An ionic liquid-based antibacterial hydrogel and a preparation method and application thereof

An antibacterial hydrogel based on ionic liquid was prepared by a one-pot method, and a three-dimensional network structure was constructed using dynamic covalent bonds. This method solves the problems of complex preparation and poor stability of hydrogels in the prior art, and achieves high efficiency antibacterial effect and controllable mechanical properties, which are suitable for medical antibacterial dressings.

CN120939283BActive Publication Date: 2025-12-12WEIFANG MEDICAL UNIV
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Patent Information

Application Number
CN202511494945.8
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2025-10-20
Publication Date
2025-12-12
Estimated Expiration
2045-10-20

AI Technical Summary

Technical Problem

Existing hydrogel preparation methods based on ionic liquids suffer from problems such as complex synthesis steps, difficulty in controlling the degree of polymerization of the backbone, poor stability, and easy destruction of the structure, resulting in poor antibacterial effects.

Method used

An antibacterial hydrogel was prepared using a one-pot method. A three-dimensional network structure was constructed by forming dynamic covalent bonds between polyvinyl alcohol, borax, tofu glycoside, 3,3'-dithiobis(propionylhydrazine), and 1-aminopropyl-3-methylimidazolium bromide. Combined with dynamic borate ester bonds, dynamic acylhydrazone bonds, and dynamic imine bonds, a stretchable and self-healing antibacterial hydrogel was formed.

Benefits of technology

It achieves a simple preparation method, stable structure, good mechanical properties and antibacterial effect, significant inhibitory effect on both Gram-negative and Gram-positive bacteria, and the ionic liquid content can be adjusted, making it suitable for medical antibacterial dressings.

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Abstract

The application discloses an antibacterial hydrogel based on ionic liquid and a preparation method and application thereof, and belongs to the technical field of biological medicines. Polyvinyl alcohol is added into deionized water and heated to completely dissolve to obtain a polyvinyl alcohol solution; sophoricoside is dissolved in the polyvinyl alcohol solution and uniformly stirred to obtain a polyvinyl alcohol / sophoricoside solution; borax, 3,3'-dithio-bis (propionyl hydrazide) and 1-aminopropyl-3-methyl imidazole bromide are added into the polyvinyl alcohol / sophoricoside solution, and the solution is continuously stirred and placed to obtain an inverted non-flowing hydrogel, which is the antibacterial hydrogel based on ionic liquid. The hydrogel prepared in the application exhibits good stretchability and healability, and shows excellent antibacterial effects on gram-negative bacteria and gram-positive bacteria; the content of the crosslinking agent and the ionic liquid shows controllability on the mechanical properties and the antibacterial properties of the hydrogel.
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Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of biological medicine, and particularly relates to an antibacterial hydrogel based on ionic liquid and a preparation method and application thereof. BACKGROUND

[0002] Bacterial infection is one of the biggest public health challenges in the world, causing millions of deaths worldwide each year. Antibiotics, as the most commonly used antibacterial agent for treating bacterial infections, are considered a milestone in modern medicine. However, the overuse of antibiotics has led to the emergence and rapid increase of drug-resistant bacteria, so it is of great significance to research and develop efficient and persistent antibacterial materials that do not produce drug resistance.

[0003] High-efficiency antibacterial materials have become a research hotspot in recent years because they can effectively reduce the use of antibacterial agents, reduce the risk of bacterial drug resistance, and reduce and avoid the risk of secondary infection caused by dressings. In order to improve the antibacterial activity of antibacterial materials, many high-efficiency antibacterial agents have been developed, mainly including polymers, antibacterial peptides, metals / metal oxides, carbon-based materials, and ionic liquid antibacterial agents. Among them, ionic liquid antibacterial agents have attracted much attention due to their high-efficiency and broad-spectrum antibacterial activity. Ionic liquids (ILs) are a class of organic molten salts composed of anions / cations that are liquid at room temperature or near room temperature. The unique physicochemical properties of ionic liquids, such as low volatility, non-flammability, designability, thermal stability, and chemical stability, make them important participants in the fields of clean energy, medicine and health, and nanomaterial preparation. For example, patent No. CN 114887112A discloses a preparation method and application of imidazole salt ionic liquid / polyvinyl alcohol pressure sensing antibacterial hydrogel dressing. The imidazole salt ionic liquid is polymerized into a long-chain polymer with acrylamide through free radical copolymerization, and then the imidazole salt ionic liquid / polyvinyl alcohol hydrogel is obtained by repeated freezing and thawing of the polyvinyl alcohol solution. The hydrogel dressing has a unique three-dimensional network structure, and the hydrogel containing ionic liquid has broad-spectrum antibacterial activity and excellent antibacterial effect on Staphylococcus aureus. Therefore, in recent years, due to the unique cationic / anionic structure of ionic liquids, ionic liquids have excellent bactericidal performance and broad-spectrum against coccobacilli, bacilli, and fungi, making them widely concerned in the field of antibacterial agents.

[0004] Hydrogel is an important carrier for preparing novel antibacterial materials due to its high water content, adjustable structure and performance. At present, the main methods for preparing ionic liquid-based hydrogel are covalent bond polymerization and non-covalent bond combination. However, the ionic liquid hydrogel prepared by covalent bond polymerization method has the problems of complex synthesis steps and difficult control of backbone polymerization degree; the ionic liquid hydrogel prepared by non-covalent bond method has the problems of poor stability and easy destruction of structure. Therefore, it is of great significance to seek and develop an ionic liquid hydrogel with simple preparation method, stable and adjustable structure for preparing biological medical antibacterial dressing with high efficient antibacterial effect. SUMMARY

[0005] In view of the above prior art, the purpose of the present application is to provide an antibacterial hydrogel based on ionic liquid and its preparation method and application. The present application takes polyvinyl alcohol as the skeleton, borax, leucodelphinidin, 3, 3'-dithiobis (propionyl hydrazide) as the crosslinking agent, and 1-aminopropyl-3-methyl imidazole bromide as the antibacterial agent to obtain ionic liquid-based hydrogel (PBDSN). The hydrogel shows good stretchability and healability, and shows excellent antibacterial effect on gram-negative bacteria and gram-positive bacteria. The content of crosslinking agent and ionic liquid shows adjustable control on the mechanical properties and antibacterial properties of the hydrogel.

[0006] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0007] In the first aspect of the present application, a preparation method of an antibacterial hydrogel based on ionic liquid is provided, and the preparation method is as follows:

[0008] Polyvinyl alcohol is added to deionized water and heated to completely dissolve to obtain a polyvinyl alcohol solution; leucodelphinidin is dissolved in the polyvinyl alcohol solution and stirred uniformly to obtain a polyvinyl alcohol / leucodelphinidin solution; borax, 3, 3'-dithiobis (propionyl hydrazide) and 1-aminopropyl-3-methyl imidazole bromide are added to the polyvinyl alcohol / leucodelphinidin solution, and continuously stirred to obtain an inverted non-flowing hydrogel, which is an antibacterial hydrogel based on ionic liquid.

[0009] Preferably, the concentration of the polyvinyl alcohol solution is 1 g / mL; and the mass ratio of leucodelphinidin to the polyvinyl alcohol solution is 1:10.

[0010] Preferably, the heating treatment time is 90℃; and the uniform stirring time is 30 min.

[0011] Preferably, the mass ratio of borax, 3, 3'-dithiobis (propionyl hydrazide), 1-aminopropyl-3-methyl imidazole bromide and the polyvinyl alcohol solution is 5:3:2~5:100.

[0012] Preferably, the time of the constant stirring is 10 min; and the time of the standing is 5 min.

[0013] In a second aspect of the present application, the ion liquid-based antibacterial hydrogel prepared by the preparation method is provided, and the antibacterial hydrogel has a three-dimensional network structure, and dynamic borate ester bonds, dynamic acylhydrazone bonds and dynamic imine bonds.

[0014] Preferably, the three-dimensional network structure is formed by borax through dynamic borate ester bonds with polyvinyl alcohol, helicidin, and the helicidin is formed into a network through dynamic acylhydrazone bonds with 3, 3'-dithiobis (propionylhydrazide), and the helicidin is also connected with 1-aminopropyl-3-methyl imidazole bromide through dynamic imine bonds.

[0015] In a third aspect of the present application, the antibacterial hydrogel is applied to preparation of medical antibacterial dressings.

[0016] Preferably, the medical antibacterial dressing is a stretchable, self-healing antibacterial material.

[0017] The present application has the following beneficial effects:

[0018] (1) The present application prepares an ion liquid-based antibacterial hydrogel through a simple one-pot method, avoids the problems of complex synthesis steps and difficulty in controlling the backbone polymerization degree in the preparation of ion liquid hydrogels based on covalent bond polymerization method, and overcomes the problems of poor stability and easy destruction of the structure in the ion liquid hydrogels prepared based on non-covalent bond method.

[0019] (2) The preparation method of the present application is simple, the prepared hydrogel has stable structure and performance, has stretchability, self-healing property and plasticity, has good inhibitory effect on gram-negative bacteria and gram-positive bacteria, and the content of the ion liquid shows the controllability of the mechanical properties and antibacterial properties of the hydrogel. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 : Characterization diagram of PBDSN hydrogel; wherein (a) is a photo of the hydrogel of different components; (b) is an ultraviolet spectrum diagram of polyvinyl alcohol (hereinafter referred to as PVA), borax (hereinafter referred to as B), helicidin (hereinafter referred to as HLC), 3, 3'-dithiobis (propionylhydrazide) (hereinafter referred to as DTPH), 1-aminopropyl-3-methyl imidazole bromide (hereinafter referred to as MimNBr) and PBDSN hydrogel (Gel-2);

[0021] Figure 2 : Infrared spectrum diagram of PVA, B, HLC, DTPH, MimNBr and PBDSN hydrogel (Gel-1, Gel-2, Gel-3); wherein (a) is a wavelength 4000~1000cm-1 Figure 1 (a) is an infrared spectrum of PBD hydrogel at the wavelength of 2000~500 cm-1; (b) is an infrared spectrum of PBD hydrogel at the wavelength of 500~2000 cm-1; -1 Figure 2 (a) is an infrared spectrum of PBDS hydrogel at the wavelength of 2000~500 cm-1; (b) is an infrared spectrum of PBDS hydrogel at the wavelength of 500~2000 cm-1;

[0022] Figure 3 Figure 3 (a) is an SEM of PBD hydrogel with the scale of 200 μm; (b) is an SEM of PBD hydrogel with the scale of 30 μm; (c) is an O element distribution map of PBD hydrogel; (d) is a Na element distribution map of PBD hydrogel; (e) is a C element distribution map of PBD hydrogel; (f) is a B element distribution map of PBD hydrogel;

[0023] Figure 4 Figure 4 (a) is an SEM of PBDS hydrogel with the scale of 200 μm; (b) is an SEM of PBDS hydrogel with the scale of 70 μm; (c) is an O element distribution map of PBDS hydrogel; (d) is a C element distribution map of PBDS hydrogel; (e) is a S element distribution map of PBDS hydrogel; (f) is a Na element distribution map of PBDS hydrogel; (g) is a N element distribution map of PBDS hydrogel; (h) is a B element distribution map of PBDS hydrogel;

[0024] Figure 5 Figure 5 (a) is an SEM of PBDSN (Gel-2) hydrogel with the scale of 200 μm; (b) is an SEM of PBDSN (Gel-2) hydrogel with the scale of 70 μm; (c) is an O element distribution map of PBDSN (Gel-2) hydrogel; (d) is a C element distribution map of PBDSN (Gel-2) hydrogel; (e) is a Na element distribution map of PBDSN (Gel-2) hydrogel; (f) is a B element distribution map of PBDSN (Gel-2) hydrogel; (g) is a S element distribution map of PBDSN (Gel-2) hydrogel; (h) is a N element distribution map of PBDSN (Gel-2) hydrogel; (i) is a total element distribution map of PBDSN (Gel-2) hydrogel;

[0025] Figure 6 Figure 6 (a) is a stress scanning curve of different hydrogels; (b) is a partial stress scanning curve of different hydrogels; (c) is a contrast diagram of elastic modulus (G’) and viscous modulus (G”) of different hydrogels; (d) is a frequency scanning curve of different hydrogels; (e) is a partial frequency scanning curve of different hydrogels; (f) is a gel point diagram of different hydrogels;

[0026] Figure 7 Figure 7 (a) is an apparent tensile diagram of PBDSN (Gel-2) hydrogel; (b) is a healing photo of PBDSN (Gel-2) hydrogel, colorless and transparent is the color of the hydrogel itself, red and blue hydrogel is the hydrogel dyed with eosin and coomassie brilliant blue; (c) is a healing process of PBDSN (Gel-2) hydrogel dyed with eosin and coomassie brilliant blue under optical microscope; (d) is a cycle test result of Gel-2 hydrogel under different strains (2%-200%-2%-200%-2%-200%); (e) is a photo of Gel-2 hydrogel shaped into different shapes;

[0027] Figure 8 Antibacterial test of PBD, PBDS and PBDSN (Gel-1, Gel-2 and Gel-3) hydrogels; wherein (a) is the inhibition rate of different composition gels on E. coli; (b) is the inhibition rate of different composition gels on S. aureus; (c) is the survival situation diagram of E. coli and S. aureus after treatment by different gels. DETAILED DESCRIPTION

[0028] It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

[0029] As introduced in the background section, at present, the preparation of antibacterial hydrogels based on ionic liquids is mainly through covalent bond polymerization and non-covalent bond combination. However, the preparation of ionic liquid hydrogels based on covalent bond polymerization method has the problems of complex synthesis steps and difficult control of backbone polymerization degree; the ionic liquid hydrogels prepared based on non-covalent bond method have the problems of poor stability and easy destruction of structure.

[0030] Based on this, the purpose of the present application is to provide an ionic liquid-based antibacterial hydrogel and a preparation method and application thereof. The present application utilizes a "one-pot method" to connect polyvinyl alcohol, borax, esculin, 3, 3'-dithiobis (propionylhydrazide) and 1-aminopropyl-3-methyl imidazole bromide salt through the formation of dynamic covalent bonds, thereby obtaining a hydrogel with a three-dimensional network structure. Whether it is polyvinyl alcohol and borax, or borax and esculin, or esculin and 3, 3'-dithiobis (propionylhydrazide), they can only be prepared into liquid materials without flexibility and mechanical properties, and cannot be used as adjuvants. The one-pot method can prepare a hydrogel with good flexibility and mechanical properties, which can be used as an antibacterial dressing. PVA is linear, the hydroxyl group of PVA and the boron of boric acid form a dynamic borate ester bond, and thus PVA and boric acid form a network; the boron of boric acid and the hydroxyl group of esculin form a dynamic borate ester bond, and thus boric acid and esculin form a network; the aldehyde group of esculin and the hydrazide group of 3, 3'-dithiobis (propionylhydrazide) form a dynamic acylhydrazone bond, and thus esculin and 3, 3'-dithiobis (propionylhydrazide) form a network, and the complex connection between the networks makes the hydrogel have a three-dimensional network structure; the aldehyde group on the esculin and the amine group of 1-aminopropyl-3-methyl imidazole bromide salt form a dynamic imine bond, and thus 1-aminopropyl-3-methyl imidazole bromide salt is connected to the three-dimensional network. If the hydrogel is made into a dressing for use in a wound, the dynamic imine bond can quickly break in the wound environment, realizing the rapid release of ionic liquid, and thus achieving better antibacterial effect. The above structure endows the hydrogel with stretchability and self-healing properties, providing a new idea for the development of new antibacterial materials.

[0031] In order for those skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below in conjunction with specific embodiments.

[0032] The test materials used in the embodiments of the present application are all conventional test materials in the art and can be purchased through commercial channels.

[0033] Example 1: Preparation of an ionic liquid-based hydrogel

[0034] Precisely weigh 0.1 g of polyvinyl alcohol into 0.1 mL of deionized water, heat to complete dissolution at 90 ℃, remove bubbles by standing, and cool to obtain a polyvinyl alcohol solution. Precisely weigh 0.1 g of quercetin into 1 g of the polyvinyl alcohol solution, stir for 5 min to obtain a polyvinyl alcohol / quercetin solution; precisely weigh 0.05 g of borax, 0.03 g of 3, 3'-dithiobis (propionohydrazide), and 1-aminopropyl-3-methyl imidazole bromide (0.02 g, 0.03 g, or 0.05 g) into the polyvinyl alcohol / quercetin solution, continuously stir for 10 min to form dynamic covalent bonds between molecules, stand for 5 min to obtain an inverted non-flowing hydrogel (PBDSN). According to the amount of 1-aminopropyl-3-methyl imidazole bromide added, the PBDSN prepared finally is recorded as Gel-1 hydrogel, Gel-2 hydrogel, and Gel-3 hydrogel, respectively. The hydrogels with different MimNBr contents are simply referred to as Gel-1 (MimNBr content is 0.02 g), Gel-2 (MimNBr content is 0.03 g), and Gel-3 (MimNBr content is 0.05 g).

[0035] Comparative Example 1

[0036] Precisely weigh 0.1 g of polyvinyl alcohol into 0.1 mL of deionized water, heat to complete dissolution at 90 ℃, remove bubbles by standing, and cool to obtain a polyvinyl alcohol solution; precisely weigh 0.05 g of borax into the polyvinyl alcohol solution, continuously stir to form dynamic covalent bonds between molecules, stand to obtain a PB viscous solution with flowability, which is recorded as PB, see Figure 1 (a).

[0037] Comparative Example 2

[0038] The difference from Example 1 is that 3, 3'-dithiobis (propionohydrazide) and 1-aminopropyl-3-methyl imidazole bromide are not added, and the hydrogel prepared finally is recorded as PBD hydrogel, see Figure 1 (a).

[0039] Comparative Example 3

[0040] The difference from Example 1 is that 1-aminopropyl-3-methyl imidazole bromide is not added, and the hydrogel prepared finally is recorded as PBDS hydrogel, see Figure 1 (a).

[0041] Comparative Example 4

[0042] The difference from Example 1 is that polyvinyl alcohol and 3, 3'-dithiobis (propionohydrazide) are not added, and a transparent solution prepared finally is recorded as BDN, see Figure 1 (a).

[0043] Comparative Example 5

[0044] The difference from Example 1 is that polyvinyl alcohol and borax are not added, and a transparent solution is finally prepared and marked as DSN, see Figure 1 (a).

[0045] Comparative Example 1, Comparative Example 4 and Comparative Example 5 prepare liquid antibacterial materials, the performance of which is affected by many factors such as environment, use mode, etc., and is difficult to control, and the viscosity and adhesion are poor, which cannot be used as crop adjuvants, and cannot be well attached to the skin or the surface of other objects, the action time is short, resulting in poor antibacterial effect.

[0046] Example 2: Characterization

[0047] The formation of dynamic covalent bonds is determined by ultraviolet absorption spectrum. The experimental results are shown in Figure 1 (b), it can be seen that compared with MimNBr, DTPH and HLC alone, the ultraviolet absorption of PBDSN solution obviously has a blue shift phenomenon, which may be caused by the increase of conjugated system due to the formation of dynamic imine bond and dynamic acylhydrazone bond, which further proves the formation of dynamic covalent bond.

[0048] On this basis, the formation of dynamic covalent bonds is further determined by infrared spectrum, and the experimental results are shown in Figure 2 (a) and Figure 2 (b). Figure 2 (a) is the infrared spectrum of pure PVA, B, HLC, DTPH, MimNBr and the formed hydrogel PB, PBD, PBDS, Gel-1, Gel-2 and Gel-3. Figure 2 (b) is a partial infrared spectrum of pure PVA, B, HLC, DTPH, MimNBr and the formed hydrogel PB, PBD, PBDS, PBDSN (Gel-1, Gel-2 and Gel-3). It can be seen that the disappearance of C=O stretching vibration peak at 1674 cm -1 and NH2 stretching vibration peak at 1568 cm -1 of MimNBr, the appearance of C=N (amide or acylhydrazone bond) stretching vibration peak at 1656 cm -1 of PBDS and PBDSN (Gel-1, Gel-2, Gel-3) proves the formation of dynamic imine (acylhydrazone) bond; in addition, 1416 and 1339 cm -1 peaks correspond to the asymmetric stretching vibration of B-O-C bond, and the bending vibration peak of B-O-B appears at 656 cm -1 of PB, PBD, PBDS and PBDSN (Gel-1, Gel-2, Gel-3), which further proves the formation of dynamic borate ester bond.

[0049] Figures 3-5 SEM images of PBD, PBDS and PBDSN (Gel-2) respectively. It can be seen that PBD, PBDS and PBDSN all present good three-dimensional network structure, and the element distribution is consistent with the content of each element; the pore size of PBD hydrogel is 10-50 μm, the pore size of PBDS hydrogel is 5-50 μm, compared with PBD, the pore size of PBDS is smaller, which indicates that the dynamic acylhydrazone bond is formed between the introduced DTPH and the aldehyde group on HLC, thereby enhancing the network structure of the gel, in addition, the pore size of PBDSN (Gel-2) hydrogel is 10-60 μm, compared with PBDS, the pore size of PBDSN (Gel-2) hydrogel is larger, which is due to the addition of ionic liquid MimNBr, forming a dynamic imine bond which is movable (only one end is fixed by a dynamic imine bond), and reducing a dynamic acylhydrazone bond which is immovable (both ends are fixed by a dynamic acylhydrazone bond), thereby causing the network structure of the gel to relax and the pore size to increase.

[0050] Example 3: Rheological and mechanical property test

[0051] Figure 6 are rheological characterization of hydrogels of different compositions prepared in Example 1 and Comparative Examples 1-3. From Figure 6 (a) it can be seen that the elastic modulus (G') of the PB sample is smaller than the viscous modulus (G'') in the whole stress scanning range, showing the rheological properties of a typical fluid; Figure 6 (b) in the G' of PBD, PBDS and PBDSN hydrogels is greater than G'', and does not change with the increase of stress, showing the rheological properties of a typical solid. In addition, Figure 6 (a) and 6 (d), at low frequency, G' is smaller than G'', showing the properties of a fluid, with the increase of frequency, G' gradually equals and exceeds G'', reaches the highest point, and then begins to decline, showing the properties of an elastomer; the intersection of G' and G'' represents the time when the gel is formed. Figure 6 (c) compared with PB, the G' max value of PBD, PBDS increases, which indicates that the addition of HLC and DTPH strengthens the entanglement between molecules and promotes the formation of network structure, but with the addition of ionic liquid MimNBr, the G' max value begins to decrease, which indicates that MimNBr has a disintegrating effect on the network structure of PBDS. Figure 6 (f) in, f cross represents the frequency at which the gel begins to form, wherein the relaxation time t relex =1 / f crossThe longer the relaxation time, the better the elastic behavior and shape plasticity of the gel. As can be seen from the figure, PBD and PBDS have a larger relaxation time compared with PB. However, the addition of ionic liquid reduces the elasticity and plasticity of the hydrogel to a certain extent.

[0052] Example 4: Self-healing, tensile and plasticity tests of Gel-2 hydrogel

[0053] A tensile test was conducted on the Gel-2 hydrogel prepared in Example 1. The Gel-2 hydrogel was formed into a strip with an initial length of 3.0 cm, which could be stretched by hand to 18.0 cm. The results are as follows: Figure 7 As shown in (a), this demonstrates that the hydrogel has good tensile properties. Cutting the hydrogel with a knife, or bringing different hydrogels into natural contact with their cross-sections or surfaces, and observing whether the hydrogel can be stretched by hand, can be used to determine whether it has self-healing properties. Figure 7 (b) Cut the long strip of Gel-2 hydrogel into two pieces, and place the two pieces of hydrogel in contact naturally. It was found that the two pieces of hydrogel could heal after 1 minute. The other three pieces of Gel-2 hydrogel were stained with eosin, Coomassie brilliant blue and unstained respectively. The three pieces of hydrogel were placed in contact naturally. The three pieces of hydrogel could heal after 1 minute. Figure 7 (c) is a microscopic photograph of the hydrogel healing process, showing that as time goes on, the gap between the two hydrogels gradually shrinks until it disappears; Figure 7 (d) Cyclic tests were conducted on the hydrogel under different strains (2%-200%-2%-200%-2%-200%). It was found that after 3 cycles, the hydrogel still maintained its initial elasticity, which indicates that the hydrogel has good self-healing properties. Figure 7 (e) The hydrogel can be molded into different shapes, such as spheres, fans, semicircles, stars, ellipses, and columns, indicating that the hydrogel has good plasticity.

[0054] Example 5: Antibacterial properties

[0055] Select Staphylococcus aureus ( S. aureus Gram-positive bacteria) and Escherichia coli ( E. coli Gram-negative bacteria were used as the test strains for the antibacterial experiment. 1 g of the hydrogels prepared in Example 1 and Comparative Examples 2-3 were placed in bacterial suspension (4 mL volume, 10% concentration). 5 The bacterial culture was co-cultured at 37 ℃ and 180 rpm for 24 h in CFU / mL solution, and then diluted and plated. The bacterial culture without hydrogel intervention was used as a control group. The bacterial plates were placed in an incubator at 37 ℃ for 12 h, and the colony growth on the LB plates of each group was observed. Figure 8 (a) and Figure 8 (b) shows that the hydrogel has certain antibacterial activity. Figure 8(c) The bacteria liquid was plated, and the number of bacteria colonies on the agar plate showed that the antibacterial activity was significantly enhanced after the addition of the ionic liquid MimNBr, proving that the ionic liquid-based hydrogel has excellent antibacterial performance.

[0056] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Various modifications and changes can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing an ionic liquid-based antibacterial hydrogel, characterized by, The preparation method is: Polyvinyl alcohol is added into deionized water and heated to completely dissolve to obtain a polyvinyl alcohol solution; the daidzin is dissolved in the polyvinyl alcohol solution, and stirred to obtain a polyvinyl alcohol / daidzin solution; borax, 3, 3'-dithiobis (propionohydrazide) and 1-aminopropyl-3-methyl imidazole bromide are added into the polyvinyl alcohol / daidzin solution, and stirred constantly, and then left to stand to obtain an inverted non-flowing hydrogel, which is an antibacterial hydrogel based on ionic liquid; The concentration of the polyvinyl alcohol solution is 1 g / mL; the mass ratio of the daidzin to the polyvinyl alcohol solution is 1:10; The mass ratio of the borax, 3, 3'-dithiobis (propionohydrazide), 1-aminopropyl-3-methyl imidazole bromide and the polyvinyl alcohol solution is 5:3:2-5:100; The time of constant stirring is 10 min; and the time of standing is 5 min.

2. The production method according to claim 1, characterized by, The time of heating treatment is 90℃; and the time of stirring uniformly is 30 min.

3. The ionic liquid-based antibacterial hydrogel obtained by the production method according to claim 1 or 2, characterized in that, The antibacterial hydrogel has a three-dimensional network structure, and dynamic borate ester bonds, dynamic acylhydrazone bonds and dynamic imine bonds.

4. The antimicrobial hydrogel of claim 3, wherein, The three-dimensional network structure is formed by borax through dynamic borate ester bonds with polyvinyl alcohol and daidzin, and daidzin forms a network with 3, 3'-dithiobis (propionohydrazide) through dynamic acylhydrazone bonds, and daidzin is also connected with 1-aminopropyl-3-methyl imidazole bromide through dynamic imine bonds.

5. Use of the antibacterial hydrogel of claim 3 or 4 in the preparation of a medical antibacterial dressing.

6. Use according to claim 5, characterized in that, The medical antibacterial dressing is a stretchable, self-healing antibacterial material.

Citation Information

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