CN103360514B - A kind of fast degradation prepares the method for water soluble oligo-chitosan - Google Patents
A kind of fast degradation prepares the method for water soluble oligo-chitosan Download PDFInfo
- Publication number
- CN103360514B CN103360514B CN201310251346.4A CN201310251346A CN103360514B CN 103360514 B CN103360514 B CN 103360514B CN 201310251346 A CN201310251346 A CN 201310251346A CN 103360514 B CN103360514 B CN 103360514B
- Authority
- CN
- China
- Prior art keywords
- chitosan
- solution
- water soluble
- superoxol
- prepares
- 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.)
- Expired - Fee Related
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The present invention discloses a kind of method that fast degradation prepares water soluble oligo-chitosan, comprises the steps: that (1) prepares chitosan solution; (2) superoxol insulation is added to chitosan solution; (3) under ultrasonic-microwave combined action condition, carry out DeR, ultrasonic power is 10 ~ 100W, and microwave power is 160 ~ 640W, and the combined action time is 1 ~ 10min; (4) alkaline solution of the solution after DeR regulates pH to neutral, after separation, drying, namely obtain chitosan oligomer.The present invention prepares water soluble oligo-chitosan with hydrogen peroxide oxidation alternating action in chitosan by utilizing microwave-ultrasonic to combine, and has the advantages such as quick preparation, easily separated purifying, technological process environmental protection, product relative molecular mass distribution be even.
Description
Technical field
The invention belongs to the method for water soluble oligo-chitosan, particularly relate to one and utilize microwave-ultrasonic to combine and hydrogen peroxide oxidation alternating action, fast degradation prepares the method for water soluble oligo-chitosan.
Background technology
Chitin is the maximum nitrogenous natural organic high-molecular compound of the outer quantity of nature isolating protein, and by biosynthetic chitin about 10,000,000,000 tons every year, being only second to Mierocrystalline cellulose, is second largest renewable resources on the earth.Chitosan is obtained through partially or completely deacetylation by chitin, and chemistry (Isosorbide-5-Nitrae)-2-amino-2-deoxidation-β-D-Glucose by name, connects with β-(Isosorbide-5-Nitrae) glycosidic link between molecule.Chitin and chitosan, due to the interaction of hydrogen bond inside and outside in its molecular structure, defines orderly macromolecular structure, and relative molecular mass is usually extremely millions of at hundreds of thousands of, and water insoluble common solvent such as grade, application is extremely restricted.
The chitosan oligomer of relatively small molecular weight (800-10000) scope is reached compared with non-degrade chitosan after degraded, its molecular weight reduces, destroy the reticulated structure of some molecules, the compactness of its crystalline structure is significantly reduced, solvability strengthens greatly, biological activity, coordination ability significantly improves, not only maintain some functional property had of non-degrade chitosan, as reduced cholesterol, hypotensive blood fat, prevent and treat diabetes, strengthening liver function, treatment is burnt, scald etc., and the chitosan oligomer of different molecular weight ranges also has physiologically active not available for many non-degrade chitosans and functional property, as humidity-preserving type, immunomodulatory, anti-cancer, regulating intestinal canal flora, functional sweetener, as nutritional fortification agent carrier, get rid of hazardous and noxious substances in body, Antimicrobial preservative, inducing plant produces toxinicide etc. many effects.Therefore, the preparation and application of chitosan oligomer have become the focus of research both at home and abroad.
At present, the preparation of chitosan oligomer mainly contains three kinds of methods: chemical degradation method, enzyme liberating method and physical degradation methods.Composite degradation method is a newer research field at present.
One, chemical degradation method: refer to and make degradation of chitosan by chemical reaction, have acid degradation method and oxidation degradation method, wherein H
2o
2oxidation style have lot of documents report, and for the production of.The open source literature relevant to chemical degradation method is as follows:
1. application number: 201010178792.3, denomination of invention: a kind of preparation method of chitosan oligomer, summary: a kind of preparation method of chitosan oligomer, by chitosan solution Hydrodynamic cavitation effect own, degraded is carried out to chitosan and manufactures chitosan oligomer, comprising: chitosan dissolves, Hydrodynamic cavitation degraded, complete to degraded after chitosan solution in add alkaline solution and regulate pH and throw out to wash and the step such as vacuum-drying, the technical process of described Hydrodynamic cavitation degraded is: be placed on by chitosan solution in basin, and carry out constant temperature by cyclic water tank, chitosan solution carries out cavitation technology by pump delivery to cavitation device, by valve V1, V2, V3, V4 regulates upstream inlet pressure, downstream Recovery and rebuild and flow, and by tensimeter and under meter monitor force and flow, solution return after cavitation technology is in basin, by cyclic water tank, temperature is controlled at 25-80 DEG C, circular treatment 0.5h-20h is carried out until reach required relative molecular mass requirement and be as the criterion in Hydrodynamic cavitation device, the method has simple and easy to do, energy consumption is low, efficiency high.But this method product yield is lower, hydrolysate is complicated, separation difficulty, and environmental pollution is serious.
2. application number: 201110125040.5, denomination of invention: a kind of production method of chitosan oligomer, summary: a kind of production method of chitosan oligomer, belongs to technical field of fine; It is characterized in that relating to the method for producing chitosan oligomer (oligochitosan) with hydrogen peroxide as oxidizing chitosan.Its chitosan mass mark is 5% ~ 35%, when reaching reaction end, n (hydrogen peroxide): n (chitosan)=1.3 ~ 5.5, and temperature of reaction is 50 DEG C ~ 90 DEG C.Reaction solution is cooled to 0 DEG C ~ 10 DEG C, is that 95% ethanol is separated out by-30 DEG C ~ 0 DEG C volume fraction, w (ethanol): w (reaction solution)=1 ~ 4.Filter cake is 99% washing with alcohol 1 ~ 5 time by-30 DEG C ~ 10 DEG C volume fractions, dries 2h ~ 8h for then 40 DEG C ~ 60 DEG C.Effect of the present invention and benefit are that chitosan oligomer molecular weight is low, and solubleness is up to 80g/100g water.Degraded is carried out in neutral medium, and product is not containing inorganic salts.Add reducing substance in reaction solution, remaining superoxide can be eliminated completely.Produce without the three wastes, product yield is high, and biological activity is high, and color and luster improves, and belongs to non-poisonous material through toxicology test.Adopt H in neutral conditions
2o
2solution carries out oxidative degradation to chitosan, but is subject to the impact on DeR of different concentration of hydrogen peroxide, proportioning, temperature and reaction times, and preparation process is complicated, and the reaction times is long, and process is difficult to control, and greatly have impact on production efficiency.
Two, enzyme liberating method: be utilize enzymatic hydrolysis, is divided into specificity enzyme liberating method and non-specific enzyme liberating method.Enzyme liberating method has reaction conditions gentleness, whole degradation process adds without other reaction reagents, be unlikely to occur that other side reaction, degradation process and degraded product relative molecular mass distribution are easy to control, chitosan oligomer yield is high, do not cause the advantages such as environmental pollution.The open source literature relevant to enzyme liberating method is as follows:
1. application number: 03128199.0, denomination of invention: the production method of chitosan enzyme-producing bacteria and chitosan oligomer, summary: the invention discloses one microorganism culturing obtain chitoanase and produce chitosan oligomer (or title amino-oligosaccharide, shell oligosaccharide) method, described microorganism is the genus bacillus obtained from seabeach, after obtaining bacterial classification, the method for enzymic fermentation is produced in induction is add appropriate chitosan and nitrogenous source, in the solution of inorganic nutrient salt, cultivate at normal temperatures and within 30-40 hour, can obtain that there is highly active chitosanase preparation, the method that enzymolysis produces sugar is mixed by a certain percentage enzyme liquid and chitosan solution, enzyme digestion reaction is carried out under very gentle condition, in short period of time, chitosan can be converted into chitosan oligomer by (4-12 hour), concentrated or drying obtains product.The bacterial classification genetic stability of the method, zymogenic rate is high, fermentation and enzymatic hydrolysis condition routinizes, speed is fast, good product quality.But the enzyme cost that enzyme process uses is higher.
2. application number: 200810056488.4, denomination of invention: a kind of processing method of preparing oligomeric chitosan by complex enzyme degradation, summary: the processing method that the invention discloses a kind of preparing oligomeric chitosan by complex enzyme degradation; Utilize different types of non-specific enzyme and α-amylase and bromeline, or cellulase, the synergy produced in degrade chitosan process improves degradation efficiency, makes the molecular-weight average of product degrade and reach about 1500Da in 5.0h.Last degraded product, through micro-filtration and nanofiltration purifying, concentrated and spraying dry, can obtain the oligopolymerization chitosan sugar product of high-quality.Compared with traditional preparation technology, this technique not only Product Activity is high, superior in quality, easy to operate, and improves production environment, is conducive to realizing industrialization.But also there is the high problem of enzyme cost in this method.
Three, Physical: be mainly ultrasonic wave, microwave, electromagenetic wave radiation edman degradation Edman.Have simple to operate, speed is fast, no coupling product, the advantages such as non-environmental-pollution, and the open source literature relevant to Physical is as follows:
1. application number: 200810156803.0, denomination of invention: the preparation method of chitosan oligomer, summary: the preparation method that the invention discloses a kind of chitosan oligomer, macromole chitosan raw material → add degraded sensitizing agent mixing → irradiation → spraying dry → aqua product → concentrated → spraying dry → powder product, have quick, easy, high yield, low cost, effectively product assay high, not to advantages such as environments, be extremely conducive to large-scale industrial production.
2. Li Jun stands, Zhang Bo, horsepower. the ultrasonic degradation of chitosan and optimised process research. Xihua Univ's journal (natural science edition) .2011,30(5): 100-103. be with natural macromolecular amount chitosan for raw material, utilize single sonication to prepare chitosan oligomer, have simple to operate, with low cost, product is simple, pollution-free, easily extracts the advantages such as recovery.
But there is the problems such as the control of chitosan oligomer degradation process and molecular weight distribution in these two kinds of methods, its relative molecular mass is higher.
Four, composite degradation method: i.e. the combinationally using of above each degradation method is a newer research field at present.We find following pertinent literature:
1. application number: 200610113614.6, denomination of invention: a kind of industrial preparation process of chitosan oligomer, summary: the industrialized production process that the invention discloses a kind of chitosan oligomer; Cellulase is adopted to degrade in conjunction with the chitosan of method to high-polymerization degree of hydrogen peroxide.In cellulose degraded, chitosan (g): cellulase A (g)=10: 1 ~ 0.8; The temperature of reaction of cellulase is 55 ~ 60 DEG C; Reaction times is 1.5 ~ 2.0h.In hydrogen peroxide oxidation degraded, hydrogen peroxide use is: chitosan (g): 30% hydrogen peroxide (mL)=1: 1.0 ~ 0.8, and the concentration of hydrogen peroxide is mass percent; Hydroperoxidation temperature is 75 ~ 80 DEG C; Reaction times is 1 ~ 2.5h.Again after micro-filtration, nanofiltration and drying, the molecular weight of gained oligopolymerization chitosan sugar product is low, distributes single.This technique is simple, operation is convenient, is suitable for scale operation.
2. application number: 200810218806.2, denomination of invention: the method preparing chitosan oligomer under steady magnetic field condition, summary: the invention discloses the method preparing chitosan oligomer under steady magnetic field condition, the method comprises: the preparation of chitosan acetic acid solution; The preparation of chitosan magnetic micro-sphere; The preparation of magnetic immobilized cellulase; The preparation of chitosan oligomer; The present invention not only can improve the degradation rate of polymer substance, and provides theoretical foundation for realizing continuous prodution, can be convenient to the recovery of enzyme simultaneously, improve the utilization ratio of immobilized enzyme, reduce costs.
3. Wang Ke army, Yang Li is strong; Xue's Jun, Li Fengyi, Hu Shanling. microwave radiation and rare earth coordination control combination technology prepare chitosan oligomer. University Of Nanchang's journal (natural sciences version) .2006,30(6): 556-559. for raw material, adopts microwave radiation and rare earth coordination control combination technology to prepare chitosan oligomer with industrial goods high molecular weight chitosan, the relative molecular mass distribution of products obtained therefrom evenly, the speed of degraded significantly improves.
Summary of the invention
The object of the invention is to solve that prior art poor process control, consuming time, power consumption, product subsequent disposal are complicated, the unequal problem of product relative molecular mass distribution, a kind of fast degradation is provided to prepare the method for water soluble oligo-chitosan, combine by utilizing microwave-ultrasonic and prepare water soluble oligo-chitosan with hydrogen peroxide oxidation alternating action in chitosan, there is the advantages such as quick preparation, easily separated purifying, technological process environmental protection, product relative molecular mass distribution be even.
For achieving the above object, the invention provides following technical scheme:
Fast degradation prepares a method for water soluble oligo-chitosan, comprises the steps:
(1) chitosan solution is prepared;
(2) superoxol insulation is added to chitosan solution;
(3) under ultrasonic-microwave combined action condition, carry out DeR, ultrasonic power is 10 ~ 100W, and microwave power is 160 ~ 640W, and the combined action time is 1 ~ 10min;
(4) alkaline solution of the solution after DeR regulates pH to neutral, and after separation, drying, namely obtain chitosan oligomer, the molecular weight of gained chitosan oligomer is 800 ~ 8000.
As further instruction, the above superoxol is in chitosan: the ratio of superoxol=1g: 1 ~ 10ml adds.
As further instruction, the above holding temperature is 30 ~ 70 DEG C, soaking time 1 ~ 60min.
As further instruction, the mass concentration of the above superoxol is 0.5 ~ 15%.
As further instruction, the concentration of the above chitosan solution is 10 ~ 50g/L, is to add acetate dissolution again after being mixed with water by chitosan.
As further instruction, the above alkaline solution is NaOH, ammoniacal liquor or KOH.
As further instruction, the above is separated, dry operation steps: be that the reaction soln after adjusting neutrality is carried out centrifugation, its parting liquid adds ethanolic soln precipitation, then centrifugation, after separation be deposited in-50 ~ 20 DEG C at vacuum-drying, namely obtain chitosan oligomer.
As further instruction, the above ethanolic soln purity is 50 ~ 100%.
In the present invention, the deacetylation of chitosan is greater than 95%.
Compared with prior art, beneficial effect of the present invention is:
(1) physics combines with chemical process, adopts ultrasonic-microwave combined and H
2o
2alternating action takes off the chitosan of acetyl in height, and the principle utilizing macromole chitosan to be insoluble to neutrality or alkaline aqueous solution makes macromole separate out, centrifugal segregation, vacuum lyophilization is carried out to product and obtains finished product, material of the present invention is cheap and easy to get, and production process is simple to operate, and production technique feasibility is high, the quality product obtained is good, relative molecular mass distribution is even, and completely water-soluble, solubleness is 100%, subsequent disposal is simple, has certain application and promotional value.
(2) adopt ultrasonic-microwave combined action, relative to single ultrasonic wave or single microwave, have better synergistic function, greatly reduce the reaction times, separation purifying technique is simple, and product water dissolubility is high.
Accompanying drawing explanation
Fig. 1 be raw materials of chitosan 1. with product chitosan oligomer infrared spectrogram 2..
As shown in Figure 1, the peak type of chitosan skeleton is substantially constant, 3367cm
-1~ 3381
-1the stretching vibration absorption peak that on place's display chitosan skeleton, hydroxyl produces because of hydrogen bond action and N-H stretching vibration; 1642 ~ 1650cm
-1stronger amino absorption peak is there is in scope; 1384cm
-1place is C-CH
3the formation vibration peak at place; 1255cm
-1place is C-H vibration peak; 1078cm
-1for C-O absorption peak, 1154cm
-1for C-O-C stretching vibration absorption peak, 897cm
-1~ 890cm
-1absorption peak caused by furanose ring vibration, be the charateristic avsorption band of β (1 → 4) glycosidic link in chitosan skeleton.
But after degraded, the charateristic avsorption band change in chitosan molecule has following features, at 3367cm
-1~ 3381
-1hydroxyl in scope changes because of its stretching vibration absorption peak strength of hydrogen bond action, and H is described
2o
2the OH that cracking goes out also can change into carbonyl a part of hydroxyl oxygen.1642cm
-1~ 1650cm
-1free amine group absorption peak strengthens, and illustrates in degradation process along with deacetylation; The C-CH at 1384cm-1 place
3the formation vibration peak at place and 1255cm
-1not there is considerable change in the C-H vibration peak at place, illustrates that ultrasonic-microwave works in coordination with 5%H
2o
2the lower ring-opening reaction that can not cause chitosan of degraded.897cm
-1~ 890cm
-1the characteristic absorbance peak intensity of β (1 → 4) glycosidic link at place changes, and illustrates that degraded causes the fracture of β (1 → 4) glycosidic link.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to the scope that embodiment represents.
Embodiment 1:
Fast degradation prepares a method for water soluble oligo-chitosan, comprises the steps:
(1) add 2% acetum after first being mixed with water by macromole chitosan again to dissolve, obtain the chitosan solution that concentration is 10g/L;
(2) add 10% superoxol insulation to the chitosan solution after dissolving, holding temperature is 30 DEG C, soaking time 5min, and superoxol is in chitosan: the ratio of superoxol=1g: 1ml adds;
(3) under ultrasonic-microwave combination condition, carry out DeR, ultrasonic power is 10W, and microwave power is 160W, and the ultrasonic-microwave combined action time is 1min.
(4) be that 4%NaOH solution regulates pH to neutral by the solution mass concentration after DeR, centrifugation, it is 50% ethanolic soln precipitation that its parting liquid adds purity, centrifugation again, after separation be deposited in 20 DEG C at vacuum-drying, namely obtain chitosan oligomer, its molecular weight is 8963.2.
Embodiment 2:
Fast degradation prepares a method for water soluble oligo-chitosan, comprises the steps:
(1) add 2% acetum after first being mixed with water by macromole chitosan again to dissolve, obtain the chitosan solution that concentration is 50g/L;
(2) add 2% superoxol insulation to the chitosan solution after dissolving, holding temperature is 70 DEG C, soaking time 60min, and superoxol is in chitosan: the ratio of superoxol=1g: 10ml adds;
(3) under ultrasonic-microwave combination condition, carry out DeR, ultrasonic power is 50W, and microwave power is 640W, and the ultrasonic-microwave combined action time is 10min.
(4) be that 4%NaOH solution regulates pH to neutral by the solution mass concentration after DeR, centrifugation, it is 100% ethanolic soln precipitation that its parting liquid adds purity, centrifugation again, after separation be deposited in-50 DEG C at vacuum-drying, namely obtain chitosan oligomer, its molecular weight is 1368.4.
Embodiment 3:
Fast degradation prepares a method for water soluble oligo-chitosan, comprises the steps:
(1) add 2% acetum after first being mixed with water by macromole chitosan again to dissolve, obtain the chitosan solution that concentration is 20g/L;
(2) add 5% superoxol insulation to the chitosan solution after dissolving, holding temperature is 60 DEG C, soaking time 5min, and superoxol is in chitosan: the ratio of superoxol=1g: 5ml adds;
(3) under ultrasonic-microwave combination condition, carry out DeR, ultrasonic power is 50W, and microwave power is 450W, and the ultrasonic-microwave combined action time is 8min.
(4) be that 4%NaOH solution regulates pH to neutral by the solution mass concentration after step (3) DeR, centrifugation, it is 95% ethanolic soln precipitation that its parting liquid adds purity, centrifugation again, after separation be deposited in-20 DEG C at vacuum-drying, namely obtain chitosan oligomer, its molecular weight is 5912.9.
Embodiment 4:
Fast degradation prepares a method for water soluble oligo-chitosan, comprises the steps:
(1) add 1% acetum after first being mixed with water by macromole chitosan again to dissolve, obtain the chitosan solution that concentration is 30g/L;
(2) add 8% superoxol insulation to the chitosan solution after dissolving, holding temperature is 40 DEG C, soaking time 30min, and superoxol is in chitosan: the ratio of superoxol=1g: 2ml adds;
(3) under ultrasonic-microwave combination condition, carry out DeR, ultrasonic power is 50W, and microwave power is 360W, and the ultrasonic-microwave combined action time is 2min.
(4) be that 4%NaOH solution regulates pH to neutral by the solution mass concentration after step (3) DeR, centrifugation, it is 85% ethanolic soln precipitation that its parting liquid adds purity, centrifugation again, after separation be deposited in 0 DEG C at vacuum-drying, namely obtain chitosan oligomer, its molecular weight is 6249.6.
Embodiment 5:
Fast degradation prepares a method for water soluble oligo-chitosan, comprises the steps:
(1) add 1% acetum after first being mixed with water by macromole chitosan again to dissolve, obtain the chitosan solution that concentration is 40g/L;
(2) add 15% superoxol insulation to the chitosan solution after dissolving, holding temperature is 70 DEG C, soaking time 1min, and superoxol is in chitosan: the ratio of superoxol=1g: 8ml adds;
(3) under ultrasonic-microwave combination condition, carry out DeR, ultrasonic power is 100W, and microwave power is 530W, and the ultrasonic-microwave combined action time is 3min.
(4) be that 4%KOH solution regulates pH to neutral by the solution mass concentration after DeR, centrifugation, it is 100% ethanolic soln precipitation that its parting liquid adds purity, centrifugation again, after separation be deposited in 0 DEG C at vacuum-drying, namely obtain chitosan oligomer, its molecular weight is 2637.6.
Prepare water soluble oligosaccharide with the method for embodiment 5, and by the method precipitated step by step, separation detection carried out to product, obtain the relation of chitosan oligomer molecular weight of product and distribution, as table 1:
Table 1
As shown in Table 1, through certain hour, reaction solution, after centrifugation drying treatment, is weighed, and fourth stage molecular weight distribution ratio is 89.71%, and average average molecular weight is about 2350.
Claims (4)
1. fast degradation prepares a method for water soluble oligo-chitosan, it is characterized in that, comprises the steps:
(1) prepare chitosan solution, the concentration of described chitosan solution is 10 ~ 50g/L, is to add acetate dissolution again after being mixed with water by chitosan;
(2) superoxol insulation is added to chitosan solution, described superoxol is in chitosan: the ratio of superoxol=1g: 1 ~ 10ml adds, described holding temperature is 30 ~ 70 DEG C, soaking time 1 ~ 60min, and the mass concentration of described superoxol is 0.5 ~ 15%;
(3) under ultrasonic-microwave combined action condition, carry out DeR, ultrasonic power is 10 ~ 100W, and microwave power is 160 ~ 640W, and the combined action time is 1 ~ 10min;
(4) alkaline solution of the solution after DeR regulates pH to neutral, after separation, drying, namely obtain chitosan oligomer.
2. fast degradation according to claim 1 prepares the method for water soluble oligo-chitosan, it is characterized in that: described alkaline solution is NaOH, ammoniacal liquor or KOH.
3. fast degradation according to claim 1 and 2 prepares the method for water soluble oligo-chitosan, it is characterized in that: described separation, dry operation steps: be that the reaction soln after adjusting neutrality is carried out centrifugation, its parting liquid adds ethanolic soln precipitation, centrifugation again, after separation be deposited in-50 ~ 20 DEG C at vacuum-drying, namely obtain chitosan oligomer.
4. fast degradation according to claim 3 prepares the method for water soluble oligo-chitosan, it is characterized in that: described ethanolic soln purity is 50 ~ 100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310251346.4A CN103360514B (en) | 2013-06-24 | 2013-06-24 | A kind of fast degradation prepares the method for water soluble oligo-chitosan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310251346.4A CN103360514B (en) | 2013-06-24 | 2013-06-24 | A kind of fast degradation prepares the method for water soluble oligo-chitosan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103360514A CN103360514A (en) | 2013-10-23 |
| CN103360514B true CN103360514B (en) | 2015-08-26 |
Family
ID=49362838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310251346.4A Expired - Fee Related CN103360514B (en) | 2013-06-24 | 2013-06-24 | A kind of fast degradation prepares the method for water soluble oligo-chitosan |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103360514B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131149A (en) * | 2015-08-13 | 2015-12-09 | 江苏大学 | Method for preparing narrow molecular weight distribution oligochitosan through ultrasonic/microwave combination |
| CN105442353B (en) * | 2015-12-28 | 2018-02-27 | 中国纺织科学研究院江南分院 | A kind of method of modifying and its dyeing of salt-free low alkali deep dye type cellulose base fiber fabric |
| CN107033308B (en) * | 2017-06-09 | 2019-03-19 | 金陵科技学院 | A method of biology base efficient retarding and water reducing agent is prepared using natural chitin |
| CN107601945B (en) * | 2017-09-04 | 2020-03-31 | 金陵科技学院 | Preparation method of carboxyl-containing modified chitin bio-based retarding superplasticizer |
| CN109456421A (en) * | 2018-10-30 | 2019-03-12 | 江南大学 | A kind of preparation of water soluble chitosan material and application method |
| CN109627355A (en) * | 2018-12-05 | 2019-04-16 | 华南理工大学 | A kind of method that ionic liquid degradation chitosan prepares Water soluble oligo chitosan |
| CN109609571A (en) * | 2018-12-21 | 2019-04-12 | 青岛颂田生物技术有限公司 | A kind of preparation method of anacidity chitosan oligosaccharide |
| CN110699386B (en) * | 2019-10-09 | 2023-01-20 | 徐州生物工程职业技术学院 | Process for producing alcohol by using chitin as basic raw material |
| CN113292060B (en) * | 2021-05-23 | 2022-04-29 | 贵州大学 | Preparation method for preparing shell oligosaccharide-based in-situ N-doped ordered mesoporous carbon by soft template method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2969431B2 (en) * | 1995-07-24 | 1999-11-02 | キトサン食品工業株式会社 | Method for producing low molecular weight chitosan and chitooligosaccharide |
| CN1281670C (en) * | 2003-11-27 | 2006-10-25 | 浙江大学 | Chemical modulatory agent for harnessing soil pollution and its preparing method |
| CN102321194B (en) * | 2011-08-12 | 2013-07-17 | 厦门蓝湾科技有限公司 | Method for preparing water-soluble chitosan with low molecular weight |
| CN103044574B (en) * | 2013-01-11 | 2015-05-06 | 河北工业大学 | Process for preparing narrow-distribution chitosan with controllable molecular weight through microwave-H2O2 combined degradation method |
-
2013
- 2013-06-24 CN CN201310251346.4A patent/CN103360514B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103360514A (en) | 2013-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103360514B (en) | A kind of fast degradation prepares the method for water soluble oligo-chitosan | |
| Huang et al. | Preparation, deproteinization and comparison of bioactive polysaccharides | |
| CN101985639B (en) | Application of alpha-L-rhamnoside enzyme in directional synthesis of isoquercitrin by biological conversion of rutin | |
| CN101463373B (en) | Preparation of high-purity immunological activity yeast beta-1,3-dextran with immunological activity | |
| CN101423855B (en) | Method for preparing polysaccharide by using lucidum strain fermented laminaria leftover | |
| CN103266154A (en) | Biological transformation method for preparing high-activity theasaponin | |
| CN102617751A (en) | Method for preparing pectin oligosaccharide (POS) through dynamic high-pressure microfluidization (DHPM) combined acid process | |
| CN102676614A (en) | Method for preparing galacto-oligosaccharide | |
| CN104745656B (en) | A kind of method that the Portugal's oligosaccharides of β 1,3 is directly produced using curdlan fermentation liquid | |
| CN102250981B (en) | Method for preparing ellagic acid by solid fermentation with granatum as raw material | |
| CN101215593B (en) | Technique for preparing oligomeric chitosan by complex enzyme degradation | |
| CN107189949A (en) | Rhizopus oryzae LJH3 and the application in bioconversion Sophoricoside prepares genistein | |
| CN103436573A (en) | Production method of biocatalytic efficient agricultural chitosan oligosaccharide | |
| CN101857890A (en) | Method for biologically converting stevioside in stevia sugar into rebaudioside | |
| CN103146784A (en) | Method for preparing chitosan oligosaccharide through degradation of chitosan by thermobifida fusca internally tangent beta-1, 4-glucanase | |
| CN102212595B (en) | Preparation method and application of water-soluble nano grain polysaccharide | |
| CN104388502A (en) | Method for preparing rice bran bioactive peptide through solid-state fermentation of mixed bacteria species | |
| CN112575050A (en) | Method for preparing diosgenin by biological conversion | |
| CN104800110B (en) | A kind of method that microbial fermentation prepares total saponin of sapindusmukerossi | |
| CN108239177A (en) | A kind of method that purifying prepares high-quality biological polysaccharide | |
| CN102676611A (en) | Process method for producing medicinal specific molecular mass glucomannan by using fresh konjac | |
| CN102703562A (en) | Method for prompting extraction of linaloe oil by utilizing flora fermentation | |
| CN102533565B (en) | Aspergillus niger capable of producing glycosidase and application thereof in improving resveratrol content in Japanese knotweed | |
| CN106834407B (en) | Method for green production of diosgenin by biological method | |
| CN101828628A (en) | Biological treatment method for effectively extracting rapeseed protein |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150826 Termination date: 20190624 |