cooling, filter through a 0.45 μm membrane, concentrate by rotary evaporation, and separate with a Bio-Gel-P6 or Superdex30 column, using 0.1mol/L (pH7) phosphate buffer for elution to obtain oligosaccharides with a degree of polymerization of 2-12, desalted with Sephadex G10, and freeze-dried to obtain a white powder, which is the oligosaccharide product of the present invention.
本实施例中褐藻胶寡糖M和G的比例为2/1至3/1，M和G的聚合度均在2-12之间，氧化剂为过氧化氢或次氯酸钠，其用量为褐藻酸钾水溶液的1-10％(按重量)。本实施例中水解在高压釜中进行温度为100-120℃，时间为2-4小时。In this example, the ratio of algin oligosaccharides M and G is 2/1 to 3/1, the degree of polymerization of M and G is between 2-12, the oxidizing agent is hydrogen peroxide or sodium hypochlorite, and its dosage is potassium alginate 1-10% (by weight) in aqueous solution. In this embodiment, the hydrolysis is carried out in an autoclave at a temperature of 100-120° C. for 2-4 hours.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011079525A CN1161368C (en) | 2001-04-07 | 2001-04-07 | Production method of phycocolloid oligosaccharide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011079525A CN1161368C (en) | 2001-04-07 | 2001-04-07 | Production method of phycocolloid oligosaccharide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1380342A true CN1380342A (en) | 2002-11-20 |
| CN1161368C CN1161368C (en) | 2004-08-11 |
Family
ID=4656848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011079525A Expired - Fee Related CN1161368C (en) | 2001-04-07 | 2001-04-07 | Production method of phycocolloid oligosaccharide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1161368C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005089776A1 (en) * | 2004-03-24 | 2005-09-29 | Ocean University Of China | Algin oligosaccharides and the derivatives thereof as well as the manufacture and the use of the same |
| CN1321139C (en) * | 2004-11-22 | 2007-06-13 | 青岛明月海藻集团有限公司 | Production process of algin oligose |
| CN100372542C (en) * | 2004-04-16 | 2008-03-05 | 中国海洋大学 | Application of algin oligosaccharides as prebiotics |
| WO2009086685A1 (en) * | 2007-12-29 | 2009-07-16 | Dalian Yaweite Bioengineering Co., Ltd. | An alginic acid with low molecular weight, its salts, uses, preparative methods, pharmaceutical compositions and foods |
| CN101037456B (en) * | 2007-04-24 | 2010-05-26 | 宁波大学 | Preparation method of algin oligosaccharide |
| CN1920002B (en) * | 2005-08-22 | 2011-06-08 | 中国海洋大学 | Novel vibrionaceae vibrio bacterial strain and application thereof |
| CN102391317A (en) * | 2011-08-05 | 2012-03-28 | 宁夏万胜生物工程有限公司 | Method for separating alginate-derived oligosaccharides from alginate-derived oligosaccharide fermentation liquor |
-
2001
- 2001-04-07 CN CNB011079525A patent/CN1161368C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005089776A1 (en) * | 2004-03-24 | 2005-09-29 | Ocean University Of China | Algin oligosaccharides and the derivatives thereof as well as the manufacture and the use of the same |
| EA011417B1 (en) * | 2004-03-24 | 2009-02-27 | Оушн Юниверсити Оф Чайна | Algin oligosaccharides and the derivatives thereof, the manufacture and the use of the same |
| US8835403B2 (en) | 2004-03-24 | 2014-09-16 | Meiyu Geng | Algin oligosaccharides and the derivatives thereof as well as the manufacture and the use of the same |
| US9493496B2 (en) | 2004-03-24 | 2016-11-15 | Ocean University Of China | Algin oligosaccharides and the derivatives thereof as well as the manufacture and the use of the same |
| US10213456B2 (en) | 2004-03-24 | 2019-02-26 | Ocean University Of China | Alginate oligosaccharides and the derivatives thereof as well as the manufacture and the use of the same |
| CN100372542C (en) * | 2004-04-16 | 2008-03-05 | 中国海洋大学 | Application of algin oligosaccharides as prebiotics |
| CN1321139C (en) * | 2004-11-22 | 2007-06-13 | 青岛明月海藻集团有限公司 | Production process of algin oligose |
| CN1920002B (en) * | 2005-08-22 | 2011-06-08 | 中国海洋大学 | Novel vibrionaceae vibrio bacterial strain and application thereof |
| CN101037456B (en) * | 2007-04-24 | 2010-05-26 | 宁波大学 | Preparation method of algin oligosaccharide |
| WO2009086685A1 (en) * | 2007-12-29 | 2009-07-16 | Dalian Yaweite Bioengineering Co., Ltd. | An alginic acid with low molecular weight, its salts, uses, preparative methods, pharmaceutical compositions and foods |
| CN102391317A (en) * | 2011-08-05 | 2012-03-28 | 宁夏万胜生物工程有限公司 | Method for separating alginate-derived oligosaccharides from alginate-derived oligosaccharide fermentation liquor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1161368C (en) | 2004-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103484513A (en) | Method for preparing small-molecule oligomeric hyaluronic acid through enzyme method | |
| CN112760311B (en) | Enzyme solution with better enzyme activity ratio of beta-mannase to alpha-galactosidase, and preparation method and application thereof | |
| JP7220670B2 (en) | Method for decomposing polysaccharides using ozone | |
| CN112813127B (en) | Method for preparing collagen peptide from chondroitin sulfate ultrafiltration waste liquid | |
| JPH04158796A (en) | Production of aqueous solution of sodium hyaluronate | |
| CN110028533A (en) | A kind of method and application of the refining amino glucosamine salt hydrochlorate from microbial fermentation solution | |
| CN104120158A (en) | Method for improving fermentation yield of low-molecular hyaluronic acid (HA) by adding hyaluronidase | |
| EP2321419A2 (en) | Process for the co-production of chitin, its derivatives and polymers containing glucose, mannose and/or galactose, by the fermentation of the yeast pichia pastoris | |
| CN101434980B (en) | Preparation of rice bran short peptide | |
| CN1380342A (en) | Method for preparing algin oligosaccharide | |
| CN102807630B (en) | Low-molecular-weight chitosan and glucosamine co-production technology | |
| CN102228125A (en) | Preparation method of algal active peptide | |
| CN107488693A (en) | The preparation method of sargassum active peptides | |
| CN104178539A (en) | Method for preparing small-molecule hyaluronic acid with specific molecular weight on large scale | |
| JP4151092B2 (en) | Method for producing oligohyaluronic acid or a salt thereof | |
| KR100370929B1 (en) | Preparing Methode for Aqueous Chitosan | |
| JP2012121963A (en) | Method for producing polyguluronic acid, method for producing polymannuronic acid, polyguluronic acid, and polymannuronic acid | |
| KR20070092941A (en) | Preparation of Condoitine Sulfate Oligosaccharides | |
| JPS6121102A (en) | Preparation of chitosan oligosaccharide | |
| CN107163163A (en) | A kind of processing method of chondroitin sulfate product | |
| CN1470533A (en) | Method for preparing low-molecular-weight chondroitin sulfate | |
| CN100542603C (en) | A kind of preparation method of sarcosine peptide glycoside injection liquid | |
| CN100542602C (en) | A kind of preparation method of injection of hydrolyzed peptide of liver | |
| CA2430277A1 (en) | The alginate having low molecular weight, methods of manufacturing it and its use | |
| JPH0222301A (en) | Production of water-soluble chitosan |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: QINGDAO OCEAN UNIVERSITY OF CHINA HOLDINGS CO., LT Free format text: FORMER OWNER: QINGDAO OCEANOLOGY UNIV. Effective date: 20130427 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 266003 QINGDAO, SHANDONG PROVINCE TO: 266071 QINGDAO, SHANDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130427 Address after: 266071 Hongkong East Road, Laoshan District, Shandong, China, No. 23, No. Patentee after: Qingdao Ocean University of China Holdings Limited Address before: 266003 No. 5 fish Hill Road, Shandong, Qingdao Patentee before: Qingdao Oceanology Univ. |
|
| ASS | Succession or assignment of patent right |
Owner name: QINGDAO HAIDA HAITANG BIOTECHNOLOGY CO., LTD. Free format text: FORMER OWNER: QINGDAO OCEAN UNIVERSITY OF CHINA HOLDINGS CO., LTD. Effective date: 20130927 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 266071 QINGDAO, SHANDONG PROVINCE TO: 266061 QINGDAO, SHANDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130927 Address after: 1704 room 182-6, Fortune Tower, No. 266061 Haier Road, Laoshan District, Shandong, Qingdao Patentee after: Qingdao haidahai sugar Biotechnology Co. Ltd. Address before: 266071 Hongkong East Road, Laoshan District, Shandong, China, No. 23, No. Patentee before: Qingdao Ocean University of China Holdings Limited |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20021120 Assignee: QINGDAO BZ OLIGO BIOTECH CO., LTD. Assignor: Qingdao haidahai sugar Biotechnology Co. Ltd. Contract record no.: 2014370000031 Denomination of invention: Production method of phycocolloid oligosaccharide Granted publication date: 20040811 License type: Exclusive License Record date: 20140324 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040811 Termination date: 20200407 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |