CN102702386A - Method for degrading chitosan - Google Patents
Method for degrading chitosan Download PDFInfo
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- CN102702386A CN102702386A CN2012101971070A CN201210197107A CN102702386A CN 102702386 A CN102702386 A CN 102702386A CN 2012101971070 A CN2012101971070 A CN 2012101971070A CN 201210197107 A CN201210197107 A CN 201210197107A CN 102702386 A CN102702386 A CN 102702386A
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Abstract
The invention belongs to the marine chemistry engineering technology, and in particular relates to a method for degrading chitosan by hydrogen peroxide with the help of microwave temperature control, comprising the following steps: dissolving high molecular weight chitosan with dilute acid to obtain a chitosan solution; adding hydrogen peroxide in the chitosan solution for reaction under microwave; and heating the obtained solution and controlling the reaction temperature under microwave to obtain chitosan of different molecular weights at different degradation time. Compared with the conventional way of degrading chitosan by heating the hydrogen peroxide, hydrogen peroxide of a lower concentration is required at the same temperature, a low molecular weight chitosan can be obtained in less time, and the basic chemical structure of the obtained low molecular weight chitosan is basically the same as that of the initial chitosan raw material.
Description
Technical field
The invention belongs to the thalassochemistry engineering, be specifically related to the auxiliary hydrogen peroxide degradation methods of chitosan of a kind of microwave temperature control.
Background technology
Chitosan is a natural linear polysaccharide, is formed by connecting through β-1,4 glycosidic link by GS and acetylglucosamine.Because chitosan source is abundant, and safety non-toxic has good bio-compatibility, with human body cell good consistency arranged, at food medicine, and agricultural, material science has very big application potential.Low-molecular weight chitoglycan and oligochitosan are the degraded products of chitosan.Compare with chitosan, low-molecular-weight chitosan and oligochitosan are water-soluble to be improved greatly, and this helps organism and utilization.Low-molecular-weight chitosan and shell widow come to light and have multiple physiologically active, and be antibiotic as antitumor, and anti-inflammatory is anti-oxidant, blood sugar regulation blood fat, strengthening immunity, activation intestinal microflora etc.
At present, the preparation method of low-molecular weight chitoglycan mainly contains acidolysis, enzymolysis, oxidative degradation etc.Use a large amount of volatile strong acid in the acidolysis, it need use strong corrosion resistant property equipment, causes environmental pollution, and degraded product is inhomogeneous.Enzymatic hydrolysis condition gentleness but cost is very high.Oxidation degradation method is the method for a kind of low cost and environmental protection, yet uses its degradation rate of hydrogen peroxide degradation chitosan slow separately, and the use of high-strength hydrogen peroxide may bring the destruction of chitosan structure.Therefore improve the degradation rate of hydrogen peroxide through other means, to avoid degradation process be very significant to the destruction of chitosan structure thereby relax degradation condition.
Summary of the invention
The purpose of this invention is to provide the auxiliary hydrogen peroxide degradation methods of chitosan of a kind of microwave temperature control.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is:
A kind of method of degrade chitosan, with high molecular weight chitosan through diluted acid dissolve chitosan solution, add ydrogen peroxide 50 in the chitosan solution and under microwave, react, microwave time heats control reaction temperature, gets the chitosan of different molecular weight according to different degradation times.
Add ydrogen peroxide 50 in the said chitosan solution and under microwave, react, after reaction back solution is neutralized to neutrality with alkali lye, alcohol precipitation, centrifugal back collecting precipitation, lyophilize promptly obtains the chitosan and the oligochitosan of different molecular weight.
Said high molecular weight chitosan dissolves through diluted acid, is high molecular weight chitosan is dissolved in the rare mineral acid or organic acid, and gained chitosan solution concentration is 1%-3% (massfraction), and used acid is hydrochloric acid, formic acid, acetate, oxalic acid, lactic acid.
The add-on of said ydrogen peroxide 50 is the 0.01%-1% (volume(tric)fraction) of chitosan solution.Add ydrogen peroxide 50 in the said chitosan solution under microwave, 40-90 ℃ of heating control reaction temperature degraded 5-180min, getting molecular weight is chitosan and the oligochitosan of 500-100000Da.
Reaction principle: hydrogen peroxide can dissociate hydroxy radical qiao and superoxide radical, and it is sugar chain degraded that these radicals can be attacked glycosidic link, yet degraded can follow some side reactions such as some oxidations to destroy sugared ring structure under high temperature and high hydrogen peroxide concentration.Under microwave condition,, microwave promotes degradation rate greatly thereby can reducing reaction activity.The physical wavelength radiation can promote dissociating of ydrogen peroxide 50, and then improves the utilization ratio of ydrogen peroxide 50, reduces the working concentration of ydrogen peroxide 50 greatly.In addition, come control reaction temperature, also can reduce the generation of side reaction through the inner type of heating of microwave.So, adopt the auxiliary hydrogen peroxide mode of microwave temperature control, thus degrade chitosan and relax the substruction that degradation condition is protected sugar chain fast.
Advantage of the present invention
1. the present invention adopts microwave-assisted hydrogen peroxide degradation chitosan, and speed of reaction improves greatly, and reaction is quick, and required time is short, effectively improves reaction conditions.
2. adopt the microwave reaction workstation; Compare with traditional heating; Used hydrogen peroxide concentration is low under the identical situation of temperature; Action time, weak point just can obtain low-molecular weight chitoglycan, made the oxidative degradation of chitosan under the demulcent condition, carry out, and resulting low-molecular weight chitoglycan and oligochitosan chemical structure are not destroyed basically.
Description of drawings
The concentration of hydrogen peroxide that Fig. 1 provides for instance of the present invention is to the influence of degradation of chitosan under microwave-assisted (■) and two kinds of patterns of traditional heating (●).
The gel exclusion chromatography collection of illustrative plates of the low-molecular weight chitoglycan that the microwave-assisted hydrogen peroxide degradation of chitosan that Fig. 2 provides for the embodiment of the invention prepares; Wherein, Fig. 2 A 658kDa spectrogram is for using the gel exclusion chromatography figure of chitosan raw material; Fig. 2 B, C and D 41.2kDa, 9.0kDa, 5.5kDa spectrogram are respectively the gel exclusion collection of illustrative plates of the low-molecular weight chitoglycan that obtains among the embodiment 2-4.
The infrared spectrogram of the low-molecular weight chitoglycan that the microwave-assisted hydrogen peroxide degradation of chitosan that Fig. 3 provides for the embodiment of the invention prepares; 658kDa mark spectrogram is for using the infrared spectrogram of chitosan raw material; 41.2kDa; 9.0kDa 5.5kDa mark spectrogram is respectively the infrared spectrogram of the low-molecular weight chitoglycan that obtains among the embodiment 2-4.
Embodiment
Below in conjunction with Figure of description the present invention is described further, and protection scope of the present invention not only is confined to following examples.
High molecular weight chitosan (658kDa) 2g is dissolved in 100ml 2% (massfraction) acetic acid gets chitosan solution; The ydrogen peroxide 50 that in chitosan solution, adds a certain amount of (accounting for the volume(tric)fraction of chitosan solution by ydrogen peroxide 50); Its ydrogen peroxide 50 ultimate density is as shown in Figure 1, adopts traditional heating and two kinds of patterns of microwave heating to carry out the degraded of chitosan, and control reaction temperature is 70 ℃; Degraded 20min; Wherein adopting microwave power in the microwave mode is 600W, utilizes gel exclusion chromatography to measure its molecular weight resulting low-molecular weight chitoglycan after the reaction, as shown in Figure 1; Under the temperature condition identical with degradation time, the needed concentration of hydrogen peroxide of chitosan microwave-assisted pattern that degraded obtains similar molecular weight will be starkly lower than the traditional heating pattern.
High molecular weight chitosan (658kDa) 2g is dissolved in 100ml 1% (massfraction) hydrochloric acid gets chitosan solution, in chitosan solution, add 1ml 30% ydrogen peroxide 50, at microwave power 600W; Control reaction temperature is 70 ℃; Degraded 10min, after solution is neutralized to neutrality with alkali lye after will reacting, alcohol precipitation; Centrifugal back collecting precipitation, lyophilize promptly obtains low-molecular-weight chitosan.It is 41.2kDa (shown in Fig. 2 B) that resulting product utilization gel exclusion chromatography is measured its molecular weight, and the ir spectra of degraded product compares (shown in Figure 3) with the ir spectra of initial chitosan raw material, finds the charateristic avsorption band 1643cm of raw materials of chitosan
-1(acid amides I), 1558cm
-1(acid amides II), 1322cm
-1(acid amides III), 1158895cm
-1(charateristic avsorption band of the basic framework of sugar ring) still exists after degraded, explains that the substruction of degraded back chitosan is not destroyed.In addition in the infrared spectrum of the low-molecular weight chitoglycan after degraded at 1735cm
-1Do not have charateristic avsorption band, explaining on the degraded back cover polysaccharide chains does not have oxidized carboxyl to occur.
Embodiment 3
High molecular weight chitosan (658kDa) 2g is dissolved in 100ml 1% (massfraction) acetic acid gets chitosan solution, in chitosan solution, add 1ml 30% ydrogen peroxide 50, at microwave power 600W; Control reaction temperature is 70 ℃; Degraded 30min, after solution is neutralized to neutrality with alkali lye after will reacting, alcohol precipitation; Centrifugal back collecting precipitation, lyophilize promptly obtains low-molecular-weight chitosan.It is 9.0kDa (shown in Fig. 2 C) that resulting product utilization gel exclusion chromatography is measured its molecular weight, and the ir spectra of degraded product compares (shown in Figure 3) with the ir spectra of initial chitosan raw material, finds the charateristic avsorption band 1643cm of raw materials of chitosan
-1(acid amides I), 1558cm
-1(acid amides II), 1322cm
-1(acid amides III), 1158895cm
-1(charateristic avsorption band of the basic framework of sugar ring) still exists after degraded, explains that the substruction of degraded back chitosan is not destroyed.In addition in the infrared spectrum of the low-molecular weight chitoglycan after degraded at 1735cm
-1Do not have charateristic avsorption band, explaining on the degraded back cover polysaccharide chains does not have oxidized carboxyl to occur.
High molecular weight chitosan (658kDa) 2g is dissolved in 100ml 2% (massfraction) hydrochloric acid gets chitosan solution, in chitosan solution, add 1ml 30% ydrogen peroxide 50, at microwave power 600W; Control reaction temperature is 70 ℃; Degraded 40min, after solution is neutralized to neutrality with alkali lye after will reacting, alcohol precipitation; Centrifugal back collecting precipitation, lyophilize promptly obtains low-molecular-weight chitosan.It is 5.5kDa (shown in Fig. 2 D) that resulting product utilization gel exclusion chromatography is measured its molecular weight, and the ir spectra of degraded product compares (shown in Figure 3) with the ir spectra of initial chitosan raw material, finds the charateristic avsorption band 1643cm of raw materials of chitosan
-1(acid amides I), 1558cm
-1(acid amides II), 1322cm
-1(acid amides III), 1158895cm
-1(charateristic avsorption band of the basic framework of sugar ring) still exists after degraded, explains that the substruction of degraded back chitosan is not destroyed.In addition in the infrared spectrum of the low-molecular weight chitoglycan after degraded at 1735cm
-1Do not have charateristic avsorption band, explaining on the degraded back cover polysaccharide chains does not have oxidized carboxyl to occur.
Claims (5)
1. the method for a degrade chitosan; It is characterized in that: with high molecular weight chitosan through diluted acid dissolve chitosan solution; Add ydrogen peroxide 50 in the chitosan solution and under microwave, react, microwave is the heating control reaction temperature down, gets the chitosan of different molecular weight according to different degradation times.
2. according to the method for the described degrade chitosan of claim 1; It is characterized in that: add ydrogen peroxide 50 in the said chitosan solution and under microwave, react; After reaction back solution is neutralized to neutrality with alkali lye; Alcohol precipitation, centrifugal back collecting precipitation, lyophilize promptly obtains the chitosan and the oligochitosan of different molecular weight.
3. according to the method for claim 1 or 2 described degrade chitosans, it is characterized in that: said high molecular weight chitosan dissolves through diluted acid, is high molecular weight chitosan is dissolved in the rare mineral acid or organic acid, and gained chitosan solution concentration is 1%-3%.
4. according to the method for the described degrade chitosan of claim 1, it is characterized in that: the add-on of said ydrogen peroxide 50 is the 0.01%-1% of chitosan solution.
5. according to the method for the described degrade chitosan of claim 1; It is characterized in that: add ydrogen peroxide 50 in the said chitosan solution under microwave; 40-90 ℃ of heating control reaction temperature degraded 5-180min, getting molecular weight is chitosan and the oligochitosan of 500-100000Da.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044574A (en) * | 2013-01-11 | 2013-04-17 | 河北工业大学 | Process for preparing narrow-distribution chitosan with controllable molecular weight through microwave-H2O2 combined degradation method |
| CN104098715A (en) * | 2014-07-16 | 2014-10-15 | 中国科学院海洋研究所 | Method for degrading chitosan through microwave-enzyme method coupling |
| CN104629099A (en) * | 2015-03-06 | 2015-05-20 | 中国科学院海洋研究所 | Method for rapidly preparing ultrahigh-concentration chitosan solution |
| CN105949350A (en) * | 2016-06-14 | 2016-09-21 | 王斐芬 | Chitosan oligosaccharide preparation method |
| CN107177648A (en) * | 2017-06-30 | 2017-09-19 | 赵景卫 | A kind of chitosan oligosaccharide enzymatic production process |
| CN109400948A (en) * | 2018-09-10 | 2019-03-01 | 中国科学院金属研究所 | A kind of method that microwave process reinforcing prepares different deacetylations and degree of polymerization series chitooligosaccharide- |
| CN109503731A (en) * | 2018-11-22 | 2019-03-22 | 贵州省现代农业发展研究所 | A method of using the hydrolysis of irradiation assisted microwave synthesis hot acid while preparing low-molecular weight chitoglycan and D- aminoglucose sulfate |
| CN112626147A (en) * | 2021-01-12 | 2021-04-09 | 中国科学院海洋研究所 | Preparation method of chitosan oligosaccharide salt |
| CN113637096A (en) * | 2021-09-15 | 2021-11-12 | 吴洪德 | Preparation method of chitosan oligosaccharide, chitosan oligosaccharide and chitosan oligosaccharide health-care product |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044574A (en) * | 2013-01-11 | 2013-04-17 | 河北工业大学 | Process for preparing narrow-distribution chitosan with controllable molecular weight through microwave-H2O2 combined degradation method |
| CN104098715A (en) * | 2014-07-16 | 2014-10-15 | 中国科学院海洋研究所 | Method for degrading chitosan through microwave-enzyme method coupling |
| CN104098715B (en) * | 2014-07-16 | 2016-07-06 | 中国科学院海洋研究所 | A kind of method of microwave-enzyme method coupling degraded chitosan |
| CN104629099A (en) * | 2015-03-06 | 2015-05-20 | 中国科学院海洋研究所 | Method for rapidly preparing ultrahigh-concentration chitosan solution |
| CN105949350A (en) * | 2016-06-14 | 2016-09-21 | 王斐芬 | Chitosan oligosaccharide preparation method |
| CN107177648A (en) * | 2017-06-30 | 2017-09-19 | 赵景卫 | A kind of chitosan oligosaccharide enzymatic production process |
| CN109400948A (en) * | 2018-09-10 | 2019-03-01 | 中国科学院金属研究所 | A kind of method that microwave process reinforcing prepares different deacetylations and degree of polymerization series chitooligosaccharide- |
| CN109400948B (en) * | 2018-09-10 | 2021-05-28 | 中国科学院金属研究所 | Method for preparing chitosan oligosaccharides with different deacetylation degrees and polymerization degrees in enhanced microwave process |
| CN109503731A (en) * | 2018-11-22 | 2019-03-22 | 贵州省现代农业发展研究所 | A method of using the hydrolysis of irradiation assisted microwave synthesis hot acid while preparing low-molecular weight chitoglycan and D- aminoglucose sulfate |
| CN112626147A (en) * | 2021-01-12 | 2021-04-09 | 中国科学院海洋研究所 | Preparation method of chitosan oligosaccharide salt |
| CN113637096A (en) * | 2021-09-15 | 2021-11-12 | 吴洪德 | Preparation method of chitosan oligosaccharide, chitosan oligosaccharide and chitosan oligosaccharide health-care product |
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Application publication date: 20121003 |