CN103360514A - Method for preparing water-soluble chitosan oligosaccharide by quick degradation - Google Patents
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Abstract
The invention discloses a method for preparing water-soluble chitosan oligosaccharide by quick degradation, which comprises the following steps: (1) preparing a chitosan solution; (2) adding a hydrogen peroxide solution into a chitosan solution, and keeping the temperature; (3) carrying out degradation reaction under the ultrasonic-microwave combined action for 1-10 minutes, wherein the ultrasonic power is 10-100 W, and the microwave power is 160-640 W; and (4) regulating the pH value of the solution after degradation reaction with an alkali solution to a neutral state, separating and drying to obtain the chitosan oligosaccharide. The microwave-ultrasonic combination and hydrogen peroxide oxidation alternately act on the chitosan to prepare the water-soluble chitosan oligosaccharide; and thus, the invention has the advantages of high preparation speed, easy separation and purification, environment-friendly technical process, uniform relative molecular mass distribution of the product, and the like.
Description
Technical field
The invention belongs to the method for water soluble oligo-chitosan, relate in particular to a kind of microwave-ultrasonic associating and hydrogen peroxide oxidation alternating action of utilizing, fast degradation prepares the method for water soluble oligo-chitosan.
Background technology
Chitin is the nitrogenous natural organic high-molecular compound of the outer quantity maximum of nature isolating protein, is only second to Mierocrystalline cellulose about 10,000,000,000 tons by biosynthetic chitin of every year, is second largest renewable resources on the earth.Chitosan is obtained through deacetylation partially or completely by chitin, and chemistry (Isosorbide-5-Nitrae)-2-amino by name-2-deoxidation-β-D-Glucose connects with β-(Isosorbide-5-Nitrae) glycosidic link between the molecule.Chitin and chitosan is because the interaction of inside and outside hydrogen bond in its molecular structure has formed orderly macromolecular structure, and relative molecular mass is usually extremely millions of at hundreds of thousands of, the water insoluble common solvent that waits, and application is extremely restricted.
Compare with degrade chitosan not through reaching than the chitosan oligomer of small molecular weight (800-10000) scope after the degraded, its molecular weight reduces, destroyed the reticulated structure of some molecules, so that the compactness of its crystalline structure significantly reduces, solvability strengthens greatly, biological activity, coordination ability obviously improves, not only kept not some functional property that has of degrade chitosan, such as reducing cholesterol, hypotensive blood fat, prevent and treat diabetes, strengthen the liver function, treatment is burnt, scald etc., and the chitosan oligomer of different molecular weight ranges also has the not available physiologically active of many not degrade chitosans and functional property, such as humidity-preserving type, immunomodulatory, anti-cancer, the regulating intestinal canal flora, functional sweetener, as the nutritional fortification agent carrier, get rid of hazardous and noxious substances in the body, antibiotic anticorrosion, inducing plant produces toxinicide etc. many effects.Therefore, the preparation and application of chitosan oligomer have become the focus of domestic and international research.
At present, the preparation of chitosan oligomer mainly contains three kinds of methods: chemical degradation method, enzyme liberating method and mechanical degradation method.The composite degradation method is a newer research field at present.
One, chemical degradation method: refer to make degradation of chitosan by chemical reaction, acid degradation method and oxidation degradation method are arranged, wherein H
2O
2The existing lot of documents report of oxidation style, and for the production of.The open source literature relevant with 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 the Hydrodynamic cavitation effect of chitosan solution own chitosan is degraded to make chitosan oligomer, comprising: add alkaline solution in the chitosan solution after chitosan dissolving, Hydrodynamic cavitation are degraded, finished to degraded and regulate pH and the steps such as throw out washing and vacuum-drying; The technical process of described Hydrodynamic cavitation degraded is: chitosan solution is placed in the basin, and carry out constant temperature by cyclic water tank, chitosan solution carries out the cavitation degraded by pump delivery to cavitation device, by valve V1, V2, V3, V4 regulates upstream inlet pressure, pressure and flow are recovered in the downstream, and by tensimeter and under meter monitor force and flow, solution after the cavitation degraded is back in the basin, by cyclic water tank temperature is controlled at 25-80 ℃, carry out circular treatment 0.5h-20h until reach required relative molecular mass requirement and be as the criterion in the Hydrodynamic cavitation device, the method has simple and easy to do, energy consumption is low, the efficient 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 the fine chemical technology field; It is characterized in that relating to the method for producing chitosan oligomer (oligochitosan) with hydrogen peroxide as oxygenant oxidation chitosan.Its chitosan mass mark is 5%～35%, when reaching reaction end, and n (hydrogen peroxide): n (chitosan)=1.3～5.5, temperature of reaction is 50 ℃～90 ℃.Reaction solution is cooled to 0 ℃～10 ℃, is that 95% ethanol is separated out with-30 ℃～0 ℃ volume fraction, w (ethanol): w (reaction solution)=1～4.Filter cake is 99% washing with alcohol 1～5 time with-30 ℃～10 ℃ volume fractions, then 40 ℃～60 ℃ oven dry 2h～8h.Effect of the present invention and benefit are that the chitosan oligomer molecular weight is low, and solubleness is up to 80g/100g water.Degraded is carried out in neutral medium, and product does not contain inorganic salts.Add reducing substance in the reaction solution, can eliminate remaining superoxide fully.Production is without the three wastes, and product yield is high, and biological activity is high, and color and luster improves, and belongs to non-poisonous material through toxicology test.Under neutrallty condition, adopt H
2O
2Solution carries out oxidative degradation to chitosan, but is subject to different concentration of hydrogen peroxide, proportioning, temperature and reaction times to the impact of DeR, and preparation process is complicated, and the reaction times is long, and process is difficult to control, has greatly affected production efficiency.
Two, enzyme liberating method: be to utilize enzymatic hydrolysis, be divided into specificity enzyme liberating method and non-specific enzyme liberating method.The enzyme liberating method have reaction conditions gentleness, whole degradation process without other reaction reagents add, be unlikely to occur other side reaction, degradation process and degraded product relative molecular mass distribute be easy to control, chitosan oligomer yield high, do not cause the advantage such as environmental pollution.The open source literature relevant with the 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 and a kind ofly obtain chitoanase and produce chitosan oligomer (or claiming amino-oligosaccharide with microorganism culturing, the shell oligosaccharide) method, described microorganism is the genus bacillus that obtains from the seabeach, inducing the method for producing enzymic fermentation behind the acquisition bacterial classification is to add an amount of chitosan and nitrogenous source, in the solution of inorganic nutrient salt, cultivate at normal temperatures and can obtain having highly active chitosanase preparation in 30-40 hour, the method that enzymolysis produces sugar is with enzyme liquid and chitosan solution mixing by a certain percentage, under very gentle condition, carry out enzyme digestion reaction, (4-12 hour) can be converted into chitosan oligomer with chitosan in short period of time, and concentrated or drying obtains product.The bacterial classification genetic stability of the method, zymogenic rate is high, the 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; Utilizing different types of non-specific enzyme is α-amylase and bromeline, or cellulase, and the synergy that produces in the degrade chitosan process improves degradation efficiency, and the molecular-weight average degraded of product is reached about 1500Da.Last degraded product process micro-filtration and nanofiltration purifying, concentrated and spraying drying can obtain high-quality oligopolymerization chitosan sugar product.Compare with traditional preparation technology, this technique not only Product Activity is high, superior in quality, easy to operate, and has improved production environment, is conducive to realize 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 operately, speed is fast, no coupling product, and the advantages such as non-environmental-pollution, the open source literature relevant with Physical is as follows:
1. application number: 200810156803.0, denomination of invention: the preparation method of chitosan oligomer, summary: the preparation method who the invention discloses a kind of chitosan oligomer, macromole chitosan raw material → adding degraded sensitizing agent mixing → irradiation → spraying drying → aqua product → concentrated → spraying drying → powder product, have quick, easy, high yield, low cost, effectively product content high, not to advantages such as environments, extremely be conducive to large-scale industrial production.
2. Li Jun is vertical, Zhang Bo, horsepower. the ultrasonic degradation of chitosan and optimised process research. Xihua Univ's journal (natural science edition) .2011,30(5): 100-103. is take natural macromolecular amount chitosan as raw material, utilizes single sonication to prepare chitosan oligomer, has simple to operate, with low cost, product is simple, and is pollution-free, easily extracts the advantages such as recovery.
But there are the problems such as the control of chitosan oligomer degradation process and molecular weight distribution in these two kinds of methods, and its relative molecular mass is higher.
Four, composite degradation method: i.e. being used in combination 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; Adopt cellulase in conjunction with the method for hydrogen peroxide the chitosan of high-polymerization degree to be degraded.In cellulose degraded, chitosan (g): cellulase A (g)=10: 1～0.8; The temperature of reaction of cellulase is 55～60 ℃; Reaction times is 1.5～2.0h.In the hydrogen peroxide oxidation degraded, the hydrogen peroxide consumption is: chitosan (g): 30% hydrogen peroxide (mL)=1: 1.0～0.8, the concentration of hydrogen peroxide are mass percent; The hydroperoxidation temperature is 75～80 ℃; Reaction times is 1～2.5h.After passing through micro-filtration, nanofiltration and drying, the molecular weight of gained oligopolymerization chitosan sugar product is low again, distributes single.This technique is simple, operation is convenient, is suitable for scale operation.
2. application number: 200810218806.2, denomination of invention: the method that under steady magnetic field condition, prepares chitosan oligomer, summary: the invention discloses the method for 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 for realizing that serialization production provides theoretical foundation, can be convenient to the recovery of enzyme, the utilization ratio of raising immobilized enzyme simultaneously, reduces cost.
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. adopts microwave radiation and rare earth coordination control combination technology to prepare chitosan oligomer take the industrial goods high molecular weight chitosan as raw material, the relative molecular mass of products obtained therefrom is more evenly distributed, and the speed of degraded significantly improves.
Summary of the invention
The object of the invention is to solve the problems such as prior art process poor controllability, consuming time, power consumption, product subsequent disposal complexity, product relative molecular mass skewness, provide a kind of fast degradation to prepare the method for water soluble oligo-chitosan, by utilizing microwave-ultrasonic associating and hydrogen peroxide oxidation alternating action to prepare water soluble oligo-chitosan in chitosan, have the advantages such as quick preparation, easily separated purifying, technological process environmental protection, product relative molecular mass are evenly distributed.
For achieving the above object, the invention provides following technical scheme:
A kind of fast degradation prepares the method for water soluble oligo-chitosan, comprises the steps:
(1) preparation chitosan solution;
(2) add the superoxol insulation to chitosan solution;
(3) carry out DeR under ultrasonic-microwave combined action condition, ultrasonic power is 10～100W, and microwave power is 160～640W, and the combined action time is 1～10min;
(4) solution after the DeR is regulated pH to neutral with alkaline solution, namely obtains chitosan oligomer after separation, drying, and the molecular weight of gained chitosan oligomer is 800～8000.
As further instruction, the above superoxol adds in the ratio of chitosan: superoxol=1g: 1～10ml.
As further instruction, the above holding temperature is 30～70 ℃, 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, be with chitosan with add again acetate dissolution after water mixes.
As further instruction, the above alkaline solution is NaOH, ammoniacal liquor or KOH.
As further instruction, the above separates, the operation steps of drying: be that the reaction soln after the accent neutrality is carried out centrifugation, its parting liquid adds ethanolic soln precipitation, again centrifugation, being deposited in after the separation-50～20 ℃ lower vacuum-drying namely obtains 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, the principle of utilizing the macromole chitosan to be insoluble to neutrality or alkaline aqueous solution is separated out macromole, centrifugal removal, product is carried out vacuum lyophilization obtain finished product, material of the present invention is cheap and easy to get, and production process is simple to operate, and the production technique feasibility is high, the quality product that obtains is good, relative molecular mass is evenly distributed, and is fully water-soluble, and solubleness is 100%, subsequent disposal is simple, has certain application and promotional value.
(2) adopt the ultrasonic-microwave combined action, with respect to single ultrasonic wave or single microwave, have better synergistic function, greatly reduced the reaction times, separation purifying technique is simple, and the product water dissolubility is high.
Description of drawings
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 place shows stretching vibration absorption peak and the N-H stretching vibration that hydroxyl produces because of hydrogen bond action on the chitosan skeleton; 1642～1650cm
-1Stronger amino absorption peak appears in the scope; 1384cm
-1The place is C-CH
3The formation vibration peak at place; 1255cm
-1The place is the C-H vibration peak; 1078cm
-1Be C-O absorption peak, 1154cm
-1Be C-O-C stretching vibration absorption peak, 897cm
-1～890cm
-1Absorption peak caused by the furanose ring vibration, be the charateristic avsorption band of β in the chitosan skeleton (1 → 4) glycosidic link.
But after the degraded, the charateristic avsorption band in the chitosan molecule changes following characteristics, at 3367cm
-1～3381
-1Hydroxyl in the scope illustrates H because its stretching vibration absorption peak strength of hydrogen bond action changes
2O
2The OH that cracking goes out also can change into carbonyl to a part of hydroxyl oxygen.1642cm
-1～1650cm
-1The free amine group absorption peak strengthens, and illustrates to be accompanied by deacetylation in the degradation process; The C-CH at 1384cm-1 place
3Formation vibration peak and the 1255cm at place
-1Considerable change does not occur 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 has caused the fracture of β (1 → 4) glycosidic link.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to the scope that embodiment represents.
Embodiment 1:
A kind of fast degradation prepares the method for water soluble oligo-chitosan, comprises the steps:
(1) first with the macromole chitosan with add again the dissolving of 2% acetum after water mixes, obtain the chitosan solution that concentration is 10g/L;
(2) chitosan solution after the dissolving adds 10% superoxol insulation, and holding temperature is 30 ℃, soaking time 5min, and superoxol is by the ratio adding of chitosan: superoxol=1g: 1ml;
(3) carry out DeR under the ultrasonic-microwave combination condition, ultrasonic power is 10W, and microwave power is 160W, and the ultrasonic-microwave combined action time is 1min.
(4) be that 4%NaOH solution is regulated pH to neutral with the solution mass concentration after the DeR, centrifugation, it is 50% ethanolic soln precipitation that its parting liquid adds purity, again centrifugation, be deposited in 20 ℃ of lower vacuum-dryings after the separation, namely obtain chitosan oligomer, its molecular weight is 8963.2.
Embodiment 2:
A kind of fast degradation prepares the method for water soluble oligo-chitosan, comprises the steps:
(1) first with the macromole chitosan with add again the dissolving of 2% acetum after water mixes, obtain the chitosan solution that concentration is 50g/L;
(2) chitosan solution after the dissolving adds 2% superoxol insulation, and holding temperature is 70 ℃, soaking time 60min, and superoxol is by the ratio adding of chitosan: superoxol=1g: 10ml;
(3) carry out DeR under the ultrasonic-microwave combination condition, ultrasonic power is 50W, and microwave power is 640W, and the ultrasonic-microwave combined action time is 10min.
(4) be that 4%NaOH solution is regulated pH to neutral with the solution mass concentration after the DeR, centrifugation, it is 100% ethanolic soln precipitation that its parting liquid adds purity, again centrifugation, being deposited in after the separation-50 ℃ lower vacuum-drying namely obtains chitosan oligomer, and its molecular weight is 1368.4.
Embodiment 3:
A kind of fast degradation prepares the method for water soluble oligo-chitosan, comprises the steps:
(1) first with the macromole chitosan with add again the dissolving of 2% acetum after water mixes, obtain the chitosan solution that concentration is 20g/L;
(2) chitosan solution after the dissolving adds 5% superoxol insulation, and holding temperature is 60 ℃, soaking time 5min, and superoxol is by the ratio adding of chitosan: superoxol=1g: 5ml;
(3) carry out DeR under the ultrasonic-microwave combination condition, ultrasonic power is 50W, and microwave power is 450W, and the ultrasonic-microwave combined action time is 8min.
(4) be that 4%NaOH solution is regulated pH to neutral with the solution mass concentration after step (3) DeR, centrifugation, it is 95% ethanolic soln precipitation that its parting liquid adds purity, again centrifugation, being deposited in after the separation-20 ℃ lower vacuum-drying, namely obtain chitosan oligomer, its molecular weight is 5912.9.
Embodiment 4:
A kind of fast degradation prepares the method for water soluble oligo-chitosan, comprises the steps:
(1) first with the macromole chitosan with add again the dissolving of 1% acetum after water mixes, obtain the chitosan solution that concentration is 30g/L;
(2) chitosan solution after the dissolving adds 8% superoxol insulation, and holding temperature is 40 ℃, soaking time 30min, and superoxol is by the ratio adding of chitosan: superoxol=1g: 2ml;
(3) carry out DeR under the ultrasonic-microwave combination condition, ultrasonic power is 50W, and microwave power is 360W, and the ultrasonic-microwave combined action time is 2min.
(4) be that 4%NaOH solution is regulated pH to neutral with the solution mass concentration after step (3) DeR, centrifugation, it is 85% ethanolic soln precipitation that its parting liquid adds purity, again centrifugation, be deposited in 0 ℃ of lower vacuum-drying after the separation, namely obtain chitosan oligomer, its molecular weight is 6249.6.
Embodiment 5:
A kind of fast degradation prepares the method for water soluble oligo-chitosan, comprises the steps:
(1) first with the macromole chitosan with add again the dissolving of 1% acetum after water mixes, obtain the chitosan solution that concentration is 40g/L;
(2) chitosan solution after the dissolving adds 15% superoxol insulation, and holding temperature is 70 ℃, soaking time 1min, and superoxol is by the ratio adding of chitosan: superoxol=1g: 8ml;
(3) carry out DeR under the ultrasonic-microwave combination condition, ultrasonic power is 100W, and microwave power is 530W, and the ultrasonic-microwave combined action time is 3min.
(4) be that 4%KOH solution is regulated pH to neutral with the solution mass concentration after the DeR, centrifugation, it is 100% ethanolic soln precipitation that its parting liquid adds purity, again centrifugation, be deposited in 0 ℃ of lower vacuum-drying after the separation, namely obtain chitosan oligomer, its molecular weight is 2637.6.
Method with embodiment 5 prepares water soluble oligosaccharide, and with the method for precipitation step by step product is carried out separation detection, obtains the relation of chitosan oligomer molecular weight of product and distribution, such as table 1:
Table 1
As shown in Table 1, through certain hour, reaction solution is weighed after the centrifugation drying treatment, and fourth stage molecular weight distribution ratio is 89.71%, and average average molecular weight is about 2350.
Claims (8)
1. a fast degradation prepares the method for water soluble oligo-chitosan, it is characterized in that, comprises the steps:
(1) preparation chitosan solution;
(2) add the superoxol insulation to chitosan solution;
(3) carry out DeR under ultrasonic-microwave combined action condition, ultrasonic power is 10 ~ 100W, and microwave power is 160 ~ 640W, and the combined action time is 1 ~ 10min;
(4) solution after the DeR is regulated pH to neutral with alkaline solution, namely obtains chitosan oligomer after separation, drying.
2. fast degradation according to claim 1 prepares the method for water soluble oligo-chitosan, it is characterized in that: described superoxol adds in the ratio of chitosan: superoxol=1g: 1 ~ 10ml.
3. fast degradation according to claim 1 and 2 prepares the method for water soluble oligo-chitosan, it is characterized in that: described holding temperature is 30 ~ 70 ℃, soaking time 1 ~ 60min.
4. fast degradation according to claim 3 prepares the method for water soluble oligo-chitosan, it is characterized in that: the mass concentration of described superoxol is 0.5 ~ 15%.
5. fast degradation according to claim 4 prepares the method for water soluble oligo-chitosan, it is characterized in that: the concentration of described chitosan solution is 10 ~ 50g/L, be with chitosan with add again acetate dissolution after water mixes.
6. fast degradation according to claim 4 prepares the method for water soluble oligo-chitosan, it is characterized in that: described alkaline solution is NaOH, ammoniacal liquor or KOH.
7. each described fast degradation prepares the method for water soluble oligo-chitosan according to claim 4-6, it is characterized in that: the operation steps of described separation, drying: be that the reaction soln after the accent neutrality is carried out centrifugation, its parting liquid adds the ethanolic soln precipitation, again centrifugation, being deposited in after the separation-50 ~ 20 ℃ lower vacuum-drying namely obtains chitosan oligomer.
8. fast degradation according to claim 7 prepares the method for water soluble oligo-chitosan, it is characterized in that: described ethanolic soln purity is 50 ~ 100%.
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| CN105131149A (en) * | 2015-08-13 | 2015-12-09 | 江苏大学 | Method for preparing narrow molecular weight distribution oligochitosan through ultrasonic/microwave combination |
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| 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 |
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| 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 |
| CN113292060A (en) * | 2021-05-23 | 2021-08-24 | 贵州大学 | Preparation method for preparing shell oligosaccharide-based in-situ N-doped ordered mesoporous carbon by soft template method |
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