CN1554267A - Method for preparing water soluble chitosan - Google Patents
Method for preparing water soluble chitosan Download PDFInfo
- Publication number
- CN1554267A CN1554267A CNA2003101116295A CN200310111629A CN1554267A CN 1554267 A CN1554267 A CN 1554267A CN A2003101116295 A CNA2003101116295 A CN A2003101116295A CN 200310111629 A CN200310111629 A CN 200310111629A CN 1554267 A CN1554267 A CN 1554267A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- solution
- water
- enzyme
- hours
- 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
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000047 product Substances 0.000 claims abstract description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 108090000790 Enzymes Proteins 0.000 claims abstract description 9
- 102000004190 Enzymes Human genes 0.000 claims abstract description 9
- 239000012265 solid product Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 12
- 229920002101 Chitin Polymers 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000000108 ultra-filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 238000010612 desalination reaction Methods 0.000 claims description 3
- 108010064696 N,O-diacetylmuramidase Proteins 0.000 claims description 2
- 108010026195 glycanase Proteins 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 235000013305 food Nutrition 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 2
- 206010028980 Neoplasm Diseases 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000002537 cosmetic Substances 0.000 abstract 1
- 230000036039 immunity Effects 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- 229940088598 enzyme Drugs 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000006276 transfer reaction Methods 0.000 description 4
- 230000000259 anti-tumor effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 108010059892 Cellulase Proteins 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- MBLBDJOUHNCFQT-LXGUWJNJSA-N aldehydo-N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 description 2
- 229940106157 cellulase Drugs 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003053 immunization Effects 0.000 description 2
- 238000002649 immunization Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ODFJOVXVLFUVNQ-UHFFFAOYSA-N acetarsol Chemical compound CC(=O)NC1=CC([As](O)(O)=O)=CC=C1O ODFJOVXVLFUVNQ-UHFFFAOYSA-N 0.000 description 1
- YZGMFQKRGXAHGX-UHFFFAOYSA-N acetic acid methanol pyridine hydrate Chemical compound O.CO.CC(O)=O.c1ccncc1 YZGMFQKRGXAHGX-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000001900 immune effect Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
Abstract
The process of preparing water soluble chitosan includes adding chitosan into 2-8 wt% concentration acetic acid aqua to compound acetic acid solution of chitosan of 2-10 wt% concentration, adding enzyme or oxidant to degrade chitosan to polymerization degree below 1000, cooling the solution to 0-10 deg.c, adding ethanol or methanol solution of acetic anhydride, stirring first at normal temperature for 2-24 hr and then at 20-40 deg.c for another 20-40 deg.c, adding alkali to regulate pH to over 8 under stirring, adding ethanol to deposit, centrifugation to obtain solid product, soaking in alcohol solution of KOH, centrifugation, alcohol washing, and drying to obtain water soluble chitosan of acetyl degree of 45-55%. The present invention has simple preparation process, and the product is used as material for tumor resisting and immunity raising medicine and health product and as additive for cosmetics and food.
Description
Technical field
The present invention relates to a kind ofly prepare that the acetyl degree is 45～55%, the novel method of the water-soluble chitosan (non-salt) of the polymerization degree below 1000, this method has been simplified the higher water-soluble chitosan preparation technology of the polymerization degree, has reduced cost.
Background technology
Chitin is to be only second to cellulosic second largest natural macromolecule amylose on the earth, but the water insoluble and most of organic solvents commonly used of macromole chitin have limited its application, so must carry out chemical modification to chitin.Chitosan be chitin take off the acetyl product.The usually said chitosan polymerization degree was greater than 10 o'clock, and is water-soluble bad, but dissolves in the aqueous solution such as acetic acid, formic acid, hydrochloric acid.Chitosan has the functional of some uniquenesses as a kind of natural alkaline polysaccharide, but its poorly water-soluble has a strong impact on its physiological activity.The water-soluble missionary society of product influences its digestion and absorption in vivo; Though the oligochitosan water soluble, molecular weight is too little, may reduce its some physiologically active.For example, studies show that recently the polymerization degree has better antitumor action and immunologic enhancement greater than 6 water-soluble low molecular weight chitosan than corresponding oligochitosan.Preparation higher degrees of polymerization water-soluble chitosan is that people wish the practical problems that solves always; discover that the acetyl degree is about the chitosan about 50%; during the ethanoyl stochastic distribution, water soluble [Sannan et al.Makromol.Chem., 1975:1191-1194].
The preparation method who has reported the higher degrees of polymerization water-soluble chitosan has following several: first method be with chitin freezing after, highly basic deacetylated [Sannan et al.Makromol.Chem., 1976,177:3589-3600; Kurita et al.Makromol.Chem., 1978:3197-3202], but this method is consuming time long, and need to use a large amount of acetone and ether; Second method is that chitosan is come acetylization reaction [Kurita et al.Chem.Lett., 1989:1597-1598] with acetic anhydride in acetate-water-methanol-pyridine, but the solvent complexity; The third method is to use NaBO
3Degraded use the acetic anhydride acetylize then in the acetum of high density (10%), yet the acetic anhydride consumption is too big earlier, is about 8～9 times [Kubota et al.Carbohydrate Research, 2000,324:268-274.] of amino mole number in the chitosan; The 4th kind of method is to use the chitosan of enzyme liberating acetyl degree 10～30%, utilize the difference of enzyme to the different sugar glycosidic bond recognition capability and the ability of cut-out, prepare low molecular weight product with the uneven distribution of kharophen in the chitosan raw material, but the polymerization degree 10 above water-soluble chitosan product yields are generally less than 20%[Qin et al.International Journal of Biological Macromolecules, 2002,31:111-117.].
Summary of the invention
The present invention proposes a kind of preparation method of higher degrees of polymerization water-soluble chitosan, the water-soluble chitosan yield that this method makes is higher, cost is lower.This product can be used as antitumor and improves the medicine of immunization and the raw material of healthcare products, or is used as the additive of makeup, food.
Main points of the present invention are: chitosan is added in 2～8wt% aqueous acetic acid, filter, be made into the chitosan-acetic acid solution of 2～10wt%, enzyme-added or oxygenant degrade chitosan reach the polymerization degree below 1000 after, solution is cooled to 0～10 ℃ then, the mole number that adds acetic anhydride is the ethanol or the methanol solution of the acetic anhydride of 0.5～10wt% of 0.5～0.7 times of amino mole number in the chitosan, stirred 2～24 hours, then to 20～40 ℃ of stirrings 2～24 hours, under agitation adding alkali transfers more than the reaction mixture pH8, add the ethanol sedimentation, centrifugal after, solid product under agitation soaks with the above 0.1～1wt%KOH alcoholic solution of its 2 times of weight, centrifugal, with alcohol washing, drying, obtain the acetyl degree and be 45～55% water-soluble chitosan.
Above-mentioned enzyme is selected from the mixture of chitoanase, chitin enzyme, glycanase, N,O-Diacetylmuramidase and two or more enzyme; Oxygenant is selected from hydrogen peroxide, hypochlorite and their mixture.
Alcohol in the above-mentioned KOH alcoholic solution is methyl alcohol or ethanol.
Above-mentioned used chitosan raw material is commercially available chitosan; Or with the aqueous sodium hydroxide solution of commercially available chitin and 35～50wt% 65～100 ℃ of reactions 4～20 hours, prepare the acetyl degree and be 15～50% chitosan.
Above-mentioned water-soluble chitosan product drying comprises spray-dried, vacuum-drying, postlyophilization is dissolved in water.
Above-mentioned water-soluble chitosan product can be used ultra-filtration membrane ultrafiltration classification or permeable membrane desalination.
The present invention's chitosan is a raw material, with mole number be in the chitosan acetic anhydride of 0.5～0.7 times of amino mole number to react the acetyl degree that makes in alcohol-aqueous acetic acid be 45～55% water-soluble chitosan, not only yield height (〉=80%), and method for making simple, consuming time short, the acetic anhydride materials are few, cost is lower.The water-soluble chitosan that makes can be used as antitumor and improves the medicine of immunization and the raw material of healthcare products, or is used as the additive of makeup, food.
Embodiment
Embodiment 1: get commercially available shrimp shell chitin 55 grams, with 1000 milliliters of 45wt% soda-lyes, 90 ℃ of reactions of temperature 20 hours, filter, after cleaning alkali lye, chitosan product (acetyl degree 20%) filters with 2500 milliliters of 2wt% acetate dissolutions, add commercially available hydrogen peroxide 10 grams, 70 ℃ of reactions, when the chitosan mean polymerisation degree drops to 500, add an amount of sodium bisulfite, solution is cooled to 5 ℃ then, 1000 milliliters of the ethanolic solns that dropping contains 12.5 gram acetic anhydride slowly stirred 12 hours, slowly stirred 24 hours to 20 ℃ then, under agitation add alkali and transfer reaction mixture pH11, add the ethanol sedimentation, centrifugal, solid product under agitation soaks for 500 milliliters with the 0.1wt%KOH methanol solution, centrifugal, with 100 ml methanol washing three times, drain vacuum-drying respectively, gained water-soluble chitosan product acetyl degree is 48.5%, yield 〉=95%.
Embodiment 2: get commercially available crab shell chitin 110 grams, with 2000 milliliters of 40wt% soda-lyes, 70 ℃ of reactions of temperature 12 hours, filter, after product (acetyl degree 32%) is cleaned alkali lye, add 2800 milliliter of 2.6% acetate dissolution, filter, the enzyme-added liquid of filtrate (produce by Wuhan, contain half cellulase and chitoanase) 50 ℃ of reactions, when the chitosan mean polymerisation degree drops to approximately 10 the time, solution is cooled to 0 ℃ then, drip 2500 milliliters of ethanol that contain 24.5 gram acetic anhydride, slowly stirred 24 hours, slowly stirred 2 hours to 28 ℃ then, under agitation add KOH and transfer reaction mixture pH9, add the ethanol sedimentation, centrifugal, solid product under agitation soaks hour with 1000 milliliters of 0.5wt%KOH ethanolic solns, and is centrifugal, uses 100 milliliters of washing with alcohol three times respectively, product is dissolved in water, lyophilize, gained water-soluble chitosan product acetyl degree is 53.5%, yield is 92%.
Embodiment 3: get commercially available shrimp shell chitosan (acetyl degree 9%) 110 grams, add 2500 milliliters of 2.9wt% acetate dissolutions, filter, filtrate adds R-10 cellulase (Japan produces) 3 grams, 48 ℃ of reactions, when the chitosan mean polymerisation degree drops to about 20 the time, solution is cooled to 0 ℃ then, 2500 milliliters of the ethanol that dropping contains 25.1 gram acetic anhydride slowly stirred 12 hours, and temperature control to 28 ℃ slowly stirred 5 hours then, under agitation add KOH and transfer reaction mixture pH9, add the ethanol sedimentation, centrifugal, solid product under agitation soaks hour with 1000 milliliters of 0.5wt%KOH ethanolic solns, centrifugal, use 150 milliliters of washing with alcohol three times respectively, product is dissolved in water, and uses NMWL 10kDa, 3kDa and the classification of 1kDa ultra-filtration membrane obtain the solution of three components, behind the filtrate vacuum concentration with middle two components, vacuum-drying gets the water-soluble chitosan product, and the average acetyl degree of products therefrom is 50.2%, and total recovery is 93%.
Embodiment 4: get commercially available crab shell chitosan (acetyl degree 15.5%) 110 grams, add 2500 milliliters of 2.9wt% acetate dissolutions, filter, in filtrate, add clorox 6 grams and hydrogen peroxide 3 grams, 60 ℃ of reactions,, add an amount of sodium bisulfite when the chitosan mean polymerisation degree drops to approximately 200 the time, behind commercially available permeable membrane or 1kDa ultra-filtration membrane desalination, solution is cooled to 10 ℃, drips 2500 milliliters of methyl alcohol containing 28.1 gram acetic anhydride, slowly stirred 12 hours, slowly stirred 12 hours to 40 ℃ then, under agitation add NaOH and transfer reaction mixture pH8, add the ethanol sedimentation, centrifugal, solid product under agitation soaked 4 hours with 1000 milliliters of 0.5wt%KOH methanol solutions, centrifugal, with 200 ml methanol washing three times, vacuum-drying gets the chitosan product respectively, the average acetyl degree of products therefrom is 51.8%, and yield is 92%.
Claims (6)
1. method for preparing water-soluble chitosan, it is characterized in that: chitosan is added in 2～8wt% aqueous acetic acid, filter, be made into the chitosan-acetic acid solution of 2～10wt%, enzyme-added or oxygenant degrade chitosan reach the polymerization degree below 1000 after, solution is cooled to 0～10 ℃ then, the mole number that adds acetic anhydride is the ethanol or the methanol solution of the acetic anhydride of 0.5～10wt% of 0.5～0.7 times of amino mole number in the chitosan, stirred 2～24 hours, to 20～40 ℃ of stirrings 2～24 hours, under agitation add alkali and transfer more than the reaction mixture pH8 then, add the ethanol sedimentation, after centrifugal, solid product under agitation soaks with the KOH alcoholic solution of 0.1 above～1wt% of its 2 times of weight, and is centrifugal, with the alcohol washing, drying obtains the acetyl degree and is 45～55% water-soluble chitosan.
2. method according to claim 1 is characterized in that: described enzyme is selected from the mixture of chitoanase, chitin enzyme, glycanase, N,O-Diacetylmuramidase and two or more enzyme; Described oxygenant is selected from hydrogen peroxide, hypochlorite and their mixture.
3. method according to claim 1 and 2 is characterized in that: the alcohol in the described KOH alcoholic solution is methyl alcohol or ethanol.
4. method according to claim 1 and 2 is characterized in that: the aqueous sodium hydroxide solution that used chitosan raw material is chitin and 35～50wt% prepares the acetyl degree and is 15～50% chitosan 65～100 ℃ of reactions 4～20 hours.
5. method according to claim 1 and 2 is characterized in that: described drying is spray-dried, vacuum-drying or the postlyophilization that is dissolved in water.
6. method according to claim 1 and 2 is characterized in that: above-mentioned water-soluble chitosan product ultra-filtration membrane ultrafiltration classification or permeable membrane desalination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101116295A CN1233664C (en) | 2003-12-23 | 2003-12-23 | Method for preparing water soluble chitosan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101116295A CN1233664C (en) | 2003-12-23 | 2003-12-23 | Method for preparing water soluble chitosan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1554267A true CN1554267A (en) | 2004-12-15 |
| CN1233664C CN1233664C (en) | 2005-12-28 |
Family
ID=34336232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101116295A Expired - Fee Related CN1233664C (en) | 2003-12-23 | 2003-12-23 | Method for preparing water soluble chitosan |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1233664C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006134614A1 (en) * | 2005-06-14 | 2006-12-21 | Genis Ehf. | Compositions of partially deacetylated chitin derivatives |
| CN102432378A (en) * | 2011-09-19 | 2012-05-02 | 北京雷力农用化学有限公司 | Foliar fertilizer and preparation method thereof |
| CN102702382A (en) * | 2012-01-17 | 2012-10-03 | 烟台大学 | Preparation method of chitosan derivative and application in anticoagulant drug |
| CN104740141A (en) * | 2015-04-16 | 2015-07-01 | 广东泰宝医疗科技股份有限公司 | Antibacterialp spray and preparation method thereof |
| CN102159218B (en) * | 2008-07-18 | 2015-12-02 | 杰尼斯Ehf公司 | For the novel chitin oligomeric composition of medical usage |
| CN106519070A (en) * | 2016-07-21 | 2017-03-22 | 广西民族大学 | A kind of water-soluble N-acetylated chitosan and preparation method thereof |
| CN107233617A (en) * | 2017-06-05 | 2017-10-10 | 浙江工业大学 | A kind of wound dressing of liquid chitosan and its preparation and application |
| CN108276506A (en) * | 2018-02-06 | 2018-07-13 | 西南科技大学 | The preparation method and its product and its product of hydrophobic chitosan are used to prepare the purposes of hemostatic material |
| CN110128567A (en) * | 2019-05-13 | 2019-08-16 | 金陵科技学院 | Method for preparing environment-friendly rust inhibitor for steel bars using natural biomass chitin polymer |
| CN113683463A (en) * | 2021-09-09 | 2021-11-23 | 苏农（广德）生物科技有限公司 | Production process of compound fertilizer based on biological agent |
-
2003
- 2003-12-23 CN CNB2003101116295A patent/CN1233664C/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9078949B2 (en) | 2005-06-14 | 2015-07-14 | Genis Hf. | Compositions of partially deacetylated chitin derivatives |
| JP2008544014A (en) * | 2005-06-14 | 2008-12-04 | ジェニス イーエイチエフ． | Composition of partially deacetylated chitin derivatives |
| RU2421467C2 (en) * | 2005-06-14 | 2011-06-20 | Дженис Эхф. | Compositions of partially deacetylated chitin derivatives |
| NO344086B1 (en) * | 2005-06-14 | 2019-09-02 | Genis Ehf | Compositions of partially deacetylated chitin polymers and oligomers, and processes for their preparation |
| US20180186899A1 (en) * | 2005-06-14 | 2018-07-05 | Genis Hf. | Compositions of partially deacetylated chitin derivatives |
| CN101248019B (en) * | 2005-06-14 | 2012-12-26 | 杰尼斯Ehf公司 | Compositions of partially deacetylated chitin derivatives |
| WO2006134614A1 (en) * | 2005-06-14 | 2006-12-21 | Genis Ehf. | Compositions of partially deacetylated chitin derivatives |
| JP2014221905A (en) * | 2005-06-14 | 2014-11-27 | ジェニス イーエイチエフ．Ｇｅｎｉｓ ｅｈｆ． | Composition of partially deacetylated chitin derivative |
| CN102159218B (en) * | 2008-07-18 | 2015-12-02 | 杰尼斯Ehf公司 | For the novel chitin oligomeric composition of medical usage |
| CN102432378A (en) * | 2011-09-19 | 2012-05-02 | 北京雷力农用化学有限公司 | Foliar fertilizer and preparation method thereof |
| CN102702382B (en) * | 2012-01-17 | 2014-04-23 | 烟台大学 | Preparation method of chitosan derivative and application in anticoagulant drug |
| CN102702382A (en) * | 2012-01-17 | 2012-10-03 | 烟台大学 | Preparation method of chitosan derivative and application in anticoagulant drug |
| CN104740141A (en) * | 2015-04-16 | 2015-07-01 | 广东泰宝医疗科技股份有限公司 | Antibacterialp spray and preparation method thereof |
| CN106519070A (en) * | 2016-07-21 | 2017-03-22 | 广西民族大学 | A kind of water-soluble N-acetylated chitosan and preparation method thereof |
| CN107233617A (en) * | 2017-06-05 | 2017-10-10 | 浙江工业大学 | A kind of wound dressing of liquid chitosan and its preparation and application |
| CN108276506A (en) * | 2018-02-06 | 2018-07-13 | 西南科技大学 | The preparation method and its product and its product of hydrophobic chitosan are used to prepare the purposes of hemostatic material |
| CN108276506B (en) * | 2018-02-06 | 2021-01-08 | 西南科技大学 | Preparation method of hydrophobic chitosan, product thereof and application of product thereof in preparation of hemostatic material |
| CN110128567A (en) * | 2019-05-13 | 2019-08-16 | 金陵科技学院 | Method for preparing environment-friendly rust inhibitor for steel bars using natural biomass chitin polymer |
| CN110128567B (en) * | 2019-05-13 | 2021-03-16 | 金陵科技学院 | Method for preparing environment-friendly type reinforcement corrosion inhibitor by using natural biomass chitin high polymer |
| CN113683463A (en) * | 2021-09-09 | 2021-11-23 | 苏农（广德）生物科技有限公司 | Production process of compound fertilizer based on biological agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1233664C (en) | 2005-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103717622B (en) | A kind of method that hemicellulose is extracted from corn fiber | |
| CN106905440B (en) | A kind of method that tremella polysaccharides extract | |
| ES2704109T3 (en) | Process for the fractionation of oligosaccharides from agricultural waste | |
| CN1233664C (en) | Method for preparing water soluble chitosan | |
| US20140120584A1 (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 | |
| CN101845471A (en) | Method for rapidly dissolving chitosan and preparing chitosan with high-concentration substrate enzymatic method | |
| CN1177856C (en) | Industrialized production method of low chitosan and chitosan oligosaccharide | |
| CN106432538A (en) | Method for preparing chitin oligosaccharides, chitooligosaccharides and chitosan oligosaccharides | |
| CN102070727A (en) | Extraction method of sodium heparin | |
| CN112175111B (en) | Method for efficiently separating wood fiber material to obtain high-purity components | |
| CN100386345C (en) | Preparation process of chito oligosaccharace hydrochloride | |
| GB2612082A (en) | Process of production of xylooligosaccharides from peels of orange fruit | |
| RU2422044C1 (en) | Method for production of pectin and food fibres of pumpkin cake | |
| KR102144574B1 (en) | Agar oligosaccharides Manufacturing Method | |
| CN118930682B (en) | Method for extracting arabinoxylan from corn fiber skin | |
| CN113652463A (en) | Method for rapidly extracting polypeptide substances from sweet potatoes | |
| CN107011451A (en) | White fungus different poly- polysaccharide and its extract, preparation method and application | |
| KR100679411B1 (en) | Manufacturing Method of Polymer Water Soluble Alkali Chitosan Using Natural Organic Germanium Water | |
| CN117024622A (en) | Preparation process of low molecular weight fucoidin and prepared fucoidin | |
| CN109422823A (en) | The preparation method of chondroitin sulfate | |
| CN105106075A (en) | Composition with nutritional and moisturizing efficacies as well as preparation method and application of composition | |
| CN102887965A (en) | Preparation method for obtaining uniform xylan from corn cob | |
| CN120309757A (en) | A preparation method of yeast beta-glucan | |
| CN1231580C (en) | Simplified method for extracting purified superoxide dismutase | |
| CN119454787A (en) | Extraction method and application of frost-removed mulberry leaf extract |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Zhejiang Anjijiaxiang Food Co., Ltd. Assignor: Xiaogan College Contract fulfillment period: 2009.5.28 to 2014.5.27 contract change Contract record no.: 2009330001935 Denomination of invention: Method for preparing water soluble chitosan Granted publication date: 20051228 License type: Exclusive license Record date: 2009.8.12 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.5.28 TO 2014.5.27; CHANGE OF CONTRACT Name of requester: ZHEJIANG PROVINCE ANJIJIAXIANG FOOD CO., LTD. Effective date: 20090812 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20051228 Termination date: 20100125 |