CN114133466B - Chitosan derivative used for food preservation and preparation method thereof - Google Patents
Chitosan derivative used for food preservation and preparation method thereof Download PDFInfo
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- CN114133466B CN114133466B CN202111430320.7A CN202111430320A CN114133466B CN 114133466 B CN114133466 B CN 114133466B CN 202111430320 A CN202111430320 A CN 202111430320A CN 114133466 B CN114133466 B CN 114133466B
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000009920 food preservation Methods 0.000 title claims description 24
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- 235000013824 polyphenols Nutrition 0.000 claims abstract description 38
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- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims abstract description 17
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- 239000004309 nisin Substances 0.000 claims description 21
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- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- AZKVWQKMDGGDSV-BCMRRPTOSA-N Genipin Chemical compound COC(=O)C1=CO[C@@H](O)[C@@H]2C(CO)=CC[C@H]12 AZKVWQKMDGGDSV-BCMRRPTOSA-N 0.000 claims description 11
- AZKVWQKMDGGDSV-UHFFFAOYSA-N genipin Natural products COC(=O)C1=COC(O)C2C(CO)=CCC12 AZKVWQKMDGGDSV-UHFFFAOYSA-N 0.000 claims description 11
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- 229940098779 methanesulfonic acid Drugs 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical group ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
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- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 2
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3526—Organic compounds containing nitrogen
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3544—Organic compounds containing hetero rings
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3562—Sugars; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
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- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microbiology (AREA)
- Food Science & Technology (AREA)
- Nutrition Science (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
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- Biochemistry (AREA)
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Abstract
The invention discloses a chitosan derivative used for food corrosion prevention and a preparation method thereof, comprising 3 steps of preparing modified chitosan, preparing tea polyphenol/epsilon-polylysine solution and preparing chitosan derivative; then reacting tea polyphenol with epsilon-polylysine, adding the reaction product into a mixed solution of modified chitosan and hyaluronic acid, and crosslinking the reaction product with the modified chitosan and the hyaluronic acid through hydrogen bond action to obtain the chitosan derivative.
Description
Technical Field
The invention relates to the technical field of polysaccharide derivative preparation, in particular to a chitosan derivative used for food preservation and a preparation method thereof.
Background
Chitosan is an emerging food additive, has natural, nontoxic, safe and efficient antiseptic property, can inhibit the growth of putrefying bacteria, and meanwhile, chitosan macromolecules with more hydroxyl groups form a reticular structure in the solution to form a macromolecule system, so that the viscosity of the solution is increased, and food ingredients are not easy to flow, thereby playing the roles of a thickening agent and a stabilizing agent.
In recent years, along with the improvement of living standard, the requirements of people on the freshness of foods are higher and higher, the preservative and fresh-keeping effects of the traditional chitosan food additive are not ideal, and improvement is needed, and patent document (CN 106962498A) discloses a nisin/chitosan nanoparticle antibacterial film, a preparation method and application, which are characterized in that nisin and gamma-polyglutamic acid are crosslinked, and then chitosan is added, so that the nisin-loaded gamma-polyglutamic acid/chitosan nanoparticle is prepared by crosslinking the nisin and the gamma-polyglutamic acid, the defect of reduced biological activity of nisin in the use process is overcome, and the utilization rate of nisin is improved; patent literature (CN 107892757 a) discloses a preparation method for preparing a porous chitosan film from a Pickering emulsion with stable Graphene Oxide (GO), and the preparation method for preparing the porous chitosan film from the Pickering emulsion is simple in process, green and environment-friendly, has low requirements on equipment, high stability of aqueous solution, uniform porous structure and easy scale, has wide application prospects in the fields of food preservation and food preservation, and has a certain research progress in the field of food preservation, but has short preservation and preservation effective time and needs to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a chitosan derivative for food preservation and a preparation method thereof, and solves the technical problem that the effective preservation time of the traditional food additive is short.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing chitosan derivatives for food preservation, comprising the steps of:
(1) Adding chitosan into methanesulfonic acid, stirring for dissolving, adding dianhydride into the solution, stirring at a low temperature for reaction for 4-8 hours, then adding nisin into the solution, reacting at 30-60 ℃ for 3-5 hours, slowly dripping the reaction solution into ethanol for precipitation under a high-speed stirring condition after the reaction is completed, washing the precipitate, and drying to obtain modified chitosan;
(2) Slowly adding the tea polyphenol solution into the epsilon-polylysine solution, adding the genipin solution for reaction, and obtaining the tea polyphenol/epsilon-polylysine solution after the reaction is finished;
(3) Adding the modified chitosan obtained in the step (1) into a hyaluronic acid solution, stirring uniformly, then adding the tea polyphenol/epsilon-polylysine solution obtained in the step (2) into the mixture, mixing uniformly, standing, and freeze-drying to obtain the chitosan derivative.
Preferably, in the step (1), the mass ratio of the chitosan, the methanesulfonic acid, the dianhydride and the nisin is 1:5-8:3-6:0.2-0.5.
Preferably, in the step (1), the dianhydride is succinic anhydride or glutaric anhydride.
Preferably, in the step (1), the low-temperature stirring temperature is-20 to-5 ℃.
Preferably, in the step (2), the mass ratio of the tea polyphenol solution, the epsilon-polylysine solution and the genipin solution is 1:1-2:0.5-1, the mass fraction of the tea polyphenol solution is 5-8%, the mass fraction of the epsilon-polylysine solution is 2-6%, and the mass fraction of the genipin solution is 0.6-0.8%.
Preferably, in the step (2), the reaction temperature is 40-80 ℃ and the reaction time is 2-3h.
Preferably, in the step (3), the mass ratio of the modified chitosan, the hyaluronic acid solution and the tea polyphenol/epsilon-polylysine solution is 5-10:30-60:5-10.
Preferably, in the step (3), the mass fraction of the hyaluronic acid solution is 2-6%.
Preferably, in the step (3), the standing time is 8-16 hours.
The invention also provides the chitosan derivative for food preservation, which is obtained by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a chitosan derivative for food preservation and a preparation method thereof, wherein the chitosan is subjected to carboxylation modification, then reacts with nisin, and nisin is loaded on the chitosan to obtain modified chitosan; then firstly reacting tea polyphenol with epsilon-polylysine, then adding the tea polyphenol into a mixed solution of modified chitosan and hyaluronic acid, and crosslinking the tea polyphenol with the modified chitosan and the hyaluronic acid through hydrogen bonding, thereby obtaining the chitosan derivative.
(2) The invention provides a chitosan derivative for food preservation and a preparation method thereof, which realize the purpose of slow release of nisin by loading nisin on chitosan microspheres, and simultaneously crosslink tea polyphenol and epsilon-polylysine and introduce the crosslinked tea polyphenol into a polymer network structure of modified chitosan and hyaluronic acid, thereby overcoming the defect of short preservation and bacteriostasis time effect caused by easy oxidation of the tea polyphenol and ensuring that the prepared food preservative has long-term preservation effect.
(3) The invention provides a chitosan derivative for food preservation and a preparation method thereof, nisin is a natural bioactive antibacterial peptide, and has strong inhibition effect on a plurality of gram-positive bacteria including food spoilage bacteria and pathogenic bacteria; the epsilon-polylysine is a polypeptide with antibacterial effect, and the mechanism of the antibacterial effect of the epsilon-polylysine is mainly dissolution of a cell wall structure of bacteria, so that other preservatives can attack microorganisms more effectively, therefore, when nisin and epsilon-polylysine are compounded for use, the invention has the synergistic antibacterial and antiseptic effects, fully utilizes the antibacterial property of each natural preservative, plays the synergistic interaction effect among the preservatives, and overcomes the defects of narrow antibacterial spectrum and limited antiseptic effects when the natural preservatives are independently used.
Detailed Description
The present invention will be described in further detail with reference to the following preferred examples, but the present invention is not limited to the following examples.
Unless otherwise specified, the chemical reagents involved in the present invention are all commercially available.
The chitosan used in this example was purchased from Shandong Orthoco Biotechnology Co., ltd, and had a molecular weight of 200000 and a degree of deacetylation of 80%.
Example 1
A method for preparing chitosan derivatives for food preservation, comprising the steps of:
(1) Adding 10g of chitosan into 50g of methanesulfonic acid, stirring and dissolving at the temperature of minus 20 ℃, adding 30g of succinic anhydride into the solution, stirring and reacting for 4 hours at the temperature of minus 20 ℃, adding 2g of nisin into the solution, reacting for 3 hours at the temperature of 30 ℃, slowly dripping the reaction solution into ethanol for precipitation under the condition of high-speed stirring after the reaction is completed, washing the precipitate, and drying to obtain the modified chitosan;
(2) Slowly adding 10g of 5wt% tea polyphenol solution into 10g of 2wt% epsilon-polylysine solution, adding 5g of 0.6wt% genipin solution, reacting for 2 hours at 40 ℃, and obtaining tea polyphenol/epsilon-polylysine solution after the reaction is finished;
(3) Adding 5g of the modified chitosan obtained in the step (1) into 30g of a 2wt% hyaluronic acid solution, uniformly stirring, then adding 5g of the tea polyphenol/epsilon-polylysine solution obtained in the step (2), uniformly mixing, standing for 8h, and freeze-drying to obtain the chitosan derivative.
Example 2
A method for preparing chitosan derivatives for food preservation, comprising the steps of:
(1) Adding 10g of chitosan into 60g of methanesulfonic acid, stirring and dissolving at the temperature of minus 10 ℃, adding 50g of succinic anhydride into the solution, stirring and reacting for 4 hours at the temperature of minus 10 ℃, adding 3g of nisin into the solution, reacting for 3 hours at the temperature of 40 ℃, slowly dripping the reaction solution into ethanol for precipitation under the condition of high-speed stirring after the reaction is completed, washing the precipitate, and drying to obtain the modified chitosan;
(2) Slowly adding 10g of a 6wt% tea polyphenol solution into 15g of a 4wt% epsilon-polylysine solution, adding 6g of a 0.8wt% genipin solution, reacting for 2 hours at 60 ℃, and obtaining a tea polyphenol/epsilon-polylysine solution after the reaction is finished;
(3) Adding 6g of the modified chitosan obtained in the step (1) into 40g of 4wt% hyaluronic acid solution, uniformly stirring, then adding 5g of the tea polyphenol/epsilon-polylysine solution obtained in the step (2), uniformly mixing, standing for 12h, and freeze-drying to obtain the chitosan derivative.
Example 3
A method for preparing chitosan derivatives for food preservation, comprising the steps of:
(1) Adding 10g of chitosan into 70g of methanesulfonic acid, stirring and dissolving at the temperature of minus 10 ℃, adding 40g of succinic anhydride into the solution, stirring and reacting for 4 hours at the temperature of minus 10 ℃, adding 4g of nisin into the solution, reacting for 3 hours at the temperature of 50 ℃, slowly dripping the reaction solution into ethanol for precipitation under the condition of high-speed stirring after the reaction is completed, washing the precipitate, and drying to obtain the modified chitosan;
(2) Slowly adding 10g of 8wt% tea polyphenol solution into 18g of 6wt% epsilon-polylysine solution, adding 8g of 0.8wt% genipin solution, reacting for 3 hours at 80 ℃, and obtaining tea polyphenol/epsilon-polylysine solution after the reaction is finished;
(3) Adding 10g of the modified chitosan obtained in the step (1) into 60g of a hyaluronic acid solution with the concentration of 6wt%, uniformly stirring, then adding 8g of the tea polyphenol/epsilon-polylysine solution obtained in the step (2), uniformly mixing, standing for 12h, and freeze-drying to obtain the chitosan derivative.
Example 4
A method for preparing chitosan derivatives for food preservation, comprising the steps of:
(1) Adding 10g of chitosan into 80g of methanesulfonic acid, stirring and dissolving at the temperature of minus 5 ℃, adding 40g of succinic anhydride into the solution, stirring and reacting for 8 hours at the temperature of minus 5 ℃, adding 5g of nisin into the solution, reacting for 5 hours at the temperature of 60 ℃, slowly dripping the reaction solution into ethanol for precipitation under the condition of high-speed stirring after the reaction is completed, washing the precipitate, and drying to obtain the modified chitosan;
(2) Slowly adding 10g of 6wt% tea polyphenol solution into 20g of 5wt% epsilon-polylysine solution, adding 10g of 0.8wt% genipin solution, reacting for 2 hours at 80 ℃, and obtaining tea polyphenol/epsilon-polylysine solution after the reaction is finished;
(3) Adding 8g of the modified chitosan obtained in the step (1) into 50g of 5wt% hyaluronic acid solution, uniformly stirring, then adding 10g of the tea polyphenol/epsilon-polylysine solution obtained in the step (2), uniformly mixing, standing for 16h, and freeze-drying to obtain the chitosan derivative.
Comparative example 1
A method for preparing chitosan derivatives for food preservation, comprising the steps of:
(1) Adding 10g of chitosan into 70g of methanesulfonic acid, stirring and dissolving at the temperature of minus 10 ℃, adding 40g of succinic anhydride into the solution, stirring and reacting for 4 hours at the temperature of minus 10 ℃, slowly dripping the reaction solution into ethanol for precipitation under the condition of high-speed stirring after the reaction is finished, washing the precipitate, and drying to obtain the modified chitosan;
(2) Slowly adding 10g of 8wt% tea polyphenol solution into 18g of 6wt% epsilon-polylysine solution, adding 8g of 0.8wt% genipin solution, reacting for 3 hours at 80 ℃, and obtaining tea polyphenol/epsilon-polylysine solution after the reaction is finished;
(3) Adding 10g of the modified chitosan obtained in the step (1) into 60g of a hyaluronic acid solution with the concentration of 6wt%, uniformly stirring, then adding 8g of the tea polyphenol/epsilon-polylysine solution obtained in the step (2), uniformly mixing, standing for 12h, and freeze-drying to obtain the chitosan derivative.
Comparative example 2
A method for preparing chitosan derivatives for food preservation, comprising the steps of:
(1) Adding 10g of chitosan into 70g of methanesulfonic acid, stirring and dissolving at the temperature of minus 10 ℃, adding 40g of succinic anhydride into the solution, stirring and reacting for 4 hours at the temperature of minus 10 ℃, adding 4g of nisin into the solution, reacting for 3 hours at the temperature of 50 ℃, slowly dripping the reaction solution into ethanol for precipitation under the condition of high-speed stirring after the reaction is completed, washing the precipitate, and drying to obtain the modified chitosan;
(2) Slowly adding 10g of 8wt% tea polyphenol solution into 18g of 6wt% epsilon-polylysine solution, and uniformly mixing to obtain tea polyphenol/epsilon-polylysine solution;
(3) Adding 10g of the modified chitosan obtained in the step (1) into 60g of a hyaluronic acid solution with the concentration of 6wt%, uniformly stirring, then adding 8g of the tea polyphenol/epsilon-polylysine solution obtained in the step (2), uniformly mixing, standing for 12h, and freeze-drying to obtain the chitosan derivative.
And (3) testing corrosion resistance: the chitosan derivatives prepared in examples 1-4 and comparative examples 1-2 were formulated into 2wt% preservative, fresh pork was taken, washed in sterile water to remove dirt, then divided into about 100g each, respectively soaked in the preservative prepared in examples 1-4 and comparative examples 1-2, after 10min of soaking, left at room temperature, and measured for TVB-N content for 7 days, 14 days and 21 days, wherein TVB-N is an alkaline nitrogen-containing substance generated by deamination and decarboxylation of decomposed proteins of meat under the action of microorganisms, the content of which is an index for judging the freshness of meat, and the national standard limit value is 15.0mg/100g, and the measurement results are shown in the following table:
safety test: the chitosan derivative prepared in example 3 is prepared into a preservative with the weight percentage of 2%, mice are respectively subjected to gastric lavage with 0.1mL/10g, 0.2mL/10g and 0.4mL/10g of the preservative, the stomach is irrigated once a day, continuous observation is carried out for 3 weeks, the acute toxic reaction and death condition of the mice after the gastric lavage are observed, and as a result, the mice are found to have central excitation or inhibition symptoms within 21 days, no symptoms of myotonia change or myotremor are found, the mice move freely and normally in gait, no abnormal breathing, eating and defecation are caused, and no mice die during the observation, so that the food preservative prepared by the invention is a nontoxic or low-toxicity preparation.
Finally, it should be noted that: the above examples are not intended to limit the present invention in any way. Modifications and improvements will readily occur to those skilled in the art upon the basis of the present invention. Accordingly, any modification or improvement made without departing from the spirit of the invention is within the scope of the invention as claimed.
Claims (6)
1. A method for preparing a chitosan derivative for food preservation, which is characterized by comprising the following steps:
(1) Adding chitosan into methanesulfonic acid, stirring for dissolving, adding dianhydride into the solution, stirring at a low temperature for reaction for 4-8 hours, then adding nisin into the solution, reacting at 30-60 ℃ for 3-5 hours, slowly dripping the reaction solution into ethanol for precipitation under a high-speed stirring condition after the reaction is completed, washing the precipitate, and drying to obtain modified chitosan;
(2) Slowly adding the tea polyphenol solution into the epsilon-polylysine solution, adding the genipin solution for reaction, and obtaining the tea polyphenol/epsilon-polylysine solution after the reaction is finished;
(3) Adding the modified chitosan obtained in the step (1) into a hyaluronic acid solution, uniformly stirring, then adding the tea polyphenol/epsilon-polylysine solution obtained in the step (2), uniformly mixing, standing, and freeze-drying to obtain a chitosan derivative;
wherein in the step (1), the mass ratio of the chitosan, the methanesulfonic acid, the dianhydride and the nisin is 1:5-8:3-6:0.2-0.5;
in the step (2), the mass ratio of the tea polyphenol solution to the epsilon-polylysine solution to the genipin solution is 1:1-2:0.5-1, the mass fraction of the tea polyphenol solution is 5-8%, the mass fraction of the epsilon-polylysine solution is 2-6%, and the mass fraction of the genipin solution is 0.6-0.8%;
in the step (3), the mass ratio of the modified chitosan, the hyaluronic acid solution and the tea polyphenol/epsilon-polylysine solution is 5-10:30-60:5-10;
in the step (3), the mass fraction of the hyaluronic acid solution is 2-6%.
2. The method for producing chitosan derivatives for food preservation according to claim 1, wherein in the step (1), the dianhydride is succinic anhydride or glutaric anhydride.
3. The method for producing a chitosan derivative for food preservation according to claim 1, wherein in the step (1), the low-temperature stirring temperature is-20 to-5 ℃.
4. The method for preparing a chitosan derivative for food preservation according to claim 1, wherein in the step (2), the reaction temperature is 40-80 ℃ and the reaction time is 2-3 hours.
5. The method for producing a chitosan derivative for food preservation according to claim 1, wherein in the step (3), the standing time is 8 to 16 hours.
6. A chitosan derivative for food preservation obtained by the preparation method according to any one of claims 1 to 5.
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