CN101508790B - Method for preparing low-molecular weight chitosan by using impulse electric field - Google Patents
Method for preparing low-molecular weight chitosan by using impulse electric field Download PDFInfo
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Abstract
The invention discloses a method for preparing low-molecular weight chitosan by utilizing pulsed electric field. The method takes high-molecular weight chitosan with molecular weight more than 2.5*10<5>g/mol as the raw material and utilizes pulsed electric field to prepare low-molecular weight chitosan with low-molecular weight less than 2.3*10<4>g/mol. The method comprises the following steps: high-molecular weight chitosan dissolution, pulsed electric field treatment, lye pH adjustment, sedimentation, centrifugation, abstersion and drying, thus obtaining the low-molecular weight chitosan. The pulsed electric field treatment is to treat chitosan solution in a pulsed electric field processor; the electric field strength is 40 to 60kV/cm, the pulse width is 10 to 100mus, the pulse frequency is 100 to 1,000Hz, the pulse waveform is square wave and the period for treating chitosan in the pulsed electric field is 1 to 1,000ms. The preparation method provided by the invention has the advantages of simplicity and feasibility, short electric field treatment period, strong practicality, energy saving and environment protection and easy popularization.
Description
Technical field
The present invention relates to a kind of preparation method of low-molecular weight chitoglycan, particularly a kind of method that adopts high-strength pulsed electrical field Processing of Preparation low-molecular weight chitoglycan.
Background technology
Chitosan is a partly or entirely deacetylated product of chitin, and its molecular chain is by multipolymer that β-(1-4)-2-acetamido-D-glucose unit and β-(1-4)-2-amino-D-glucose unit is formed.Contain active amino in the chitosan molecule, amino can positively charged, is unique natural alkaline polysaccharide.Have activity hydroxy again on the sugar ring, thereby chitosan have good wetting ability and water-retentivity again.
Multiple bioactive functions such as that chitosan has is antibiotic, decreasing cholesterol, reducing blood-fat, raise immunity, anti-tumor function are widely used in industries such as food, biology, medical science, agricultural, environment, material.Chitosan is deacetylated to some extent by chitin, and molecular weight has inseparable getting in touch but modern study shows the molecular weight of chitosan with its purposes about 1,000,000 usually.The chitosan nature difference of different molecular weight is very big, and sometimes even show diametrically opposite characteristic, and many unique functions of above-mentioned chitosan only just show when its molecular mass is reduced to a certain degree.Therefore, degraded preparation chitosan oligomer becomes the focus of current research.At present, the main traditional method of degradation of chitosan comprises: chemical degradation method, enzyme liberating method and mechanical degradation method.The now disclosed physical technique about the preparation low-molecular weight chitoglycan mainly comprises: Chinese invention patent application 200610113538.9 discloses a kind of sensitizing radiation degradation method for preparing low-molecular weight chitoglycan, at first that purified chitosan solid is even with the aqueous solution that contains sensitizing agent, form the semi-solid sample, with mineral acid or organic acid for adjusting pH to 4, wherein the mass concentration of chitosan is 16～25%, the mass concentration of sensitizing agent is 15～30%, use ray room temperature irradiation-induced degradation then, absorbed dose is 1～10kGy; Irradiation product is spray-dried or through the vacuum-drying son amount chitosan that makes low score; Chinese invention patent application 200610116248.X discloses a kind of method for preparing low molecular weight water-soluble shitosan, and this method is to be raw material with the chitin, utilizes microwave radiation, the preparation low molecular weight water-soluble shitosan; Chinese invention patent 200410010767.9 discloses the method that a kind of radiation method prepares small molecular weight or water-soluble chitosan, uses
60The Co gamma-radiation carries out irradiation-induced degradation to polymer chitosan, and degraded product obtains small molecules or water-soluble chitosan through post-processing steps such as dissolving, decolourings.
The shortcoming of these methods is:
1) irradiation-induced degradation is very high to equipment requirements, may produce hazardous and noxious substances simultaneously,
2) microwave radiation prepares low-molecular weight chitoglycan and belongs to periodical operation, is unfavorable for serialization production.
Many shortcomings such as 3) chemical degradation method exists the cost height, yields poorly, sour debris need be handled;
4) the enzyme liberating method also have such as the used enzyme cost of degraded too high, the zymotechnique complexity, can't mass industrialized production etc. problem.
The pulsed electrical field treatment technology is the green processing technology of emerging during the nearly last ten years a kind of food, is mainly used in the cold sterilization of liquid material etc.Its high field (greater than 20kV/cm) can directly cause the polarization of microorganism cells perforate membrane, thalline death, and its spike pulse (less than 100 μ s) and low frequency (less than 1000Hz) can guarantee to be in non-heated condition.Chinese invention patent ZL01130064.7 has announced a kind of high-voltage pulse electric field sterilization method and device thereof, Chinese invention patent ZL02152160.6 has announced the method for design of the treater of pulsed electrical field sterilizing device, and Chinese invention patent ZL200410077405.1 has announced a kind of Prepolarized pulse electric field disinfectant method and equipment thereof; Highfield also is applied to other foodstuffs industry and handles, announced the sedimentary device of a kind of employing highfield removal soy sauce as Chinese patent ZL00260065.X, Chinese patent ZL200410052115.1 has announced the method for a kind of electromagnetic field acceleration cognac oak ageing, and Chinese patent application 200710031217.9 discloses a kind of physical field Wine aging method and device thereof.But these patented technologies all do not relate to the method that adopts the strong pulse electric field treatment to prepare low-molecular weight chitoglycan.
Summary of the invention
The objective of the invention is to that (molecular weight is greater than 2.5 * 10 by adopting strong pulse electric field treatment high molecular weight chitosan
5G/mol, deacetylation is greater than 60%), a kind of preparation low-molecular weight chitoglycan is provided, and (molecular weight is less than 2.3 * 10
4G/mol) physical method.
The present invention can be achieved by the following technical programs:
A kind of method of utilizing pulsed electrical field to prepare low-molecular weight chitoglycan may further comprise the steps:
(1) chitosan dissolving, high molecular weight chitosan is added in the lysate, described lysate is mineral acid, aqueous solutions of organic acids, aqueous hydrogen peroxide solution or is added with mineral acid or the organic acid aqueous hydrogen peroxide solution, wherein the mass concentration of chitosan in solution is 1～15%, mineral acid or organic acid mass concentration are 0.5～15%, and the mass concentration of hydrogen peroxide is 1～30%; Described high molecular weight chitosan is that viscosity-average molecular weight is greater than 1.0 * 10
5G/mol, deacetylation is greater than 60% chitosan; Described mineral acid is a hydrochloric acid, and described organic acid is formic acid, acetate, citric acid or lactic acid;
(2) pulsed electrical field is handled: chitosan solution is handled in the pulsed electrical field treater; Electric field strength is 40～60kV/cm, pulse width 10～100 μ s, and pulse-repetition 100～1000Hz, pulse waveform is a square wave, the time that chitosan is subjected to the pulsed electrical field processing is 10～1000ms;
(3) add alkaline solution in the chitosan solution after burst process, regulate pH to 6～8, staticly settle, the centrifugal throw out that gets;
(4) throw out is with acetone or ether washing 1～3 time, the vacuum-drying son amount chitosan that promptly makes low score.
The described pulsed electrical field treatment time is preferably 300～500ms.
Described electric field strength is preferably 45～55kV/cm.
Described alkaline solution is preferably NaOH, NaOH, KOH and NaHCO
3One or more of solution.
Described alkaline concentration is 0.5～2mol/L.
Described low-molecular weight chitoglycan is that viscosity-average molecular weight is less than 2.3 * 10
4The chitosan of g/mol.
Compared with prior art, the present invention has the following advantages:
(1) adopt the pulsed electrical field legal system to be equipped with low-molecular weight chitoglycan, preparation time is short, and the burst process time is the several seconds, is shorter than the chemical method chemical time of needed a few hours greatly;
(2) in preparation process, avoided adding a large amount of chemical reagent, thereby reduced follow-up cleaning and waste water control, belonged to green cleaning processing;
(3) the burst process process is carried out at normal temperatures, and the method consumed energy that in contrast to heat is little.
Embodiment
Below in conjunction with embodiment the present invention is described further, but embodiments of the present invention are not limited thereto.
Embodiment 1
With high molecular weight chitosan (viscosity-average molecular weight M
η=3.0 * 10
5G/mol, deacetylation is greater than 90%) with contain acetic acid water solution and mix, wherein the mass concentration of chitosan is 1%, the mass concentration of acetate is 3%.With continuous constant flow pump chitosan solution is pumped into pulse electric field device, regulating electric field strength simultaneously is 40kV/cm, pulse width 10 μ s, and pulse-repetition 1000Hz, pulse waveform is a square wave, the burst process time is 10ms.Add the 0.5mol/L sodium hydroxide solution in the chitosan solution after burst process, regulate pH to 6.0, staticly settle, the centrifugal throw out that gets.Throw out is with washing with acetone 2 times, vacuum-drying son amount chitosan (the viscosity-average molecular weight M that promptly makes low score
η=2.3 * 10
4G/mol, productive rate 85%).
Embodiment 2
With high molecular weight chitosan (viscosity-average molecular weight M
η=6.8 * 10
5G/mol, deacetylation is greater than 80%) even with the aqueous solution that contains hydrogen peroxide, wherein the mass concentration of chitosan is 10%, the mass concentration of hydrogen peroxide is 15%.With continuous constant flow pump chitosan solution is pumped into pulse electric field device, regulating electric field strength simultaneously is 50kV/cm, pulse width 50 μ s, and pulse-repetition 100Hz, pulse waveform is a square wave, the burst process time is 200ms.Add in the chitosan solution after burst process and contain 1.0mol/L sodium bicarbonate and 0.5mol/L potassium hydroxide mixing solutions, regulate pH to 7.2, staticly settle, the centrifugal throw out that gets.Throw out is with ether washing 3 times, vacuum-drying son amount chitosan (the viscosity-average molecular weight M that promptly makes low score
η=1.6 * 10
4G/mol, productive rate 85%).
Embodiment 3
With high molecular weight chitosan (viscosity-average molecular weight M
η=4.5 * 10
5G/mol, deacetylation is greater than 70%) even with the aqueous solution that contains formic acid and lactic acid, wherein the mass concentration of chitosan is 7%, and the mass concentration of formic acid is 8%, and the mass concentration of lactic acid is 12%.With continuous constant flow pump chitosan solution is pumped into pulse electric field device, regulating electric field strength simultaneously is 45kV/cm, pulse width 80 μ s, and pulse-repetition 500Hz, pulse waveform is a square wave, the burst process time is 300ms.Add the 2.0mol/L sodium hydroxide solution in the chitosan solution after burst process, regulate pH to 6.8, staticly settle, the centrifugal throw out that gets.Throw out is with ether washing 2 times, vacuum-drying son amount chitosan (the viscosity-average molecular weight M that promptly makes low score
η=1.7 * 10
4G/mol, productive rate 88%).
Embodiment 4
With high molecular weight chitosan (viscosity-average molecular weight M
η=5.5 * 10
5G/mol, deacetylation is greater than 85%) with contain aqueous solution of hydrochloric acid and mix, wherein the mass concentration of chitosan is 15%, the mass concentration of hydrochloric acid is 9%.With continuous constant flow pump chitosan solution is pumped into pulse electric field device, regulating electric field strength simultaneously is 55kV/cm, pulse width 30 μ s, and pulse-repetition 800Hz, pulse waveform is a square wave, the burst process time is 400ms.Add the 1.0mol/L sodium hydroxide solution in the chitosan solution after burst process, regulate pH to 7.1, staticly settle, the centrifugal throw out that gets.Throw out is with washing with acetone 1 time, vacuum-drying son amount chitosan (the viscosity-average molecular weight M that promptly makes low score
η=1.2 * 10
4G/mol, productive rate 90%).
Embodiment 5
With high molecular weight chitosan (viscosity-average molecular weight M
η=2.5 * 10
5G/mol, deacetylation is greater than 60%) even with the aqueous solution that contains citric acid, wherein the mass concentration of chitosan is 5%, the mass concentration of citric acid is 6%.With continuous constant flow pump chitosan solution is pumped into pulse electric field device, regulating electric field strength simultaneously is 60kV/cm, pulse width 100 μ s, and pulse-repetition 300Hz, pulse waveform is a square wave, the burst process time is 1000ms.Add the 1.2mol/L sodium hydroxide solution in the chitosan solution after burst process, regulate pH to 8.0, staticly settle, the centrifugal throw out that gets.Throw out is with washing with acetone 3 times, vacuum-drying son amount chitosan (the viscosity-average molecular weight M that promptly makes low score
η=2.2 * 10
4G/mol, productive rate 82%).
The foregoing description adopts the pulsed electrical field legal system to be equipped with low-molecular weight chitoglycan, and preparation time is short, and the burst process time is 10～1000ms, is shorter than the chemical method chemical time of needed a few hours greatly; Just add lysate in the preparation process at high molecular weight chitosan, lysate is mineral acid, aqueous solutions of organic acids, aqueous hydrogen peroxide solution or is added with mineral acid or the organic acid aqueous hydrogen peroxide solution, avoided adding a large amount of chemical reagent, thereby reduced follow-up cleaning and waste water control, belonged to green cleaning processing; The burst process process is carried out at normal temperatures, and the method consumed energy that in contrast to heat is little.
Claims (6)
1. method of utilizing pulsed electrical field to prepare low-molecular weight chitoglycan is characterized in that may further comprise the steps:
(1) chitosan dissolving, high molecular weight chitosan is added in the lysate, described lysate is mineral acid, aqueous solutions of organic acids, aqueous hydrogen peroxide solution or is added with mineral acid or the organic acid aqueous hydrogen peroxide solution, wherein the mass concentration of chitosan in solution is 1～15%, mineral acid or organic acid mass concentration are 0.5～15%, and the mass concentration of hydrogen peroxide is 1～30%; Described high molecular weight chitosan is that viscosity-average molecular weight is greater than 1.0 * 10
5G/mol, deacetylation is greater than 60% chitosan; Described mineral acid is a hydrochloric acid, and described organic acid is formic acid, acetate, citric acid or lactic acid;
(2) pulsed electrical field is handled: chitosan solution is handled in the pulsed electrical field treater; Electric field strength is 40～60kV/cm, pulse width 10～100 μ s, and pulse-repetition 100～1000Hz, pulse waveform is a square wave, the time that chitosan is subjected to the pulsed electrical field processing is 10～1000ms;
(3) add alkaline solution in the chitosan solution after pulsed electrical field is handled, regulate pH to 6～8, staticly settle, the centrifugal throw out that gets;
(4) throw out is with acetone or ether washing 1～3 time, the vacuum-drying son amount chitosan that promptly makes low score.
2. the method for utilizing pulsed electrical field to prepare low-molecular weight chitoglycan according to claim 1 is characterized in that: the described pulsed electrical field treatment time is 300～500ms.
3. the method for utilizing pulsed electrical field to prepare low-molecular weight chitoglycan according to claim 1 is characterized in that: described electric field strength is 45～55kV/cm.
4. the method for utilizing pulsed electrical field to prepare low-molecular weight chitoglycan according to claim 1 is characterized in that: described alkaline solution is NaOH, KOH and NaHCO
3One or more of solution.
5. the method for utilizing pulsed electrical field to prepare low-molecular weight chitoglycan according to claim 4 is characterized in that: described alkaline concentration is 0.5～2mol/L.
6. the method for utilizing pulsed electrical field to prepare low-molecular weight chitoglycan according to claim 1 is characterized in that: described low-molecular weight chitoglycan is that viscosity-average molecular weight is less than 2.3 * 10
4The chitosan of g/mol.
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| CN102875696B (en) * | 2012-09-11 | 2014-11-12 | 华南理工大学 | Device and method for preparing low molecular weight water-soluble chitosan through synergy of pulsed electric field and ozone |
| CN110693772B (en) * | 2019-11-12 | 2021-11-23 | 烟台新时代健康产业日化有限公司 | Preparation method of seaweed anti-inflammatory extract applied to cosmetics |
| CN112063766A (en) * | 2019-12-23 | 2020-12-11 | 沈阳农业大学 | Polysaccharide degradation method by liquid-phase pulse discharge plasma |
| CN113637096A (en) * | 2021-09-15 | 2021-11-12 | 吴洪德 | Preparation method of chitosan oligosaccharide, chitosan oligosaccharide and chitosan oligosaccharide health-care product |
| CN114751999A (en) * | 2022-05-17 | 2022-07-15 | 英都斯特(无锡)感应科技有限公司 | Green preparation method of acidolysis polysaccharide |
| CN115886234B (en) * | 2022-12-01 | 2024-01-30 | 武汉海泰聚诚工程有限公司 | Brewing process of soy sauce |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1354018A (en) * | 2001-12-12 | 2002-06-19 | 华南理工大学 | High-voltage pulse electric field sterilization method and its equipment |
| CN1563106A (en) * | 2004-03-29 | 2005-01-12 | 中国科学院长春应用化学研究所 | Preparing water soluble chitosan or in small molecular weight through radiation method |
| CN1923854A (en) * | 2006-09-20 | 2007-03-07 | 东华大学 | Preparation method for low molecular weight water-soluble shitosan |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1354018A (en) * | 2001-12-12 | 2002-06-19 | 华南理工大学 | High-voltage pulse electric field sterilization method and its equipment |
| CN1563106A (en) * | 2004-03-29 | 2005-01-12 | 中国科学院长春应用化学研究所 | Preparing water soluble chitosan or in small molecular weight through radiation method |
| CN1923854A (en) * | 2006-09-20 | 2007-03-07 | 东华大学 | Preparation method for low molecular weight water-soluble shitosan |
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