CN114014955B - N, O-carboxymethyl chitosan containing thiazole salt and preparation and application thereof - Google Patents
N, O-carboxymethyl chitosan containing thiazole salt and preparation and application thereof Download PDFInfo
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- 150000003557 thiazoles Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 67
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims abstract description 27
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- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 7
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- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 claims description 2
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- 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
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Abstract
The invention relates to the fields of functional food, health care products, daily chemicals and the like, in particular to a thiazole salt-containing foodN,O-carboxymethyl chitosan and its preparation and use. Containing thiazole saltsN,OThe carboxymethyl chitosan is shown as a formula I, wherein the average value range of the polymerization degree n is 10-1300. The invention has the advantages that a plurality of active groups are simultaneously introduced into 2-site amino and 6-site hydroxyl of chitosan, and tests on antioxidant activity and bacteriostatic activity show that the thiazole salt-containing chitosanN,OThe carboxymethyl chitosan has strong antioxidant activity and antibacterial activity, and the derivative has good water solubility. In addition, the preparation process of the derivative is simple, the yield is high, the operation is easy, the large-scale industrialization is easy, and the derivative can be widely popularized to the fields of functional foods, health-care products and daily chemicals.
Description
Technical Field
The invention relates to the fields of functional food, health care products, daily chemicals and the like, in particular to a thiazole salt-containing foodN,O-carboxymethyl chitosan and its preparation and use.
Background
As the only natural alkaline polysaccharide in nature, chitosan has unique physicochemical properties due to the special structure of amino groups in the molecule. The chitosan is a natural, nontoxic and rich renewable biological resource, has good biocompatibility and biodegradability, has multiple biological activities of immunoregulation, antibiosis, antioxidation, anti-inflammation and the like, and is widely applied to chemical industry, pesticides and medicinesAnd foods, etc.N,OCarboxymethyl chitosan is one of the most important chitosan derivatives, and is prepared by the substitution reaction of active hydroxyl and amino on a chitosan molecular chain with chloroacetic acid under specific conditions. Compared with the chitosan, the chitosan-chitosan composite material has the advantages that,N,Othe carboxymethyl chitosan has good water solubility, certain antibacterial activity, hygroscopicity, anti-inflammatory effect and the like, but compared with common antibacterial agents, antioxidants and the like,N,Ocarboxymethyl chitosan has a relatively weak biological activity, which is not sufficient to support its large-scale industrial development.
The antioxidant and the antibacterial agent have wide application in the fields of food, health products, daily chemicals and the like. Antioxidants and antibacterial agents are the most commonly used food additives in the food industry, and on the one hand, antioxidants can prevent spoilage by exerting an antioxidant effect, thereby reducing the generation of toxic substances, and on the other hand, antioxidants can delay the loss of nutrients and the change of the color and luster of foods by inhibiting the oxidation of fats and oils to produce unhealthy compounds. On the other hand, the antibacterial agent can achieve the purposes of improving the quality of food, prolonging the storage period of the food and ensuring the safety of the food by inhibiting the growth of microorganisms. In addition, for human body, antioxidants play an indispensable role in delaying body aging, promoting cardiovascular and cerebrovascular health and inhibiting the growth of malignant tumors, and are main active substances in various functional foods and health care products.
As a directional, efficient and convenient synthesis means, the chemical modification can improve and even endow the polysaccharide with new functions so as to meet different requirements. To pairN,OCarboxymethyl chitosan is subject to further research at present, because it is subjected to targeted chemical structure modification, so that the bioactivity of carboxymethyl chitosan can be enhanced, a large number of novel functional products can be provided, and high-valued development of chitosan can be realized, so that the economic value of chitosan can be improved.
Disclosure of Invention
To solve the above technical problems, the present invention provides a thiazole salt-containing compositionN,O-carboxymethyl chitosan and its preparation and use.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
thiazole salt-containingN,OCarboxymethyl chitosan, thiazole salt-containingN,O-carboxymethyl chitosan is represented by formula one:
wherein the average value range of the polymerization degree n is 10-1300.
Thiazole salt-containingN,OThe preparation method of the (E) -carboxymethyl chitosan comprises the steps of taking chitosan as a raw material, carrying out carboxymethylation on 2-amino and 6-hydroxyl simultaneously, and then reacting with 2-aminothiazole to obtain the (E) -carboxymethyl chitosanN,OGrafting 2-aminothiazole derivative with carboxymethyl chitosan, and reacting the product with methyl iodide to obtain thiazole saltN,O-carboxymethyl chitosan.
Specifically, the method comprises the following steps:
（1）N,O-synthesis of carboxymethyl chitosan: dispersing chitosan in isopropanol to swell for 1-2 h, then dropwise adding sodium hydroxide aqueous solution into the swelled chitosan for 1-2 h for alkalization; then adding chloroacetic acid aqueous solution, and continuing to react for 4-6 h at 50-60 ℃ to obtainN,O-carboxymethyl chitosan, wherein the molar ratio of chitosan, sodium hydroxide, chloroacetic acid is 1: 4-6: 4-6;
（2）N,O-synthesis of carboxymethyl chitosan grafted 2-aminothiazole: will be provided withN,ODissolving carboxymethyl chitosan in dimethyl sulfoxide, sequentially adding 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride to activate for 1-2 h, and adding 2-aminothiazole andNhydroxy succinimide, reacting for 18-24 h at 25 ℃ in a dark place, and obtaining the product after reactionN,O-carboxymethyl chitosan grafted 2-aminothiazole, wherein,N,O-the molar ratio of carboxymethyl chitosan, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 2-aminothiazole, N-hydroxysuccinimide compound is 1:1-3:4-6: 1-3;
(3) containing thiazole saltsN,O-synthesis of carboxymethyl chitosan: mixing the aboveN,ODissolving carboxymethyl chitosan grafted 2-aminothiazole in dimethyl sulfoxideDissolving in sulfone, dripping methyl iodide, refluxing at 70-80 deg.C for 6-8 hr to obtain thiazole saltN, O-carboxymethyl chitosan, whereinN,OThe molar weight ratio of the-carboxymethyl chitosan grafted 2-aminothiazole to the methyl iodide is 1: 3-6.
In the step (1), chitosan is dispersed into isopropanol, and the concentration of the chitosan in the dispersion liquid is 10-20 wt%;
dropwise adding sodium hydroxide aqueous solution into the swelled chitosan by times, wherein 1-1.5 mL of sodium hydroxide aqueous solution is dropwise added each time, and the time interval for dropwise adding sodium hydroxide is 10-20 minutes; wherein, the concentration of the sodium hydroxide aqueous solution is 40 to 45 percent;
the concentration of the chloroacetic acid aqueous solution is 10-20%.
Precipitating and washing a product obtained after the reaction in the step (1) by using absolute ethyl alcohol, filtering and freeze-drying to obtainN,O-carboxymethyl chitosan.
In the step (2), theN,O-carboxymethyl chitosan is dissolved in a solution obtained in dimethyl sulfoxideN,OThe concentration of the-carboxymethyl chitosan is 10-20%.
Precipitating and washing the product obtained after the reaction in the step (2) by using absolute ethyl alcohol to obtain the catalystN,O-carboxymethyl chitosan grafted 2-aminothiazole.
In the step (3), theN,ODissolving carboxymethyl chitosan grafted 2-aminothiazole in dimethyl sulfoxide to obtain solutionN,OThe concentration of the-carboxymethyl chitosan grafted 2-aminothiazole is 10-20%.
Thiazole salt-containingN,OUse of carboxymethyl chitosan, said thiazole salt-containingN,O-the use of carboxymethyl chitosan as an antioxidant or antibacterial agent in the field of functional foods, health products or daily chemicals.
The invention has the advantages that:
(1) the invention relates to a method for producing thiazole-containing saltsN,OThe carboxymethyl chitosan takes amino and hydroxyl of the chitosan as active sites, and introduces carboxymethyl groups and thiazole salt groups through chemical modification, so that the active groups take the chitosan as a main body to play antioxidant activity and antibacterial activity, and simultaneously, the advantages of no toxicity, degradability, good biocompatibility and the like of the chitosan are maintained. Fruit of Chinese wolfberryThe results of the experiments prove that the thiazole salt is containedN,OThe carboxymethyl chitosan has excellent antioxidant activity and antibacterial activity and has high application potential.
(2) The thiazole salt-containing compound obtained by chemical modificationN,OThe water solubility of the carboxymethyl chitosan is improved, the application range is expanded, and the application prospect is improved.
(3) In the synthesis process, the invention has the advantages of simple experimental steps, simple and convenient operation, wide raw materials and higher product synthesis yield, and can be widely applied to the fields of functional foods, health-care products, daily chemicals and the like.
Drawings
FIG. 1 is a view for showing thiazole salt-containing compounds provided in examples of the present inventionN,O-synthetic scheme for carboxymethyl chitosan.
FIG. 2 is an infrared spectrum of chitosan provided in an embodiment of the present invention; 3416 cm-1The position is the stretching vibration of OH on the chitosan, 2876 cm-1Stretching vibration of position CH, 1088 cm-1Stretching vibration of C-O on chitosan is adopted.
FIG. 3 is a schematic diagram of an embodiment of the present inventionN,O-infrared spectrum of carboxymethyl chitosan; 3417 cm-1Is arranged asN,OStretching vibration of OH on carboxymethyl chitosan at 1732 cm in comparison with the Chitosan IR spectrum-1A new characteristic absorption peak appears, belonging to the characteristic absorption of COOH after the chitosan introduces carboxymethyl, proving thatN,OSuccessful synthesis of carboxymethyl chitosan.
FIG. 4 is a schematic diagram of an embodiment of the present inventionN,O-infrared spectrogram of carboxymethyl chitosan grafted 2-aminothiazole; 3397 cm-1Is arranged asN,OStretching vibration of OH on carboxymethyl chitosan grafted 2-aminothiazole, withN,OComparison of infrared spectrum of-carboxymethyl chitosan at 1662 cm-1A new characteristic absorption peak appears at the position, which is attributed to the characteristic absorption of an amido bond generated after the reaction of an amino group and a carboxyl group, and is at 1538 cm-1A new characteristic absorption peak appears, which is attributed to the characteristic absorption of the introduced thiazole group, and proves thatN,OSuccessful synthesis of carboxymethyl chitosan grafted 2-aminothiazole.
FIG. 5 shows the present inventionExamples provide for thiazole-containing saltsN,O-infrared spectrum of carboxymethyl chitosan; andN,Othe infrared spectrum of the-carboxymethyl chitosan grafted 2-aminothiazole is 1662 cm-1A new characteristic absorption peak appears, which belongs to the characteristic absorption of amido bond generated after the reaction of amino and carboxyl, and is at 1483 cm-1A new characteristic absorption peak is appeared and is attributed to N-CH on the introduced thiazole salt3Characteristic absorption of thiazole saltN,OSuccessful synthesis of carboxymethyl chitosan.
Detailed Description
The following examples are further illustrative of the present invention, but the present invention is not limited to the preparation method and use in the present embodiment.
Example 1
Synthesis of thiazole-containing salt of target Compound as shown in FIG. 1N,O-synthetic route for carboxymethyl chitosan:
（1）N,O-synthesis of carboxymethyl chitosan: dispersing 0.01 mol of chitosan (see figure 2) in 10 mL of isopropanol to swell for 1 h, then dropwise adding (10 minutes at intervals) 4 mL of 40% sodium hydroxide aqueous solution into the swelled chitosan solution for 4 times, and alkalifying for 1 h; adding 36 mL of 10% chloroacetic acid aqueous solution after alkalization, and continuing to react for 4 h at 50 ℃; finally precipitating and washing by absolute ethyl alcohol, filtering and freeze-drying to obtainN,OCarboxymethyl chitosan (see figure 3);
（2）N,O-synthesis of carboxymethyl chitosan grafted 2-aminothiazole: 0.01 mol ofN,ODissolving carboxymethyl chitosan in 12 mL of dimethyl sulfoxide, adding 0.01 mol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to activate for 1 h, then adding 0.04 mol of 2-aminothiazole and 0.01 mol of 2-aminothiazoleNReacting hydroxy succinimide at 25 deg.C in dark for 18 h, precipitating with anhydrous ethanol, and washing to obtain final productN,OCarboxymethyl chitosan grafted 2-aminothiazole (see figure 4);
(3) containing thiazole saltsN,O-synthesis of carboxymethyl chitosan: mixing the above 0.01 molN,ODissolving the-carboxymethyl chitosan grafted 2-aminothiazole in 40 mL of dimethyl sulfoxide, and then dropwise adding methyl iodide 4.5 m into the solutionL, refluxing and reacting for 6 h at 70 ℃, then precipitating and washing by using absolute ethyl alcohol to obtain thiazole salt-containing compound shown as the formula IN,OCarboxymethyl chitosan, n =50 (see fig. 5).
Example 2
The difference from the embodiment 1 is that:
（1）N,O-synthesis of carboxymethyl chitosan: 0.01 mol of chitosan is dispersed in 13 mL of isopropanol to swell for 1.5 h, then 5 mL of 40% sodium hydroxide aqueous solution is added dropwise (15 minutes at each time interval) into the swelled chitosan solution for 4 times, and alkalization is carried out for 1.5 h; adding 45 mL of 10% chloroacetic acid aqueous solution after alkalization, and continuing to react for 5 h at the temperature of 55 ℃; finally precipitating and washing by absolute ethyl alcohol, filtering and freeze-drying to obtainN,O-carboxymethyl chitosan;
（2）N,O-synthesis of carboxymethyl chitosan grafted 2-aminothiazole: 0.01 mol ofN,ODissolving carboxymethyl chitosan in 16 mL of dimethyl sulfoxide, adding 0.02 mol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to activate for 1 h, then adding 0.05 mol of 2-aminothiazole and 0.02 mol of 2-aminothiazoleNReacting hydroxy succinimide at 25 deg.C in dark for 20 hr, precipitating with anhydrous ethanol, and washing to obtain final productN,O-carboxymethyl chitosan grafted 2-aminothiazole;
(3) containing thiazole saltsN,O-synthesis of carboxymethyl chitosan: mixing the above 0.01 molN,ODissolving the-carboxymethyl chitosan grafted 2-aminothiazole in 45 mL of dimethyl sulfoxide, dropwise adding 5 mL of iodomethane into the solution, carrying out reflux reaction at 75 ℃ for 7 h, then precipitating with absolute ethyl alcohol and washing to obtain the thiazole salt-containing compound shown in the formula IN,O-carboxymethyl chitosan, n = 500.
Example 3
The difference from the embodiment 1 is that:
（1）N,O-synthesis of carboxymethyl chitosan: dispersing 0.01 mol of chitosan in 15 mL of isopropanol to swell for 2 h, then dropwise adding 6 mL of 40% sodium hydroxide aqueous solution into the swelled chitosan solution for 4 times (each time at intervals of 20 minutes), and alkalizing for 2 h; adding 50 mL of 10% chloroacetic acid aqueous solution after alkalization, and continuing to react for 6 h at the temperature of 55 ℃; finally using anhydrous waterPrecipitating with ethanol, washing, filtering, and lyophilizing to obtainN,O-carboxymethyl chitosan;
（2）N,O-synthesis of carboxymethyl chitosan grafted 2-aminothiazole: 0.01 mol ofN,ODissolving carboxymethyl chitosan in 20 mL of dimethyl sulfoxide, adding 0.03 mol of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to activate for 1 h, then adding 0.06 mol of 2-aminothiazole and 0.03 mol of 2-aminothiazoleNReacting hydroxy succinimide at 25 deg.C in dark for 24 hr, precipitating with anhydrous ethanol, and washing to obtain final productN,O-carboxymethyl chitosan grafted 2-aminothiazole;
(3) containing thiazole saltsN,O-synthesis of carboxymethyl chitosan: mixing the above 0.01 molN,ODissolving the-carboxymethyl chitosan grafted 2-aminothiazole in 50 mL of dimethyl sulfoxide, dropwise adding 5.5 mL of iodomethane into the solution, carrying out reflux reaction at 80 ℃ for 8 h, then precipitating with absolute ethyl alcohol and washing to obtain the thiazole salt-containing compound shown in the formula IN,O-carboxymethyl chitosan, n = 1300.
Application example 1
Determination of antioxidant Activity
1) Determination of superoxide anion scavenging antioxidant capacity: respectively measuring chitosan,N,O-carboxymethyl chitosan,N,O-carboxymethyl chitosan grafted 2-aminothiazole, thiazole salt-containingN,OThe superoxide anion scavenging ability of carboxymethyl chitosan and comparison (table 1). The operation process is as follows:
the experimental chitosan in the examples,N,O-carboxymethyl chitosan,N,O-carboxymethyl chitosan grafted 2-aminothiazole, thiazole salt-containingN,OAnd (3) respectively carrying out vacuum freeze drying on the carboxymethyl chitosan to constant weight to obtain test samples, and respectively preparing solutions with the concentrations of 0.2, 0.4, 0.8, 1.6 and 3.2 mg/mL by using Tris-HCl buffer solutions (called as Tris (hydroxymethyl) aminomethane 1.9382 g, adding 0.8 mL of concentrated HCl, dissolving with deionized water and fixing the volume to 1000 mL) for different samples. Taking 1.5 mL of different sample solutions with different concentrations, 1.5 mL of Tris-HCl buffer solution and 0.5 mL of NADH (468 mu M), adding 0.5 mL of PMS (60 mu M) into the reaction solution, mixing in a test tube to obtain final concentrations of 0.1, 0.2, 0.4, 0.8 and 1.6 mg/mL, and keeping the final concentrations at room temperatureThe reaction was kept away from light for 5 minutes, and the absorbance was measured at 560 nm, and the blank set was made up of 0.5 mL of Tris-HCl buffer solution in place of NADH (Note: the samples to be measured were measured three times, and the average value was taken). The superoxide anion radical scavenging capacity is calculated as follows:
wherein
Is the absorbance of the blank set, and,
is the absorbance of the sample set.
2) Determination results of superoxide anion scavenging antioxidant capacity:
TABLE 1 Chitosan,N,O-carboxymethyl chitosan,N,O-carboxymethyl chitosan grafted 2-aminothiazole and thiazole salt-containing compoundsN,O-superoxide anion scavenging ability of carboxymethyl chitosan (%)
As can be seen from table 1, when active groups such as thiazole salt and carboxymethyl group are introduced into chitosan molecules by chemical structure modification, the antioxidant ability of chitosan can be significantly improved. The obtained thiazole salt-containing compoundsN,OThe carboxymethyl chitosan has excellent antioxidant performance, as shown in the table: containing thiazole saltsN,OThe carboxymethyl chitosan has excellent scavenging effect on superoxide anion free radicals, and the scavenging rate reaches 100% at the concentration of 0.8 mg/mL.
Application example 2
Bacteriostatic Activity assay
1) Assay for inhibition of staphylococcus aureus: respectively measuring chitosan,N,O-carboxymethyl chitosan,N,O-carboxymethyl chitosan grafted 2-aminothiazole, thiazole salt-containingN,OPara-gold using carboxymethyl chitosan as sampleInhibition of Staphylococcus aureus and comparison (tables 2, 3). The operation process is as follows:
weighing 10 g of tryptone, 5 g of yeast extract and 10 g of sodium chloride in a beaker, adding a small amount of purified water, dissolving, supplementing water to 1000 mL, adjusting the pH to 7, and subpackaging in conical bottles with the volumes of 20 mL, 19 mL and 18 mL respectively. Sealing, and autoclaving for 30 min. The sample to be tested is dissolved by distilled water, and the original concentration is 10 mg/mL.
In a clean bench, 2 mL, 1 mL and 0.2 mL of sample solutions are added into 18 mL, 19 mL and 20 mL of culture media respectively to prepare culture media with sample contents of 1 mg/mL, 0.5 mg/mL and 0.1 mg/mL respectively. And respectively inoculating equal volumes of rejuvenated test bacteria suspension into the culture medium containing the sample and the control by taking equal volumes of sterile water as a negative control and medium with equal volumes as a blank control, and culturing at 37 ℃ for 24 hours. In the culture process, the absorbance of the bacterial suspension at the wavelength of 600 nm is measured for 8 hours and 16 hours respectively, the bacteriostasis rate is calculated, the experiment is repeated for three times, and the bacteriostasis rate calculation formula is as follows:
wherein
The absorbance of the blank control bacterial suspension at 600 nm,
is the absorbance at 600 nm before the blank control bacterial suspension is cultured,
is the absorbance of the bacterial suspension of the sample to be detected at 600 nm,
the absorbance at 600 nm before the bacterial suspension of the sample to be detected is cultured.
2) Assay for inhibition of staphylococcus aureus:
TABLE 2 chitosan after 8 h of incubation,N,O-carboxymethyl chitosan,N,O-carboxymethyl chitosan grafted 2-aminothiazole and thiazole salt-containing compoundsN,O-inhibitory Activity of carboxymethyl Chitosan on Staphylococcus aureus (%)
TABLE 3 chitosan after 16 h of incubation,N,O-carboxymethyl chitosan,N,O-carboxymethyl chitosan grafted 2-aminothiazole and thiazole salt-containing compoundsN,O-inhibitory Activity of carboxymethyl Chitosan on Staphylococcus aureus (%)
As can be seen from tables 2 and 3, when active groups such as thiazole salt and carboxymethyl group are introduced into chitosan molecules by chemical structure modification, the antibacterial ability of chitosan can be significantly improved. The obtained thiazole salt-containing compoundsN,OCarboxymethyl chitosan is excellent in bacteriostasis.
In general, the thiazole salt-containing compoundsN,OCarboxymethyl chitosan has excellent antioxidant activity and antibacterial activity, and has good water solubility. Meanwhile, the method has the advantages of simple experimental steps, simple and convenient operation, wide raw materials and high product synthesis yield, and provides technical support for developing a novel antioxidant and antibacterial agent applied to the fields of functional foods, health-care products, daily chemicals and the like.
Claims (9)
1. Thiazole salt-containingN,O-carboxymethyl chitosan, characterized in that: containing thiazole saltsN,O-carboxymethyl chitosan is represented by formula one:
wherein the average value range of the polymerization degree n is 10-1300.
2. A thiazole salt-containing composition according to claim 1N,O-a process for the preparation of carboxymethyl chitosan, characterized in that: using chitosan as raw material, firstly carrying out carboxymethylation on 2-amino and 6-hydroxyl at the same time, and then reacting with 2-aminothiazole to obtain the chitosanN,OGrafting 2-aminothiazole derivative with carboxymethyl chitosan, and reacting the product with methyl iodide to obtain thiazole saltN,O-carboxymethyl chitosan.
3. Thiazole salt-containing composition according to claim 2N,O-a process for the preparation of carboxymethyl chitosan, characterized in that:
（1）N,O-synthesis of carboxymethyl chitosan: dispersing chitosan in isopropanol to swell for 1-2 h, then dropwise adding sodium hydroxide aqueous solution into the swelled chitosan for 1-2 h for alkalization; then adding chloroacetic acid aqueous solution, and continuing to react for 4-6 h at 50-60 ℃ to obtainN,O-carboxymethyl chitosan, wherein the molar ratio of chitosan, sodium hydroxide, chloroacetic acid is 1: 4-6: 4-6;
（2）N,O-synthesis of carboxymethyl chitosan grafted 2-aminothiazole: will be provided withN,ODissolving carboxymethyl chitosan in dimethyl sulfoxide, sequentially adding 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride to activate for 1-2 h, and adding 2-aminothiazole andNhydroxy succinimide, reacting for 18-24 h at 25 ℃ in a dark place, and obtaining the product after reactionN,O-carboxymethyl chitosan grafted 2-aminothiazole, wherein,N,O-the molar ratio of carboxymethyl chitosan, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 2-aminothiazole, N-hydroxysuccinimide compound is 1:1-3:4-6: 1-3;
(3) containing thiazole saltsN,O-synthesis of carboxymethyl chitosan: mixing the aboveN,ODissolving the-carboxymethyl chitosan grafted 2-aminothiazole in dimethyl sulfoxide, dripping methyl iodide after dissolving, and carrying out reflux reaction at 70-80 ℃ for 6-8 h to obtain the thiazole salt-containing productN,O-carboxymethyl chitosan, whereinN,O-carboxymethyl chitosan grafting 2-aminothiazole, methyl iodideThe molar ratio of (A) to (B) is 1: 3-6.
4. Process for preparing thiazole-containing salts according to claim 3N,O-a process for the preparation of carboxymethyl chitosan, characterized in that: in the step (1), chitosan is dispersed into isopropanol, and the concentration of the chitosan in the dispersion liquid is 10-20 wt%;
dropwise adding sodium hydroxide aqueous solution into the swelled chitosan by times, wherein 1-1.5 mL of sodium hydroxide aqueous solution is dropwise added each time, and the time interval for dropwise adding sodium hydroxide is 10-20 minutes; wherein, the concentration of the sodium hydroxide aqueous solution is 40 to 45 percent;
the concentration of the chloroacetic acid aqueous solution is 10-20%.
5. Process for preparing thiazole-containing salts according to claim 3 or 4N,O-a process for the preparation of carboxymethyl chitosan, characterized in that: precipitating and washing a product obtained after the reaction in the step (1) by using absolute ethyl alcohol, filtering and freeze-drying to obtainN,O-carboxymethyl chitosan.
6. Process for preparing thiazole-containing salts according to claim 3N,O-a process for the preparation of carboxymethyl chitosan, characterized in that: in the step (2), theN,O-carboxymethyl chitosan is dissolved in a solution obtained in dimethyl sulfoxideN,OThe concentration of the-carboxymethyl chitosan is 10-20%.
7. Process for preparing thiazole-containing salts according to claim 3 or 6N,O-a process for the preparation of carboxymethyl chitosan, characterized in that: precipitating and washing the product obtained after the reaction in the step (2) by using absolute ethyl alcohol to obtain the catalystN,O-carboxymethyl chitosan grafted 2-aminothiazole.
8. Process for preparing thiazole-containing salts according to claim 3N,O-a process for the preparation of carboxymethyl chitosan, characterized in that: in the step (3), theN,ODissolving carboxymethyl chitosan grafted 2-aminothiazole in dimethyl sulfoxide to obtain solutionN,OThe concentration of the-carboxymethyl chitosan grafted 2-aminothiazole is 10-20%.
9. A kind ofThiazole salt-containing composition according to claim 1N,O-use of carboxymethyl chitosan, characterized in that: of the thiazole-containing saltN,O-the use of carboxymethyl chitosan as an antioxidant or antibacterial agent in the field of functional foods, health products or daily chemicals.
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