CN113248737A - Preparation method of self-repairing antibacterial hydrogel - Google Patents
Preparation method of self-repairing antibacterial hydrogel Download PDFInfo
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- CN113248737A CN113248737A CN202110652933.9A CN202110652933A CN113248737A CN 113248737 A CN113248737 A CN 113248737A CN 202110652933 A CN202110652933 A CN 202110652933A CN 113248737 A CN113248737 A CN 113248737A
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J2305/04—Alginic acid; Derivatives thereof
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Abstract
The invention discloses a preparation method of self-repairing antibacterial hydrogel, which comprises the following steps: modifying L-cysteine (Cys) on a branched chain of carboxymethyl Chitosan (CSA) to obtain cysteine-carboxymethyl chitosan (Cys-CS-COOH); step two, oxidizing Sodium Alginate (SA) by sodium periodate to obtain aldehyde sodium alginate (SA-CHO); and step three, adding 3-butyn-2-one into the SA-CHO solution, uniformly mixing, adding an equal volume of cysteine-carboxymethyl chitosan solution (Cys-CSA), stirring, and standing to obtain the antibacterial self-repairing hydrogel. The method provided by the invention is simple, the gelling condition is mild, and the hydrogel has self-repairing and bacteriostatic functions, so that more practical applications of the hydrogel can be met.
Description
Technical Field
The invention belongs to the field of antibacterial engineering materials, and relates to a preparation method of self-repairing antibacterial hydrogel.
Background
The antibacterial material is a novel functional material with the function of killing or inhibiting microorganisms, and has extremely wide application prospect in the fields of medical treatment, household products, household appliances, food packaging and the like. The self-repairing hydrogel is a novel intelligent material, has huge potential application value in the fields of biological pharmacy, daily chemical industry and the like, and has certain requirements on the antibacterial property of the material in the fields. The traditional preparation method of the antibacterial hydrogel mainly embeds the antibacterial factors in the hydrogel, the antibacterial effect is realized through release, the released antibacterial factors are easy to pollute the environment, and the hydrogel faces strict environmental supervision requirements. Therefore, the development of novel antibacterial self-repairing hydrogel has certain urgency.
Organic matters with bactericidal and bacteriostatic properties in nature, such as chitosan, sodium alginate and other secondary metabolites of living organisms which can produce specific inhibitory action on bacteria. At present, chitosan and sodium alginate are natural polysaccharides, have oxidation resistance, antibacterial property, biocompatibility and the like, and are widely applied to the fields of biological pharmacy, daily chemical industry and the like.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a self-repairing antibacterial hydrogel, the preparation method is simple and easy to operate, the gelling condition is mild, and the prepared hydrogel has good antibacterial and self-repairing functions.
The invention provides a preparation method of self-repairing antibacterial hydrogel, which comprises the following steps:
s1, dropping a mixed solution of EDC and NHS into a carboxymethyl chitosan solution, then adding cysteine (Cys), reacting for 8-12h, dialyzing, and freeze-drying to obtain cysteine-carboxymethyl chitosan (Cys-CSA);
s2, adding sodium alginate solution into sodium periodate, reacting for 6-12h in a dark place to obtain reaction liquid, adding glycol to remove residual sodium periodate in the reaction liquid, dialyzing, and freeze-drying to obtain aldehyde sodium alginate (SA-CHO);
s3, respectively preparing a cysteine-carboxymethyl chitosan aqueous solution and an aldehyde sodium alginate aqueous solution;
s4, adding 3-butyn-2-one into the aldehyde sodium alginate aqueous solution, and uniformly mixing to obtain an aldehyde sodium alginate aqueous solution containing 3-butyn-2-one;
s5, mixing the aldehyde sodium alginate aqueous solution containing the 3-butyne-2-ketone with the cysteine-carboxymethyl chitosan aqueous solution, stirring, and standing to obtain the antibacterial self-repairing hydrogel.
Further, in step S1, the amount of the mixed solution of EDC and NHS is 1mL and the amount of cysteine is 100-200mg per 100mL of carboxymethyl chitosan solution.
Furthermore, in the mixed solution of EDC and NHS, the concentration of EDC is 94.5-189mg/mL, and the concentration of NHS is 57-114 mg/mL.
Further, the dialysis specifically comprises: dialyzed against 0.01M aqueous sodium chloride for 3 days.
Further, in step S2, the concentration of the sodium alginate solution is 10-20 mg/mL.
Further, in step S2, the mass ratio of sodium alginate in the sodium alginate solution to sodium periodate is 1: 3.
Further, in step S2, the dosage of ethylene glycol is: ethylene glycol was added in an amount of 0.5 to 1mL per 100mL of the reaction mixture.
Further, in step S3, the concentration of the aldehyde sodium alginate aqueous solution is 40-45 mg/mL; the concentration of the cysteine-carboxymethyl chitosan aqueous solution is 40-45 mg/mL.
Further, in step S3, the concentration of the 3-butyn-2-one in the aldehyde sodium alginate aqueous solution containing the 3-butyn-2-one is 10 ul/mL.
Further, in step S3, the volume ratio of the aldehyde sodium alginate aqueous solution containing 3-butyn-2-one to the cysteine-carboxymethyl chitosan aqueous solution is 1: 1.
Compared with the prior art, the hydrogel is successfully prepared based on the reversible reaction of Schiff base and nucleophilic; the method is simple and effective, the operation is simple and convenient, and the gelling condition is mild; the prepared hydrogel not only has an antibacterial effect, but also has a good self-repairing effect, and has a good application prospect in the field of antibacterial engineering materials.
Drawings
FIG. 1 is a physical representation of the products prepared in comparative example 1 and example 1. Wherein FIG. 1 is the product of comparative example 1 to the left; FIG. 1 is the product of example 1 (self-healing antimicrobial hydrogel) on the right;
FIG. 2 is a self-healing graph of a self-healing antimicrobial hydrogel made according to example 1. Wherein the hydrogel is cut open at the left side of the figure 2; FIG. 2 is a view of the hydrogel healing process;
FIG. 3 is an antimicrobial pattern of the self-healing antimicrobial hydrogel prepared in example 1. Wherein the left of figure 3 is a diagram of the hydrogel inhibiting escherichia coli; FIG. 3 is a graph showing the inhibition of Staphylococcus aureus by the hydrogel.
Detailed Description
Example 1
1) Dropping 1mL of mixed solution of 189mg/mL EDC and 114mg/mL NHS into 100mL of carboxymethyl Chitosan (CSA) solution with the concentration of 10mg/mL, then adding 200mg of cysteine (Cys), reacting for 12h, dialyzing for 3 days by using 0.01M sodium chloride (NaCl) aqueous solution, and freeze-drying to obtain pure cysteine-modified carboxymethyl chitosan (Cys-CSA).
2) Preparing 100mL of SA solution with the concentration of 20mg/mL, adding 6g of sodium periodate with the concentration of 60mg/mL, reacting for 12 hours in a dark place, adding 1mL of glycol to remove excessive sodium periodate, reacting for 2 hours, dialyzing for 3 days, and freeze-drying to obtain the aldehyde sodium alginate (SA-CHO).
3) Respectively preparing a 45mg/mL cysteine modified carboxymethyl chitosan (Cys-CSA) aqueous solution and an aldehyde sodium alginate (SA-CHO) aqueous solution;
4) adding 3-butyn-2-one into SA-CHO aqueous solution in a dark place to obtain aldehyde sodium alginate aqueous solution containing 3-butyn-2-one, wherein the concentration of the aldehyde sodium alginate aqueous solution is 10ul/mL, mixing 0.5mL of aldehyde sodium alginate aqueous solution containing 3-butyn-2-one with 0.5mL of cystine modified carboxymethyl chitosan (Cys-CSA) aqueous solution in an equal volume, stirring and standing to obtain the self-repairing antibacterial hydrogel.
Example 2
1) Dripping 1mL of mixed solution of 94.5mg/mL EDC and 57mg/mL NHS into 100mL of carboxymethyl Chitosan (CSA) solution with the concentration of 5mg/mL, then adding 100mg of cysteine (Cys) with the concentration of 1mg/mL, reacting for 8h, dialyzing for 3 days by using 0.01M sodium chloride (NaCl) aqueous solution, and freeze-drying to obtain pure cysteine modified carboxymethyl chitosan (Cys-CSA).
2) Preparing 100mL of SA solution with the concentration of 10mg/mL, adding 3g of sodium periodate with the concentration of 30mg/mL, reacting for 6 hours in a dark place, adding 1mL of glycol to remove excessive sodium periodate, and adding glycol with the volume ratio of the glycol to the solution of 0.5: 100, reacting for 2h, dialyzing for 3 days, and freeze-drying to obtain pure aldehyde sodium alginate (SA-CHO).
3) Respectively preparing 40mg/mL cysteine modified carboxymethyl chitosan (Cys-CSA) aqueous solution and aldehyde sodium alginate (SA-CHO) aqueous solution;
4) adding 3-butyn-2-one into SA-CHO aqueous solution in a dark place to obtain aldehyde sodium alginate aqueous solution containing 3-butyn-2-one, wherein the concentration of the aldehyde sodium alginate aqueous solution is 10ul/mL, mixing 1mL of aldehyde sodium alginate aqueous solution containing 3-butyn-2-one and 1mL of cystine modified carboxymethyl chitosan (Cys-CSA) aqueous solution, and stirring and standing to obtain the self-repairing antibacterial hydrogel.
Example 3
1) Dropping 1mL of mixed solution of 189mg/mL EDC and 114mg/mL NHS into 100mL of carboxymethyl Chitosan (CSA) solution with the concentration of 10mg/mL, then adding 200mg of cysteine (Cys) with the concentration of 2mg/mL, reacting for 8h, dialyzing for 3 days by using 0.01M sodium chloride (NaCl) aqueous solution, and freeze-drying to obtain pure cysteine modified carboxymethyl chitosan (Cys-CSA).
2) Preparing 100mL of SA solution with the concentration of 20mg/mL, adding 6g of sodium periodate with the concentration of 60mg/mL, reacting for 10 hours in a dark place, adding 1mL of glycol to remove excessive sodium periodate, reacting for 2 hours, dialyzing for 3 days, and freeze-drying to obtain the aldehyde sodium alginate (SA-CHO).
3) Respectively preparing a 43mg/mL cysteine modified carboxymethyl chitosan (Cys-CSA) aqueous solution and an aldehyde sodium alginate (SA-CHO) aqueous solution;
4) adding 3-butyn-2-one into SA-CHO aqueous solution in a dark place to obtain aldehyde sodium alginate aqueous solution containing 3-butyn-2-one, wherein the concentration of the aldehyde sodium alginate aqueous solution is 10ul/mL, and 1mL of the aldehyde sodium alginate aqueous solution containing 3-butyn-2-one is mixed with 1mL of cystine modified carboxymethyl chitosan (Cys-CSA) aqueous solution, and stirring and standing to obtain the self-repairing antibacterial hydrogel.
Comparative example 1 (without 3-butyn-2-one)
1) Dropping 1mL of mixed solution of 189mg/mL EDC and 114mg/mL NHS into 100mL of carboxymethyl Chitosan (CSA) solution with the concentration of 10mg/mL, then adding 200mg of cysteine (Cys), reacting for 12h, dialyzing for 3 days by using 0.01M sodium chloride (NaCl) aqueous solution, and freeze-drying to obtain pure cysteine-modified carboxymethyl chitosan (Cys-CSA).
2) Preparing 100mL of SA solution with the concentration of 20mg/mL, adding 6g of sodium periodate with the concentration of 60mg/mL, reacting for 12 hours in a dark place, adding 1mL of glycol to remove excessive sodium periodate, reacting for 2 hours, dialyzing for 3 days, and freeze-drying to obtain the aldehyde sodium alginate (SA-CHO).
3) Respectively preparing a 45mg/mL cysteine modified carboxymethyl chitosan (Cys-CSA) aqueous solution and an aldehyde sodium alginate (SA-CHO) aqueous solution;
4) 0.5mL of aldehyde sodium alginate aqueous solution and 0.5mL of cystine modified carboxymethyl chitosan (Cys-CSA) aqueous solution are mixed in equal volume, stirred and kept stand.
FIG. 1 is a physical representation of the products prepared in comparative example 1 and example 1. Wherein FIG. 1 is the product of comparative example 1 to the left; FIG. 1 is the product of example 1 (self-healing antimicrobial hydrogel) on the right; as can be seen from FIG. 1, if the aldehyde sodium alginate aqueous solution does not contain 3-butyn-2-one, the final product cannot form hydrogel; if 3-butyn-2-one is contained, a hydrogel pattern can be formed.
The self-repairing antibacterial hydrogel prepared in example 1 is cut and placed in a glass dish, and the hydrogel is healed after 60 seconds, and the process is schematically shown in FIG. 2. Wherein the hydrogel is cut open at the left side of the figure 2; figure 2 is the right view of the hydrogel healing process. As can be seen from FIG. 2, the hydrogel prepared in example 1 has a good self-repairing effect.
FIG. 3 is an antimicrobial pattern of the self-healing antimicrobial hydrogel prepared in example 1. Wherein the left of figure 3 is a diagram of the hydrogel inhibiting escherichia coli; FIG. 3 is a graph showing the inhibition of Staphylococcus aureus by the hydrogel.
Examples of the experiments
The self-repairing antibacterial hydrogel obtained in example 1 is co-cultured with escherichia coli or staphylococcus aureus and incubated at 37 ℃ for 12 hours, and the result is shown in fig. 3, wherein the left side of fig. 3 in fig. 3 is a diagram of the hydrogel inhibiting escherichia coli; FIG. 3 is a graph showing the inhibition of Staphylococcus aureus by the hydrogel. As can be seen from FIG. 3, the hydrogel obtained in example 1 had a good antibacterial effect.
Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (10)
1. A preparation method of self-repairing antibacterial hydrogel is characterized by comprising the following steps:
s1, dropping a mixed solution of EDC and NHS into a carboxymethyl chitosan solution, then adding cysteine (Cys), reacting for 8-12h, dialyzing, and freeze-drying to obtain cysteine-carboxymethyl chitosan (Cys-CSA);
s2, adding sodium alginate solution into sodium periodate, reacting for 6-12h in a dark place to obtain reaction liquid, adding glycol to remove residual sodium periodate in the reaction liquid, dialyzing, and freeze-drying to obtain aldehyde sodium alginate (SA-CHO);
s3, respectively preparing a cysteine-carboxymethyl chitosan aqueous solution and an aldehyde sodium alginate aqueous solution;
s4, adding 3-butyn-2-one into the aldehyde sodium alginate aqueous solution, and uniformly mixing to obtain an aldehyde sodium alginate aqueous solution containing 3-butyn-2-one;
s5, mixing the aldehyde sodium alginate aqueous solution containing the 3-butyne-2-ketone with the cysteine-carboxymethyl chitosan aqueous solution, stirring, and standing to obtain the antibacterial self-repairing hydrogel.
2. The method of claim 1, wherein the EDC and NHS mixed solution is added in an amount of 1mL and the cysteine is added in an amount of 100-200mg per 100mL of the carboxymethyl chitosan solution in step S1.
3. The method of claim 2, wherein the mixed solution of EDC and NHS has a EDC concentration of 94.5-189mg/mL and a NHS concentration of 57-114 mg/mL.
4. The method according to claim 1, wherein the dialysis is in particular: dialyzed against 0.01M aqueous sodium chloride for 3 days.
5. The method of claim 1, wherein in step S2, the sodium alginate solution has a concentration of 10-20 mg/mL.
6. The method of claim 5, wherein in step S2, the mass ratio of sodium alginate in the sodium alginate solution to sodium periodate is 1: 3.
7. The method according to claim 1, wherein in step S2, the ethylene glycol is used in an amount of: ethylene glycol was added in an amount of 0.5 to 1mL per 100mL of the reaction mixture.
8. The preparation method according to claim 1, wherein in step S3, the concentration of the aldehyde-based sodium alginate aqueous solution is 40-45 mg/mL; the concentration of the cysteine-carboxymethyl chitosan aqueous solution is 40-45 mg/mL.
9. The method of claim 1, wherein in step S3, the concentration of 3-butyn-2-one in the aqueous solution of the aldehydized sodium alginate containing 3-butyn-2-one is 10 ul/mL.
10. The method of claim 1, wherein in step S3, the volume ratio of the aldehydized sodium alginate aqueous solution containing 3-butyn-2-one to the cysteine-carboxymethyl chitosan aqueous solution is 1: 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114524952A (en) * | 2022-03-11 | 2022-05-24 | 南通大学 | Preparation method of high-adhesion natural eggshell membrane chitosan hydrogel |
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| CN101463145A (en) * | 2009-01-12 | 2009-06-24 | 武汉理工大学 | Carboxymethyl chitosan / oxidized sodium alginate self-crosslinking antibacterial hydrogel material |
| CN101554367A (en) * | 2009-05-19 | 2009-10-14 | 武汉理工大学 | Method for preparing sulfhydryl carboxymethyl chitosan microgel applicable to mucosa delivery |
| CN110128682A (en) * | 2018-02-02 | 2019-08-16 | 华东理工大学 | Sulfydryl-cross-link hydrogel material and the preparation method and application thereof |
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Patent Citations (3)
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| CN101463145A (en) * | 2009-01-12 | 2009-06-24 | 武汉理工大学 | Carboxymethyl chitosan / oxidized sodium alginate self-crosslinking antibacterial hydrogel material |
| CN101554367A (en) * | 2009-05-19 | 2009-10-14 | 武汉理工大学 | Method for preparing sulfhydryl carboxymethyl chitosan microgel applicable to mucosa delivery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114524952A (en) * | 2022-03-11 | 2022-05-24 | 南通大学 | Preparation method of high-adhesion natural eggshell membrane chitosan hydrogel |
| CN114524952B (en) * | 2022-03-11 | 2023-09-15 | 南通大学 | Preparation method of high-adhesion natural eggshell membrane chitosan hydrogel |
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