CN114349979A - Self-healing and antibacterial ternary composite hydrogel material and preparation method and application thereof - Google Patents

Abstract

The invention relates to a self-healing and antibacterial ternary composite hydrogel material and a preparation method and application thereof. The ternary composite hydrogel material has a three-dimensional porous structure, and comprises the main components of beta-cyclodextrin, tertiary aminated polyethyleneimine, polyvinyl alcohol and water.

Description

Self-healing and antibacterial ternary composite hydrogel material and preparation method and application thereof

Technical Field

The invention relates to an antibacterial hydrogel material and a preparation method thereof, and more particularly relates to a self-healing antibacterial ternary composite hydrogel material, a preparation method thereof and application thereof in an antibacterial hydrogel dressing for an infectious wound surface.

Background

In recent years, due to frequent traffic accidents, the number of patients with acute and chronic wound injuries increases year by year. If the wound surface is damaged improperly, infection is easily caused, and an infectious wound surface is formed and is difficult to repair. At present, sterile gauze, sterile plaster and the like are mainly used as traditional dressings for wound repair clinically, but the traditional dressings do not have antibacterial performance, are poor in skin adhesion, are easy to fall off to cause secondary infection, are easy to adhere to wound tissues and difficult to remove, and are not beneficial to bacterial killing and wound healing of infectious wounds. It is therefore highly desirable to invent an ideal wound dressing to solve this problem.

The ideal dressing should have the characteristics of absorbing exudate, being easy to remove and replace, being safe, antibacterial and pollution-free, promoting wound repair and the like; the hydrogel is a hydrophilic polymer material with a three-dimensional network structure formed by crosslinking through the actions of covalent bonds, hydrogen bonds and the like, has unique water-swelling-absorbable and soft-elastic characteristics, strong group designability and good biocompatibility, and is very suitable for the design requirement of an ideal dressing. In addition, when the hydrogel is applied to wound repair, the hydrogel can protect the wound from external secondary damage, and can directly contact the skin and promote cell migration, collagen deposition and capillary formation, so that the wound repair is realized.

In order to solve the problems, Chinese patent application No. 202110287281.3 discloses that sodium alginate nano-silver antibacterial hydrogel dressing is obtained by reacting sodium alginate with carbohydrazide and other organic solvents to prepare a mixed solution, adding silver nitrate after dialysis and stirring. However, the antibacterial gel formed by the method does not have self-healing performance and the gel has poor tensile property, so that when the antibacterial gel is applied to wound dressing, the dressing is easy to crack and fall off, and the dressing is ineffective; in addition, the hydrogel formed by the method does not have self-healing performance, so the service life of the material is relatively short, and the application of the hydrogel in wound repair is limited.

beta-CD is a natural molecule derived from starch, is a cyclic oligosaccharide formed by bonding 7 glucose units, has a special cavity structure, can be used for loading and releasing drugs, can form gel by interacting with guest molecules, provides possibility for designability by multiple reaction sites, and is widely used for hydrogel construction. However, the single-component beta-CD gel has poor mechanical property and no antibacterial activity, so that the application of the single-component beta-CD gel to the repair of chronic wounds such as bacterial infection is greatly limited.

Disclosure of Invention

In view of the above problems in the prior art, the present invention aims to provide a hydrogel material with good antibacterial property and self-healing property for repairing infective wounds and a preparation method thereof. The antibacterial hydrogel can be well attached to the skin, and has good biocompatibility, excellent antibacterial performance, good tensile property and good self-healing performance.

In one aspect, the invention provides a self-healing and antibacterial ternary composite hydrogel material which has a three-dimensional porous structure and mainly comprises beta-cyclodextrin, tertiary aminated polyethyleneimine, polyvinyl alcohol and water.

Preferably, the three-dimensional network structure is obtained by chemically crosslinking beta-cyclodextrin and tertiary aminated polyethyleneimine and then physically crosslinking the crosslinked beta-cyclodextrin and the tertiary aminated polyethyleneimine with polyvinyl alcohol. Wherein, part of cyclodextrin participates in chemical reaction to form binary polymer with polyethyleneimine; and hydroxyl in the cyclodextrin can form a physical crosslinking point with amino in polyethyleneimine and hydroxyl in polyvinyl alcohol to form a physical crosslinking network.

In the invention, the cationic polymer polyethyleneimine is subjected to tertiary amination treatment by epoxy chloropropane and is chemically modified with beta-cyclodextrin, so that the cyclodextrin matrix gel has excellent antibacterial performance and certain biocompatibility. The amino group of polyethyleneimine can improve the adhesive capacity of the gel, and can be well attached to skin tissues. Meanwhile, the mechanical property of the binary compound can be improved by polyvinyl alcohol, and the biocompatibility is further improved; and the amino and the hydroxyl can form a physical cross-linked network, so that the self-healing performance of the hydrogel is endowed, and the stability of the gel is improved.

Preferably, the composition of the ternary complex hydrogel material comprises: 0.5-10 wt% of beta-cyclodextrin, 1-4 wt% of tertiary aminated polyethyleneimine, 0.1-30 wt% of polyvinyl alcohol and 56-98 wt% of water, wherein the total amount is 100 wt%. The combination of these components, and the above-mentioned ratio ranges of the components, which give the composite hydrogel of the present invention an excellent balance of the above-mentioned self-healing property, antibacterial property and biocompatibility, are determined by a large number of experiments.

Preferably, the storage modulus G 'of the ternary composite hydrogel material is higher than the loss modulus G', wherein the range of G 'is 10-10000 Pa, and the range of G' is 0-10000 Pa.

Preferably, the ternary composite hydrogel material still maintains a gel state under 1000% shear strain and has deformability.

On the other hand, the invention provides a preparation method of a self-healing and antibacterial ternary composite hydrogel material, which comprises the following steps:

(A) in an alkaline environment, modifying polyethyleneimine by using an organic solvent at the temperature of 0-50 ℃ to obtain tertiary amination polyethyleneimine;

(B) performing chemical crosslinking on cyclodextrin and tertiary aminated polyethyleneimine at the temperature of 20-80 ℃ to obtain binary composite hydrogel;

(C) and (3) mixing (blending) the obtained binary composite hydrogel with a polyvinyl alcohol solution at the temperature of 20-95 ℃, and then standing, defoaming and freezing and thawing to obtain the self-healing antibacterial ternary composite hydrogel. Wherein the blending and freeze-thawing of step (C) are two steps, the purpose of blending is to make it well mixed and uniform, and the freeze-thawing is to generate physical cross-linking points by crystallization.

Preferably, in step (a), the alkaline environment is provided by an alkaline aqueous solution; the alkali comprises at least one of sodium hydroxide, potassium hydroxide and sodium bicarbonate; the concentration of the alkaline aqueous solution is 0.01-2 mol/L; the organic solvent is epoxy chloropropane; the addition amount of the organic solvent epichlorohydrin is 11.48-114.85 wt% of the mass of the polyethyleneimine.

Preferably, in the step (B), the tertiary amination polyethyleneimine solution and ultrapure water are mixed, then the beta-cyclodextrin and the cross-linking agent are added for complete dissolution, and the reaction is carried out for 0.5 to 8 hours at the temperature of 20 to 80 ℃; the cross-linking agent is epichlorohydrin; the addition amount of the cross-linking agent is 10.43-104.32 wt% of beta-cyclodextrin.

Preferably, in the step (C), the concentration of the polyvinyl alcohol solution is 3-30 wt%;

the standing and defoaming are carried out at normal temperature and normal pressure for 0.5-24 hours;

the freezing and thawing comprises the following steps: freezing for 2-12 h at-20 to-18 ℃, and then unfreezing at 4-25 ℃; preferably, the number of times of freeze thawing is 1-5 times.

On the other hand, the invention also provides application of the self-healing and antibacterial ternary composite hydrogel material in preparation of antibacterial hydrogel dressings for infectious wounds.

Has the advantages that:

in the invention, the ternary composite hydrogel is prepared through a physical and chemical reaction and has stronger antibacterial performance (for the concentration of 10)⁷The killing rate of the CFU/mL staphylococcus aureus and the escherichia coli is 100 percent), the self-healing performance and the biocompatibility are good. The storage modulus G 'of the hydrogel is higher than the loss modulus G', the range of G 'is 10-10000 Pa, and the range of G' is 0-10000 Pa. The hydrogel can bear larger shear strain, still keeps a gel state under 1000% shear strain, and has stronger deformability.

Drawings

FIG. 1 is a sol-gel optical image of the ternary composite gel prepared in example 1, demonstrating that a uniform, stable composite gel can be successfully prepared;

FIG. 2 is the results of rheological testing of the ternary composite gel (CPP) prepared in example 1, wherein the storage modulus (G') of the ternary gel CPP is significantly higher than the gel loss modulus (G "), further confirming the successful and stable preparation of the gel. Compared with the polyvinyl alcohol (PVA) gel prepared in comparative example 2, the storage modulus and the loss modulus of the composite gel are improved, which shows that the composite gel has stronger strength and stability. And the b diagram in fig. 2 can confirm that the gel still maintains a good gel state under 1000% strain, and the composite gel is proved to have excellent tensile property and good deformability;

fig. 3 is a self-healing performance characterization of the ternary composite gel prepared in example 2, wherein after cutting and dyeing the strip-shaped gel, a "boat" -shaped gel can be obtained by splicing, and after freezing and thawing, the "boat" -shaped hydrogel can bear a certain stretch, which proves that the gel has excellent self-healing performance;

fig. 4 shows that the CPP gel prepared in example 1 is subjected to a tensile test after being destroyed and then self-healed, and the test result shows that the gel has an excellent self-healing effect and can still bear 150% of tensile force. Namely, after the gel is completely destroyed by cutting, the gel can still have certain tensile property after being spliced again;

FIG. 5 is a representation of cytotoxicity of the ternary complex gel prepared in example 1, confirming that the gel has no significant cytotoxicity to mouse fibroblast L929 and good biocompatibility;

FIG. 6 is a fluorescence micrograph of cells alive and dead of the ternary complex gel prepared in example 1. After co-culturing the gel with L929 cells, live and dead staining was performed on the cells, and a fluorescence micrograph was taken (in which live cells were green and dead cells were red). Live and dead staining results further confirm that the gel has good biocompatibility;

FIG. 7 shows the results of plating bacteria at a concentration of 10 in 1mL⁷The CFU/mL of Staphylococcus aureus and Escherichia coli were co-cultured with 100. mu.l of the gel for 24 hours, and then plated. The bacterial plate coating result shows that the antibacterial effect of the ternary composite gel is excellent;

FIG. 8 shows the results of in vivo antibacterial experiments on animals, which confirm that the gel still has significant antibacterial effect in animals;

fig. 9 shows the healing of the infected wound of the animal, and the experimental result shows that the ternary complex gel CPP (group D) prepared according to example 1 has a significant healing promoting effect on the infected wound compared with comparative examples 1 and 2.

Detailed Description

The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.

In the present disclosure, the main components of the ternary composite hydrogel are beta-cyclodextrin, tertiary aminated polyethyleneimine and polyvinyl alcohol, which are formed by physical and chemical reactions, and the majority of the rest is water. Wherein part of cyclodextrin participates in chemical reaction to form binary polymer with polyethyleneimine. And hydroxyl in the cyclodextrin can form a physical crosslinking point with amino in polyethyleneimine and hydroxyl in polyvinyl alcohol to form a physical crosslinking network.

In an optional embodiment, the mass ratio of each component in the ternary composite hydrogel is as follows: 0.5-10% of beta-cyclodextrin, 1-4% of tertiary amination polyethyleneimine, 0.01-52% of polyvinyl alcohol and 30-98% of water, wherein the total amount is 100 wt%.

In a further preferred mode, the ternary self-healing composite hydrogel comprises the following components in percentage by mass: 0.5-5 wt% of beta-cyclodextrin, 1-4 wt% of polyethyleneimine, 0.1-30 wt% of polyvinyl alcohol and 61-98 wt% of water, wherein the total amount is 100 wt%.

In the invention, the cyclodextrin and the polyethyleneimine in the ternary composite hydrogel are subjected to chemical reaction through a cross-linking agent epichlorohydrin, and then are physically blended with polyvinyl alcohol and prepared by a freeze-thawing method. The self-healing hydrogel system contains a large amount of hydrogen bonds and physical microcrystals. The hydrogel has a large number of hydrogen bonds and physical microcrystalline areas, so that the hydrogel has excellent self-healing capability. When the intermolecular force of the gel is weakened under the action of external force, the physical network is damaged, the gel generates microcracks, and the external force is dissipated; and after the external force is removed, the intermolecular hydrogen bonds at the microcracks are reformed to form a new physical network, and the microcracks are repaired to complete self-healing.

The following is an exemplary illustration of the method of preparing self-healing, antimicrobial ternary complex hydrogel materials.

In an alkaline environment, at the temperature of 0-50 ℃, an organic solvent is used for modifying polyethyleneimine to prepare tertiary amination polyethyleneimine. The alkaline environment is provided by an aqueous alkaline solution. The alkaline aqueous solution comprises one or more of sodium hydroxide, potassium hydroxide and sodium bicarbonate. The concentration of the alkaline aqueous solution can be 0.01-2 mol/L. The organic solvent is epichlorohydrin, and the addition amount of the epichlorohydrin is as follows: and the polyethyleneimine is 0.2-2 mL and 2 mL.

As a detailed example, 2mL of polyethyleneimine is added to 1-5 mL of an alkaline solution, and the solution is stirred at room temperature until dissolved, thereby obtaining an alkaline solution of polyethyleneimine. Dropwise adding a certain amount of epoxy chloropropane into an alkali solution of polyethyleneimine under the condition of stirring at a certain temperature, and keeping stirring for 2 hours to obtain the tertiary aminated polyethyleneimine.

And (3) reacting cyclodextrin with tertiary amination polyethyleneimine at the temperature of 20-80 ℃ to prepare the binary composite hydrogel. Adding ultrapure water (2-10 mL) into tertiary amination polyethyleneimine solution (0.5-5 mL), weighing beta-cyclodextrin (1.134-5.670 g), adding into the system, and stirring at uniform speed for 20min until complete dissolution. And dropwise adding 0.2-2 ml of epoxy chloropropane into the system, and continuously reacting for 0.5-8 h at the temperature of 20-80 ℃.

And blending the binary composite hydrogel with a polyvinyl alcohol solution with a certain concentration at the temperature of 20-95 ℃ to obtain a mixture. The concentration range of the polyvinyl alcohol solution is 3-30 wt%. As an example, 50-100 mL of aqueous solution is added into a beaker at a temperature ranging from 95-98 ℃, and polyvinyl alcohol is fully dissolved in the aqueous solution to obtain a polyvinyl alcohol solution. And (3) controlling the rotating speed to be 200-600 rpm/min, and fully mixing the binary composite hydrogel with the dissolved polyvinyl alcohol solution to obtain a mixture (substantially gel).

Standing and defoaming the blended mixture, and then performing freeze thawing for multiple times to prepare the self-healing antibacterial ternary composite hydrogel. Standing for defoaming at normal temperature and normal pressure, wherein the defoaming time is 0.5-24 h. Freeze-thawing comprises: freezing and thawing. Wherein the freezing temperature can be-20 to-18 ℃. The freezing time can be 2-12 h. Wherein the thawing temperature can be 4-25 ℃, and the thawing time can be 2-12 h. As an example, after being uniformly mixed, the gel is injected into a mold, is kept stand for defoaming, is frozen in a refrigerator with the temperature of-20 ℃ for 2-12 hours after defoaming, and is then unfrozen at normal temperature for 2-12 hours.

More preferably, the composite gel can form a microcrystalline region through multiple times (1-5 times, preferably 1-3 times) of freeze thawing, so that the strength and stability of the gel are improved. The self-healing effect is poor for more than 5 times, the performance of the material is not obviously improved, and the time for preparing the material is long.

If not specifically stated, the temperature involved in the above preparation process is generally normal temperature (20-25 ℃), and the reaction pressure is generally normal pressure.

The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. In the following examples and comparative examples, the tensile properties of the gel are expressed in terms of elongation at break (%), and a higher value indicates a better deformable property of the gel; the viscoelastic property of the gel is represented by the storage modulus and the loss modulus, and when the storage modulus G 'is larger than G', the gel is proved to be formed and have good stability; the antibacterial rate (%) indicates the antibacterial effect of the gel, and a higher value indicates better antibacterial performance; the biocompatibility of the gel is expressed in terms of cell viability (%), and a higher value indicates a better biocompatibility of the gel. And (3) splicing the gel after the gel is completely destroyed to represent whether the self-healing performance exists or not: if the gel can be spliced into new gel again and bear the self weight, the self-healing performance is proved; otherwise, it is not.

Example 1

(A) Dissolving 2mL of polyethyleneimine in 1mL of NaOH solution with the concentration of 0.01mol/L under the condition of ice-water bath, and adding 400 mu L of epoxy chloropropane to prepare tertiary aminated polyethyleneimine;

(B) reacting 1.134g of cyclodextrin and 200 mu L of epoxy chloropropane with the tertiary aminated polyethyleneimine obtained in the step (A) at 60 ℃ to prepare binary composite hydrogel;

(C) and (3) raising the temperature to 95 ℃, blending the binary composite hydrogel obtained in the step (B) with 15% polyvinyl alcohol (50mL), and standing for defoaming. And (3) freezing and thawing for 3 times (each freezing and thawing is performed for 2-12 h in a refrigerator at the temperature of-20 ℃ and then thawing for 2-12 h at the temperature of 20 ℃) to prepare the ternary composite hydrogel. Then, characterization of relevant physicochemical and biological properties was performed, and the test results are listed in table 1. The composition of the obtained ternary composite hydrogel material comprises: beta-cyclodextrin 1.62 wt%, tertiary aminated polyethyleneimine 2.94 wt%, polyvinyl alcohol 22.46 wt% and the balance of water.

Example 2

The process of example 1 is repeated in the proportions described above, with the difference that: only the temperature conditions of example 1, step a, were changed to 10 ℃. Then, characterization of relevant physicochemical and biological properties was performed, and the test results are listed in table 1.

Example 3

The process of example 1 is repeated in the proportions described above, with the difference that: only the temperature in example 1, step B, was changed to 70 ℃. Beta-cyclodextrin 1.62 wt%, tertiary aminated polyethyleneimine 2.94 wt%, polyvinyl alcohol 22.46 wt% and the balance of water. Then, characterization of relevant physicochemical and biological properties was performed, and the test results are listed in table 1.

Example 4

The process of example 1 is repeated in the proportions described above, with the difference that: only the temperature in step C of example 1 was changed to 90 ℃. The composition of the obtained ternary composite hydrogel material comprises: beta-cyclodextrin 1.62 wt%, tertiary aminated polyethyleneimine 2.94 wt%, polyvinyl alcohol 22.46 wt% and the balance of water. Then, characterization of relevant physicochemical and biological properties was performed, and the test results are listed in table 1.

Example 5

The process of example 1 is repeated in the proportions described above, with the difference that: only in step C of example 1, the concentrations of polyvinyl alcohol were changed to 5 wt%, 10 wt%, 20 wt%, 25 wt%, and 30 wt%, respectively;

when the concentration of the polyvinyl alcohol solution is 5 wt%, the composition of the obtained ternary composite hydrogel material comprises: 1.89 wt% of beta-cyclodextrin, 3.44 wt% of polyethyleneimine, 8.35 wt% of tertiary aminated polyvinyl alcohol and the balance of water;

when the concentration of the polyvinyl alcohol solution is 10 wt%, the composition of the obtained ternary composite hydrogel material comprises: 1.74 wt% of beta-cyclodextrin, 3.17 wt% of polyethyleneimine, 15.4 wt% of tertiary aminated polyvinyl alcohol and the balance of water;

when the concentration of the polyvinyl alcohol solution is 20 wt%, the composition of the obtained ternary composite hydrogel material comprises: 1.51 wt% of beta-cyclodextrin, 2.75 wt% of polyethyleneimine, 26.7 wt% of tertiary aminated polyvinyl alcohol and the balance of water;

when the concentration of the polyvinyl alcohol solution is 25 wt%, the composition of the obtained ternary composite hydrogel material comprises: 1.42 wt% of beta-cyclodextrin, 2.58 wt% of polyethyleneimine, 31.3 wt% of tertiary aminated polyvinyl alcohol and the balance of water;

then, characterization of relevant physicochemical and biological properties was performed, and the test results are listed in table 1.

Example 6

The process of example 1 is repeated in the proportions described above, with the difference that: the number of freeze-thaw cycles was 0. A uniform gel was not formed without freezing, and the scratch test was not performed because the gel was a viscous liquid.

Example 7

The process of example 1 is repeated in the proportions described above, with the difference that: the number of freeze-thaw cycles was 1.

Example 8

The process of example 1 is repeated in the proportions described above, with the difference that: the number of freeze-thaw cycles was 5.

Example 9

The process of example 1 is repeated in the proportions described above, with the difference that: the number of freeze-thaw cycles was 7.

Comparative example 1

The binary composite hydrogel is prepared only according to the mixture ratio in the example 1 and the steps A and B:

(A) dissolving 2mL of polyethyleneimine in 1mL of NaOH solution with the concentration of 0.01mol/L under the condition of ice-water bath, and adding 400 mu L of epoxy chloropropane to prepare tertiary amination polyethyleneimine;

(B) at 60 ℃, 1.134g of cyclodextrin and 200 mu L of epoxy chloropropane react with tertiary aminated polyethyleneimine to prepare the binary composite hydrogel. Then, characterization of relevant physicochemical and biological properties was performed, and the test results are listed in table 1.

Comparative example 2

PVA gel was prepared according to the formulation and procedure C of example 1 only. Preparing polyvinyl alcohol with the mass concentration of 15% at the temperature of 95 ℃, fully dissolving, defoaming, and freezing and thawing for 3 times to obtain the hydrogel. Then, characterization of relevant physicochemical and biological properties was performed, and the test results are listed in table 1.

The test data for tensile, antimicrobial and biocompatibility of the hydrogels obtained in the examples and comparative examples in table 1 illustrate that:

as can be seen from Table 1, the hydrogel materials prepared in the examples of the present invention are significantly superior to those of comparative examples 1 and 2, both in single properties and in combination. Above-mentioned self-healing performance has or not the test to need the mar experiment inspection, and concrete mar experimental step includes: an equal volume of hydrogel was prepared in a clean disc mold of the same size and cut with a knife along the diameter of the disc to completely destroy the hydrogel. The disrupted hydrogel was then allowed to stand at room temperature (25 deg.C) and time was taken until the scratches on the hydrogel were completely "healed" and the time was stopped. (the complete 'healing' standard is that the scratch on the surface of the hydrogel disappears completely, and the hydrogel cannot be separated along the original scratch position by poking the hydrogel at the original scratch position by using forceps.) the self-healing performance of the hydrogel is judged by observing the time required for the complete healing of the scratch. Wherein "none" means: after the scratch test is carried out, timing is started, the scratch is not changed after 30min of observation, and the hydrogel is divided into two parts and can not be healed into a whole. The tensile elongation is collectively referred to as tensile elongation at break, i.e.: (Length stretched to Break L₁Original length L₀) Original length L₀*100％。

Claims (10)

1. The self-healing antibacterial ternary composite hydrogel material is characterized by having a three-dimensional porous structure and mainly comprising beta-cyclodextrin, tertiary aminated polyethyleneimine, polyvinyl alcohol and water.

2. The ternary composite hydrogel material according to claim 1, wherein the three-dimensional network structure is obtained by chemically crosslinking beta-cyclodextrin and tertiary aminated polyethyleneimine and then physically crosslinking with polyvinyl alcohol.

3. The ternary complex hydrogel material according to claim 1, wherein the composition of the ternary complex hydrogel material comprises: 0.5-10 wt% of beta-cyclodextrin, 1-4 wt% of tertiary aminated polyethyleneimine, 0.01-52 wt% of polyvinyl alcohol and 30-98 wt% of water, wherein the total amount is 100 wt%.

4. The ternary composite hydrogel material according to any one of claims 1 to 3, wherein the ternary composite hydrogel material has a storage modulus G 'higher than a loss modulus G ", wherein G' is in the range of 10 to 10000Pa and G" is in the range of 0 to 10000 Pa.

5. The ternary composite hydrogel material according to any one of claims 1 to 3, wherein the ternary composite hydrogel material remains in a gel state and is deformable under a shear strain of 1000%.

6. A method for preparing a self-healing, antibacterial ternary complex hydrogel material according to any one of claims 1 to 5, comprising:

(A) in an alkaline environment, modifying polyethyleneimine by using an organic solvent at the temperature of 0-50 ℃ to obtain tertiary amination polyethyleneimine;

(B) performing chemical crosslinking on cyclodextrin and tertiary aminated polyethyleneimine at the temperature of 20-80 ℃ to obtain binary composite hydrogel;

(C) and mixing the obtained binary composite hydrogel with a polyvinyl alcohol solution at the temperature of 20-95 ℃, and standing, defoaming and freezing and thawing to obtain the self-healing antibacterial ternary composite hydrogel.

7. The method according to claim 6, wherein in the step (A), the alkaline environment is provided by an alkaline aqueous solution; the alkali comprises at least one of sodium hydroxide, potassium hydroxide and sodium bicarbonate; the concentration of the alkaline aqueous solution is 0.01-2 mol/L; the organic solvent is epoxy chloropropane; the addition amount of the epichlorohydrin is 11.48-114.85 wt% of the mass of the polyethyleneimine.

8. The preparation method according to claim 6, wherein in the step (B), the tertiary aminated polyethyleneimine solution and ultrapure water are mixed, then the beta-cyclodextrin and the cross-linking agent are added for complete dissolution, and the reaction is carried out at 20-80 ℃ for 0.5-8 h; the crosslinking agent is epichlorohydrin, and the addition amount of the epichlorohydrin is 10.43-104.32 wt% of beta-cyclodextrin.

9. The method according to claim 6, wherein in the step (C), the concentration of the polyvinyl alcohol solution is 3 to 30 wt%;

the standing and defoaming are carried out at normal temperature and normal pressure for 0.5-24 hours;

the freezing and thawing comprises the following steps: freezing for 2-12 h at-20 to-18 ℃, and then unfreezing at 4-25 ℃; preferably, the number of times of freeze thawing is 1-5 times.

10. Use of the self-healing, antibacterial ternary composite hydrogel material according to any one of claims 1 to 5 in the preparation of antibacterial hydrogel dressings for infectious wounds.

Images