CN103266153B - Production method of modified chitosan - Google Patents
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- CN103266153B CN103266153B CN201310238862.3A CN201310238862A CN103266153B CN 103266153 B CN103266153 B CN 103266153B CN 201310238862 A CN201310238862 A CN 201310238862A CN 103266153 B CN103266153 B CN 103266153B
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Abstract
The invention belongs to the field of biological engineering and relates to chitosan modification. The chitosan modification comprises the following steps of: adding protein or polypeptide; adding transglutaminase; adjusting the pH value; removing precipitates after full reaction; and desalting and drying for modification. The modified chitosan produced by the technical scheme disclosed by the invention is good in water solubility, does not generate precipitate at the pH value of 3-10, and is small in viscosity. Moreover, the functions including strong adsorption, antibacterial property and the like of the chitosan are kept, and the application prospect is extensive.
Description
Technical field
The invention belongs to bioengineering field, particularly relate to a kind of production method of modified chitosan.
Technical background
Chitosan (chitosan) is that the chitin (chitin) extensively existed by nature obtains through deacetylation, and chemical name is Chitosan (1-4)-2-amino-B-D glucose.There is a large amount of amino in macromolecular structure due to it and with a large amount of positive charges, thus to electronegative all kinds of objectionable impuritiess, there is powerful adsorption.The premium propertiess such as the biological functionality of this natural polymer and consistency, blood compatibility, security, microbic resolvability are by all trades and professions extensive concern, there is physiological functions such as controlling cholesterol, anti-bacteria, prevention and corntrol hypertension, absorption and excretion heavy metal, maintenance humidity, enhancing immunity, achieve major progress in the applied research of the numerous areas such as medicine, food, chemical industry, makeup, water treatment, METAL EXTRACTION and recovery, biochemistry and biomedical engineering.
But chitosan can only be dissolved in some rare mineral acids or organic acid, can not be directly soluble in water, which greatly limits its application.In order to address this problem, people, by adopting serial of methods, make chitosan energy water-soluble.As: the chitosan mineral acid that 1. various energy is water-soluble or organic acid hydrochlorate, as chitosan hydrochloride, chitosan lactate and Chitosan citrate etc.; 2. degradation of chitosan is made to be can water-soluble low-molecular weight chitoglycan by chemistry or biological method; 3. chitosan chemical modification object that can be water-soluble, as: cm-chitosan etc.; 4. accurately controlled by the acidylate degree of chemical reaction to chitosan, control its acylation degree 50% ~ 60%.
But all there are some defects in these methods, although as chitosan mineral acid or organic acid hydrochlorate water-soluble, can Precipitation when pH value is greater than 6.2; The physiologically active of low-molecular weight chitoglycan greatly reduces as germ resistance, adsorptivity etc. or disappears; There is certain safety issue in chitosan chemical modification object, its physiologically active also exists change or loses simultaneously; Carry out accurately controlling not only more difficult realization to the acidylate degree of chitosan, in security and physiologically active, also there is same problem.
Summary of the invention
Low in order to solve chitosan solvability, Precipitation is understood when pH value is greater than 6.2, the problems such as viscosity is large, the invention provides a kind of good water solubility, pH3-10 does not precipitate, viscosity is little, and also retain the modified chitosan production method of the functions such as the original strong adsorptivity of chitosan, germ resistance, concrete technical scheme is as follows:
A kind of production method of modified chitosan, comprise the following step: (1) is got chitosan and is dissolved in organic acid or inorganic acid solution, regulate pH4.0-6.2, (2) add acry radical donor, then add Transglutaminase EC2.3.2.13,25-85 DEG C of fully reaction, regulate pH6.2-7.0, filter and remove precipitation, desalination, dry; Described chitosan or chitosan inorganic acid salt: acry radical donor: Transglutaminase EC2.3.2.13 mass ratio is=1:0.01-1:0.1; The described acry radical donor that adds is add protein or polypeptide utilizes the γ-carboxamide groups of its glutamine residue as acry radical donor.
Described mineral acid or organic acid soln are the hydrochloric acid of 0.1-1mol/L, acetic acid, lactic acid or citric acid; Described Transglutaminase EC2.3.2.13 is 2000U/g.
In order to reach better effect:
PH is regulated to be 6.2;
Described acry radical donor is the mixture of one or more in glutin, soybean protein, casein, collagen protein, silk fibroin, polypeptide, is preferably glutin; Described polypeptide is preferably gsh.
Described chitosan: acry radical donor: Transglutaminase EC2.3.2.13 mass ratio is 1:0.2:0.1.
Dialysis or ultrafiltration desalination are taked in described desalination; Described drying is spraying dry or vacuum-drying.
Modified chitosan is the derivative of Chitosan (1-4)-2-amino-B-D glucose, can dissolve under pH3-10 condition.
Glutamine turns ammonia (amine) enzyme, another name: trans-glutaminases, English name: Glutamine trasaminase (TG), animal can be derived from, plant and microorganism, it is (or interior) acyl group shift reaction between a kind of catalytic proteins, it can in catalytic proteins polypeptide generation molecule and intermolecular generation covalent cross-linking, thus improve the structure and function of protein, to the character of protein as foaminess, emulsifying property, emulsifying stability, thermostability, the Be very effective such as water-retentivity and gelling ability, and then improve the local flavor of food, mouthfeel, quality and outward appearance etc., be widely used at food processing field, can be applicable to fishery technology, ham, sausage, Noodles, bean curd etc.
The present invention relates to the bio-modification of chitosan, can make chitosan while the original absorption of reservation, flocculation, the function such as antibacterial, water soluble, and can not precipitate when pH value is greater than 6.2, its solubility property significantly improves than unmodified chitosan when pH value is greater than 6.2, and the viscosity of chitosan can be reduced, thus greatly strengthen the scope of application of chitosan.Its ultimate principle is: the transacylate function utilizing Transglutaminase EC2.3.2.13; be connected containing glutamine or the various materials (protein, peptide etc.) containing glutamine by amido linkage with the primary amine groups of chitosan, thus reach the object of the bio-modification of chitosan.
Technical solution of the present invention is carried out chitosan biological modification and is had following beneficial effect:
1, modified chitosan good water solubility, pH value can not precipitate between 3.0-10.0, and can make chitosan while the original absorption of reservation, flocculation, the function such as antibacterial, the scope of application is wider, is particularly useful for the physiological environment of human body;
3, the viscosity of chitosan can be reduced, thus greatly strengthen the scope of application of chitosan;
4, raw material is for using food grade or pharmaceutical grade raw material (TG enzyme, proteins and peptides etc.), and have the characteristic such as biological functionality and consistency, blood compatibility, security, microbic resolvability, security is good;
5, enzymatic reaction condition is gentle, reaction efficiency is high, environmentally friendly;
6, by modified chitosan that the present invention produces, retain chitosan original bioactive while, owing to having the water-soluble and wider pH scope of application, and it is more safe and reliable, be particularly useful for the physiological pH environment of human body, its using value having tool large in fields such as medical and health, health therapy, food-processing, chemical industry and biotechnology.
Embodiment
The biosynthesizing of embodiment 1 chitosan glutin and application
The biosynthesizing of chitosan glutin: get chitosan 100 grams, to be dissolved in the hydrochloric acid of 0.1-1.0 M (under mol/L with) (or get 100 grams of chitosan hydrochlorides, and soluble in water), with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 4.0-6.2, add glutin 1-100 gram (soluble in water in advance), add TG enzyme 5 grams (2000 U/g), in 25 DEG C-85 DEG C reaction 1-48 hour, after reaction terminates, with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 6.2-7.0, cross elimination precipitation, to dialyse or after ultrafiltration desalination, spraying dry or vacuum-drying, chitosan glutin.
Embodiment 2
Get chitosan 100 grams, to be dissolved in the hydrochloric acid of 0.1-1.0 M (or get 100 grams of chitosan hydrochlorides, and soluble in water), with the NaHCO of NaOH or 0.1N of 0.1N
3regulate pH6.2.Add acry radical donor glutin, then add 2000 U/g Transglutaminase EC2.3.2.13s, 25-85 DEG C of fully reaction, after reaction terminates, with the NaHCO of NaOH or 0.1N of 0.1N
3regulate pH6.2, filter and remove precipitation, desalination, spraying dry or vacuum-drying; Chitosan or chitosan inorganic acid salt: glutin: Transglutaminase EC2.3.2.13 mass ratio is=1:0.2:0.1.
The biosynthesizing of embodiment 3 chitosan collagen protein and application
Get chitosan 100 grams, to be dissolved in the hydrochloric acid of 0.1-1.0 M (or get 100 grams of chitosan hydrochlorides, and soluble in water), with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 4.0-6.2, add collagen protein 1-100 gram (soluble in water in advance), add TG enzyme 5 grams, in 25 DEG C-85 DEG C reaction 1-48 hour, after reaction terminates, with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 6.2-7.0, cross elimination precipitation, to dialyse or after ultrafiltration desalination, spraying dry or vacuum-drying, chitosan collagen protein.
The biosynthesizing of embodiment 4 chitosan soybean protein and application
Get chitosan 100 grams, to be dissolved in the acetic acid of 0.1-1.0 M (or get 100 grams of chitosan acetate, and soluble in water), with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 4.0-6.2, add soybean protein 1-100 gram (soluble in water in advance), add TG enzyme 15 grams, in 25 DEG C-85 DEG C reaction 1-48 hour, after reaction terminates, with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 6.2-7.0, cross elimination precipitation, to dialyse or after ultrafiltration desalination, spraying dry or vacuum-drying, chitosan soybean protein.
The caseic biosynthesizing of embodiment 5 chitosan and application
Get chitosan 100 grams, to be dissolved in the lactic acid of 0.1-1.0 M (or get 100 grams of chitosan lactates, and soluble in water), with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 4.0-6.2, add casein 1-100 gram (soluble in water in advance), add TG enzyme 6 grams, in 25 DEG C-85 DEG C reaction 1-48 hour, after reaction terminates, with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 6.2-7.0, cross elimination precipitation, to dialyse or after ultrafiltration desalination, spraying dry or vacuum-drying, chitosan casein.
The biosynthesizing of embodiment 6 chitosan gsh and application
Get chitosan 100 grams, to be dissolved in the citric acid of 0.1-1.0 M (or get 100 grams of Chitosan citrates, and soluble in water), with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 4.0-6.2, add gsh 0.1-20 gram (soluble in water in advance), add TG enzyme 12 grams, in 25 DEG C-85 DEG C reaction 1-48 hour, after reaction terminates, with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 6.2-7.0, cross elimination precipitation, to dialyse or after ultrafiltration desalination, spraying dry or vacuum-drying, chitosan gsh.
The biosynthesizing of embodiment 7 chitosan ovalbumin and application
Get chitosan 100 grams, to be dissolved in the hydrochloric acid of 0.1-1.0 M (or get 100 grams of chitosan hydrochlorides, and soluble in water), with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 4.0-6.2, add ovalbumin 1-100 gram (soluble in water in advance), add TG enzyme 5 grams, in 25 DEG C-85 DEG C reaction 1-48 hour, after reaction terminates, with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 6.2-7.0, cross elimination precipitation, to dialyse or after ultrafiltration desalination, spraying dry or vacuum-drying, chitosan ovalbumin.
The biosynthesizing of embodiment 8 chitosan/silk fibroin and application
Get chitosan 100 grams, to be dissolved in the hydrochloric acid of 0.1-1.0 M (or get 100 grams of chitosan hydrochlorides, and soluble in water), with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 4.0-6.2, add silk fibroin 1-100 gram (soluble in water in advance), add TG enzyme 5 grams, in 25 DEG C-85 DEG C reaction 1-48 hour, after reaction terminates, with the NaHCO of NaOH or 0.1N of 0.1N
3adjust the pH value of solution to 6.2-7.0, cross elimination precipitation, to dialyse or after ultrafiltration desalination, spraying dry or vacuum-drying, chitosan/silk fibroin.
The performance comparison test of embodiment 9 modified chitosan
Example 1 gained modified chitosan (chitosan glutin), when being greater than 6.2 to its bacteriostasis rate, viscosity and pH, the index such as solubleness is tested, can before modified after chitosan Performance comparision as following table:
| Performance index | Before modified | Modified |
| To intestinal bacteria inhibiting rate (1mg/ml) | 99.8% | 99.6% |
| To streptococcus aureus inhibiting rate (1mg/ml) | 100% | 100% |
| To aspergillus niger inhibiting rate (1mg/ml) | 86% | 84.5% |
| Viscosity (20mg/ml, 37 DEG C)) | 45-55cP | 10-12cP |
| Solubleness during pH 7.0 | 0-1% | 4-10% |
Claims (6)
1. the production method of a modified chitosan, it is characterized in that comprising the following step: (1) is got chitosan and is dissolved in organic acid or inorganic acid solution, regulate pH4.0-6.2, (2) add acry radical donor, then add Transglutaminase EC2.3.2.13,25-85 DEG C of fully reaction, regulate pH6.2-7.0, filter and remove precipitation, desalination, dry; Described chitosan or chitosan inorganic acid salt: acry radical donor: Transglutaminase EC2.3.2.13 mass ratio is=1:0.2:0.1; The described acry radical donor that adds is add protein or polypeptide utilizes the γ-carboxamide groups of its glutamine residue as acry radical donor; Described mineral acid or organic acid soln are the hydrochloric acid of 0.1-1mol/L, acetic acid, lactic acid or citric acid; Described Transglutaminase EC2.3.2.13 is 2000U/g.
2. the method for claim 1, is characterized in that regulating pH to be 6.2.
3. the method for claim 1, is characterized in that described acry radical donor is the mixture of one or more in glutin, soybean protein, casein, collagen protein, silk fibroin, polypeptide.
4. the method for claim 1, is characterized in that described acry radical donor is glutin.
5. the method for claim 1, is characterized in that described polypeptide is gsh.
6. the method for claim 1, is characterized in that dialysis or ultrafiltration desalination are taked in described desalination; Described drying is spraying dry or vacuum-drying.
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Effective date of registration: 20190517 Address after: 330000 North First Floor of Jianchang Industrial Park Overseas Building, 203 Gaoxin Road, Nanchang High-tech Industrial Development Zone, Jiangxi Province Patentee after: NANCHANG L-LIANG INDUSTRIAL CO., LTD. Address before: 330031 No. 605 Fenglin Avenue, Changbei Economic Development Zone, Nanchang City, Jiangxi Province Patentee before: Jiangxi Science & Technology Normal University |