Ginkgo natural extract copolymerized antibacterial conductive gel as well as preparation method and application thereof

Abstract

The invention discloses a ginkgo natural extract copolymerized antibacterial conductive gel as well as a preparation method and application thereof. The conductive gel is prepared from the following raw materials in parts by mass: 1 to 10 parts of ginkgo natural extract, 1 to 8 parts of imidazolyl alkenyl amic acid compound, 0.02 to 0.1 part of stabilizer, 0.01 to 0.2 part of emulsifier, 0.5 to 1 part of organic silicon cross-linking agent, 1 to 5 parts of modifier, 0.05 to 0.3 part of organic oxidant, 1 to 10 parts of natural polysaccharide, 15 to 25 parts of organic solvent and 10 to 30 parts of water. The gingko natural extract has an antibacterial effect, micro-current is conducted by the gingko natural extract through a macromolecular chain and aromatic continuous conjugated structures in flavonoids and olefinic terpenoids, the antibacterial and conductive gel which is low in toxicity and can be applied to organism tissue repair is prepared, and the gel serving as a flexible medium can conduct electric signals and also can be used for repairing tissues of organisms. The foreign matter reaction risk can be reduced through the antibacterial function, meanwhile, the toxicity of metal ion leakage is avoided, and the method has unique advantages in the micro-current related fields such as flexible electronic sensors and bioelectrical stimulation dressings.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of functional materials, and relates to a conductive gel, in particular to a ginkgo biloba natural extract copolymerized antibacterial conductive gel and a preparation method and application thereof. BACKGROUND

[0002] A hydrogel is a three-dimensional network polymer material capable of absorbing and retaining a large amount of water. Due to its good biocompatibility, water retention and flexibility, it has a wide application prospect in the fields of biological medicine, tissue engineering, wound care and the like.

[0003] The ordinary hydrogel on the market has obvious limitations. In terms of antibacterial performance, most hydrogels do not have or only have weak antibacterial ability. In the application process, especially in the fields of biological medicine and health products, it is easy to become a breeding ground for bacteria, thereby causing infection and a series of problems. In terms of electrical conductivity, increasing conductive fillers (such as carbon nanotubes, graphene) can improve electrical conductivity, but will significantly reduce the flexibility of the hydrogel and may cause excessive electrical stimulation to the tissue. For example, too high content of polyaniline will make the hydrogel hard, the tensile strength will decrease from 0.75 MPa to 0.3 MPa, and the elongation at break will decrease by 50%. This imbalance is particularly prominent in scenarios requiring high deformation.

[0004] It is very meaningful to integrate antibacterial and conductive capabilities in the hydrogel and achieve a balance. In future applications, the gel can meet the multiple needs of complex application scenarios. For example, in the field of wound dressings, the conductive property not only promotes cell migration and angiogenesis through electrical stimulation, but also monitors the resistance change in real time during the wound healing process, realizing intelligent management; and the antibacterial property can effectively inhibit bacterial infection, reduce inflammation, and accelerate tissue repair. The synergistic effect significantly improves the applicability of the hydrogel in complex scenarios such as chronic wound treatment and diabetic foot ulcers. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a ginkgo biloba natural extract copolymerized antibacterial conductive gel and a preparation method and application thereof. The ginkgo biloba natural extract with antibacterial ability is selected as the conductive medium to prepare an antibacterial and conductive gel with low toxicity, which can be applied to biological tissue repair.

[0006] In order to achieve the above purpose, the following technical solutions are adopted:

[0007] A ginkgo biloba natural extract copolymerized antibacterial conductive gel, in terms of mass fraction, the raw materials include the following components:

[0008] 1-10 parts of natural extract of Ginkgoaceae, 1-8 parts of imidazole-based olefin amide acid compound, 0.02-0.1 part of stabilizer, 0.01-0.2 part of emulsifier, 0.5-1 part of silicone crosslinking agent, 1-5 parts of modifier, 0.05-0.3 part of organic oxidizing agent, 1-10 parts of natural polysaccharide, 15-25 parts of organic solvent, 10-30 parts of water.

[0009] The application also has the following technical features:

[0010] Preferably, the natural extract of Ginkgoaceae includes one or more of ginkgol, total flavonoids of Ginkgo biloba, and bilobalide;

[0011] The extraction method of the natural extract of Ginkgoaceae includes:

[0012] The dried Ginkgo biloba leaves are crushed to 20-40 mesh, dissolved in acetone solution, ultrasonically treated at room temperature for 3-5 hours, washed with distilled water for three times, washed with 30%-50% ethanol solution, and the products are collected and dried to obtain the natural extract of Ginkgoaceae.

[0013] Preferably, the imidazole-based olefin amide acid compound includes any one of N-benzimidazolyl acrylamide, N-(p-hydroxyphenyl)-N-(imidazolyl) acrylamide, and benzimidazole propenoic acid.

[0014] Preferably, the stabilizer includes any one of polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose, polyethylene glycol, and chitosan.

[0015] Preferably, the emulsifier includes any one or mixture of any proportion of the following: sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium stearate, Tween-80, Tween-60, Span-60, and Span-80.

[0016] Preferably, the silicone crosslinking agent includes any one of vinyl tributyl ketoxime silane, γ-methacryloyloxy propyl trimethoxysilane, and vinyl triethoxysilane.

[0017] Preferably, the modifier includes any one or more of the following: lysine, arginine, 1H-imidazole-1-carboxamidine hydrochloride, tetramethyl guanidine lactate, 1,3-di-o-tolyl guanidine salt, methyl guanidino glycine salt, and p-hydroxyphenyl guanidine sulfate.

[0018] The organic oxidizing agent includes any one of pyridine chlorochromate, pyridine dichromate, Swern oxidation system, or aluminum alcoholate.

[0019] Preferably, the natural polysaccharide includes any one of cellulose, starch, and alginic acid.

[0020] The organic solvent includes any one of methanol, ethanol, acetone, dimethyl sulfoxide.

[0021] The application also protects a preparation method of the ginkgoaceae natural extract copolymerized antibacterial conductive gel as described above, comprising the following steps:

[0022] Step one, taking raw materials by mass fraction, 1-8 parts of imidazole-based olefin amide acid compound and 0.5-1 parts of organic silicon crosslinking agent are sequentially dissolved in 10-15 parts of organic solvent, 0.01-0.2 parts of emulsifier is added, and stirring is uniform to obtain a prepolymer solution;

[0023] Step two, 0.05-0.3 parts of organic oxidizing agent is dissolved in 5-10 parts of organic solvent, 1-10 parts of natural polysaccharide is added, stirring is carried out at room temperature under nitrogen protection for 24-48 hours, and then the solid product is collected by centrifugal separation, washed with ethanol for 3 times, and dried to obtain oxidized natural polysaccharide;

[0024] Step three, 1-5 parts of modifier and 1-10 parts of ginkgoaceae natural plant and the obtained oxidized natural polysaccharide in step two are dissolved in 10-30 parts of water, constant temperature oscillation reaction is carried out at 30-40 DEG C for 8-12 hours, then the prepolymer solution obtained in step one is added, 0.02-0.1 parts of stabilizer is added, stirring reaction is carried out at 50-70 DEG C for 30-60 minutes, and then the conductive gel is formed by pouring into a mold and standing reaction.

[0025] The application also protects the application of the ginkgoaceae natural extract copolymerized antibacterial conductive gel as described above as a flexible electronic sensor or a biological electric stimulation antibacterial dressing.

[0026] Compared with the prior art, the application has the following technical effects:

[0027] The ginkgoaceae natural extract with broad-spectrum antibacterial property is used as a conductive medium, flavonoids and enetere compounds in the ginkgoaceae natural extract can realize electronic conduction through delocalized pi electrons, and the high molecular chain (especially the hydrophilic and charged chain) can realize ionic conduction through bearing electrolyte ions, and when the two cooperate, the micro-current can be effectively conducted, and a "electron-ion" mixed conduction mechanism is formed; the ginkgoaceae natural extract has broad-spectrum antibacterial property; the flavonoids and enetere compounds in the ginkgoaceae natural extract are ingeniously combined with Schiff base and the like structure, the micro-current is conducted through the aromaticity continuous conjugated structure of the high molecular chain and the flavonoids and enetere, a low-toxicity antibacterial conductive gel capable of being applied to biological tissue repair is prepared, the gel as a "flexible medium" can not only conduct electric signals, but also reduce the risk of foreign body reaction through the antibacterial function, and meanwhile, the toxicity caused by the leakage of metal ions is avoided, the gel has unique advantages in the field of micro-current related flexible electronic sensors, biological electric stimulation dressings and the like, and has great application potential.

[0028] The imidazole-based olefin amide acid compound has good gel-forming performance, can form a stable three-dimensional network structure through a cross-linking reaction, and provides a basic skeleton support for the hydrogel; meanwhile, the imidazole-based olefin amide acid compound generally has good biocompatibility, which makes the application of the hydrogel in the biomedical field possible; in addition, the structure of the imidazole-based olefin amide acid compound is easy to modify and functionalize, facilitating the reaction and combination with other substances, and providing convenience for introducing various functional groups into the hydrogel.

[0029] The organic silicon compound is used as the cross-linking agent, and compared with a traditional cross-linking agent, the organic silicon compound has the characteristics of good chemical stability, high and low temperature resistance, and biocompatibility; the organic silicon is biologically inert by nature, is not easy to cause an immune response or skin irritation, has a hydrophobic surface characteristic that can block external pollutants while allowing water vapor to pass through, maintains normal skin respiration, and the hydrophobic surface of the organic silicon can reduce bacterial adhesion and physically prevent colony formation; when the organic silicon is used as the cross-linking agent, the olefin compound can be effectively cross-linked to form a stable three-dimensional network structure, and the mechanical properties, thermal stability, and solvent resistance of the hydrogel can be improved to a certain extent.

[0030] The Schiff base structure is introduced through the modifier to achieve efficient antibacterial effect: the Schiff base structure is grafted through the reaction of the modifier and the natural polysaccharide, so that the hydrogel has super-high antibacterial performance, and the problem that the hydrogel is easy to cause bacterial infection in the application process is effectively solved; the Schiff base structure generally has antibacterial ability, and the activity is derived from the interaction of the imine group with the biological molecules of bacteria and the synergistic effect of the substituent group; the nitrogen atom in the imine group has a lone pair of electrons, can coordinate with metal ions (such as Fe 2+ , Cu 2+ , etc.) in the body of bacteria (such as Fe 2+ , Cu 2+ , etc.) to participate in the catalysis or metabolism of bacterial enzymes, or can be combined with active groups (such as amino groups and sulfhydryl groups) in bacterial proteins and nucleic acids, thereby destroying the biological macromolecular structure and function of bacteria; such compounds have important application potential in the fields of new antibacterial drugs and antibacterial coatings (such as the surface of medical materials) due to the easy modification of the structure and the wide antibacterial spectrum. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 A gel cross-linking structure diagram of the antibacterial conductive gel prepared in Example 1. DETAILED DESCRIPTION

[0032] The specific content of the present application is further explained and described in detail in combination with the following examples.

[0033] The extraction methods of the natural extracts of Ginkgoaceae in the following examples include:

[0034] The dried ginkgo leaves are crushed to 20-40 mesh, dissolved in acetone solution, ultrasonically treated at room temperature for 3-5 h, washed with distilled water for 3 times, then washed with 30%-50% ethanol solution, and the products are collected and dried to obtain the natural extract of ginkgo family.

[0035] Example 1

[0036] The present example provides a preparation method of a copolymerized antibacterial conductive gel of natural extract of ginkgo family, comprising the following steps:

[0037] Step one, 1 part of N-benzimidazolyl acrylamide and 0.5 part of vinyl triethoxysilane are sequentially dissolved in 10 parts of acetone, 0.01 part of sodium dodecyl sulfate (SDS) is added, and stirred uniformly to obtain a prepolymer solution;

[0038] Step two, 0.05 part of PCC is dissolved in 10 parts of methanol, 1 part of starch is added, and stirred at room temperature for 24 h under nitrogen protection, then the reaction solution is centrifuged to separate the supernatant, and the solid product is collected by suction filtration, washed with ethanol for 3 times, and dried to obtain oxidized starch;

[0039] Step three, 1 part of lysine, 1 part of ginkgol, and the oxidized starch prepared in step two are dissolved in 10 parts of water, and reacted at 30°C for 8 h, then added to the prepolymer solution obtained in step one, 0.02 part of polyvinyl alcohol (PVA) is added, and stirred at 50°C for 30 min, then poured into a mold, and left to form a conductive gel.

[0040] Figure 1 The gel cross-linking structure diagram of the antibacterial conductive gel prepared in Example 1 is shown in FIG. 1. Figure 1 As shown in FIG. 1, the imidazolyl olefin amide acid compound, the organic silicon cross-linking agent, the oxidized natural polysaccharide, and the natural extract of ginkgo family are connected to each other by chemical bonds and functional groups to form a complex cross-linking network; the imidazolyl olefin amide acid compound forms an amide bond, the organic silicon cross-linking agent forms a silicon-oxygen-silicon bond, and the esterification reaction of the oxidized natural polysaccharide all form covalent bond cross-linking to provide strong cross-linking strength and stability; the hydrogen bonds of the oxidized natural polysaccharide and the natural extract of ginkgo family, and the non-covalent bonds formed by the π-π stacking interaction of the natural extract of ginkgo family also play an important role in the cross-linking process.

[0041] Example 2

[0042] The present example provides a preparation method of a copolymerized antibacterial conductive gel of natural extract of ginkgo family, comprising the following steps:

[0043] Step one, 2 parts of N-benzimidazolyl acrylamide and 0.6 parts of γ-methacryloyloxypropyl trimethoxysilane are sequentially dissolved in 10 parts of ethanol, 0.05 parts of sodium stearate is added, and stirred uniformly to obtain a prepolymer solution;

[0044] Step two, 0.05 parts of pyridine chlorochromate (PCC) is dissolved in 10 parts of methanol, 2 parts of starch is added, and the reaction is stirred at room temperature for 24 hours under nitrogen protection. Then the reaction solution is centrifuged to separate the supernatant, and the solid product is collected by suction filtration and washed with ethanol for 3 times, and dried to obtain oxidized starch;

[0045] Step three, 2 parts of 1H-imidazole-1-carboxamide hydrochloride and 2 parts of ginkgo are dissolved in 10 parts of water, and the reaction is oscillated at 30°C for 8 hours. Then it is added to the prepolymer solution obtained in step one, 0.04 parts of polyvinyl alcohol (PVA) is added, and the reaction is stirred at 50°C for 35 minutes. Pour into the mold and stand to form a conductive gel.

[0046] Example 3

[0047] The present embodiment gives a preparation method of a ginkgo biloba natural extract copolymerized antibacterial conductive gel, which comprises the following steps:

[0048] Step one, 3 parts of N-benzimidazolyl acrylamide and 0.7 parts of vinyl tributyl ketoxime silane are sequentially dissolved in 10 parts of methanol, 0.08 parts of Tween-80 is added, and the mixture is stirred uniformly to obtain a prepolymer solution;

[0049] Step two, 0.08 parts of PCC is dissolved in 10 parts of methanol, 5 parts of starch is added, and the reaction is stirred at room temperature for 36 hours under nitrogen protection. Then the reaction solution is centrifuged to separate the supernatant, and the solid product is collected by suction filtration and washed with ethanol for 3 times, and dried to obtain oxidized starch;

[0050] Step three, 5 parts of arginine and 8 parts of ginkgo are dissolved in 20 parts of water, and the reaction is oscillated at 40°C for 10 hours. Then it is added to the prepolymer solution obtained in step one, 0.1 parts of polyvinyl alcohol (PVA) is added, and the reaction is stirred at 60°C for 60 minutes. Pour into the mold and stand to form a conductive gel.

[0051] Example 4

[0052] The present embodiment gives a preparation method of a ginkgo biloba natural extract copolymerized antibacterial conductive gel, which comprises the following steps:

[0053] Step one, 1 part of benzimidazole acrylate and 0.5 part of γ-methacryloyloxypropyl trimethoxysilane are sequentially dissolved in 10 parts of DMSO, 0.01 parts of Tween-60 is added, and the mixture is stirred uniformly to obtain a prepolymer solution;

[0054] Step two, 0.05 parts of pyridine dichromate (PDC) is dissolved in 5 parts of DMSO, 1 part of cellulose is added, and the reaction is stirred at room temperature for 24 hours under nitrogen protection. Then the reaction solution is centrifuged to separate the supernatant, and the solid product is collected by suction filtration and washed with ethanol for 3 times, and dried to obtain oxidized cellulose;

[0055] Step three, 1 part tetramethyl guanidine lactate and 1 part ginkgo biloba extract, the oxidized cellulose prepared in step two were dissolved in 10 parts of water, constant temperature oscillation reaction at 30℃ for 8h, then added to the prepolymer solution obtained in step one, 0.02 parts of sodium carboxymethyl cellulose (CMC-Na) was added, stirred at 50℃ for 30min, poured into a mold, and the conductive gel was formed by standing reaction.

[0056] Example 5

[0057] The present example gives a preparation method of a ginkgo biloba natural extract copolymer antibacterial conductive gel, comprising the following steps:

[0058] Step one, 5 parts of benzimidazole acrylate and 1 part of vinyl triethoxysilane were dissolved in 15 parts of acetone in turn, 0.05 parts of sodium dodecyl benzene sulfonate (SDBS) was added, stirred uniformly, and a prepolymer solution was obtained;

[0059] Step two, 0.05 parts of PDC was dissolved in 10 parts of ethanol, 1 part of cellulose was added, stirred at room temperature for 36h under nitrogen protection, then the reaction solution was centrifuged to separate the supernatant, the solid product was collected by suction filtration, washed with ethanol for 3 times, and dried to obtain oxidized cellulose;

[0060] Step three, 3 parts of 1,3-di-o-tolyl guanidine salt, 3 parts of ginkgo biloba extract, and the oxidized cellulose prepared in step two were dissolved in 10 parts of water, constant temperature oscillation reaction at 35℃ for 12h, then added to the prepolymer solution obtained in step one, 0.02 parts of hydroxypropyl methyl cellulose (HPMC) was added, stirred at 60℃ for 30min, poured into a mold, and the conductive gel was formed by standing reaction.

[0061] Example 6

[0062] The present example gives a preparation method of a ginkgo biloba natural extract copolymer antibacterial conductive gel, comprising the following steps:

[0063] Step one, 8 parts of benzimidazole acrylate and 1 part of vinyl triethoxysilane were dissolved in 13 parts of ethanol in turn, 0.1 parts of Tween-60 was added, stirred uniformly, and a prepolymer solution was obtained;

[0064] Step two, 0.1 parts of PDC was dissolved in 10 parts of methanol, 1 part of cellulose was added, stirred at room temperature for 36h under nitrogen protection, then the reaction solution was centrifuged to separate the supernatant, the solid product was collected by suction filtration, washed with ethanol for 3 times, and dried to obtain oxidized cellulose;

[0065] Step three, 5 parts of 1, 3-di-o-tolyl guanidine salt, 5 parts of total ginkgo flavones, the oxidized cellulose prepared in step two was dissolved in 15 parts of water, constant temperature oscillation reaction at 40℃ for 12h, then added to the prepolymer solution obtained in step one, 0.05 parts of hydroxypropyl methyl cellulose (HPMC) was added, stirring reaction at 60℃ for 30min, poured into the mold, and the conductive gel was formed by standing reaction.

[0066] Example 7

[0067] The present example gives a preparation method of a ginkgo family natural extract copolymer antibacterial conductive gel, comprising the following steps:

[0068] Step one, 1 part of N- (p-hydroxyphenyl) -N- (imidazolyl) acrylamide and 0.5 parts of γ-methacryloyloxypropyl trimethoxysilane were dissolved in 10 parts of methanol, 0.03 parts of SDS was added, stirred uniformly, and a prepolymer solution was obtained;

[0069] Step two, 0.1 parts of Swern oxidation system was dissolved in 10 parts of acetone, 4 parts of alginic acid was added, stirring reaction at room temperature for 24h under nitrogen protection, then the reaction liquid was centrifuged to separate the supernatant, and the solid product was collected by suction filtration, washed with ethanol for 3 times, and dried to obtain oxidized alginic acid;

[0070] Step three, 2 parts of methyl guanidine glycine salt, 5 parts of ginkgo biloba lactone, and the oxidized alginic acid prepared in step two were dissolved in 10 parts of water, constant temperature oscillation reaction at 35℃ for 8h, then added to the prepolymer solution obtained in step one, 0.05 parts of polyethylene glycol (PEG) was added, stirring reaction at 70℃ for 45min, poured into the mold, and the conductive gel was formed by standing reaction.

[0071] Example 8

[0072] The present example gives a preparation method of a ginkgo family natural extract copolymer antibacterial conductive gel, comprising the following steps:

[0073] Step one, 4 parts of N- (p-hydroxyphenyl) -N- (imidazolyl) acrylamide and 0.8 parts of γ-methacryloyloxypropyl trimethoxysilane were dissolved in 15 parts of DMSO, 0.08 parts of Span-60 was added, stirred uniformly, and a prepolymer solution was obtained;

[0074] Step two, 0.2 parts of aluminum alcohol salt was dissolved in 8 parts of acetone, 8 parts of alginic acid was added, stirring reaction at room temperature for 36h under nitrogen protection, then the reaction liquid was centrifuged to separate the supernatant, and the solid product was collected by suction filtration, washed with ethanol for 3 times, and dried to obtain oxidized alginic acid;

[0075] Step three, 4 parts of methyl guanidine glycine salt, 8 parts of ginkgo lactone, the oxidized alginic acid prepared in step two was dissolved in 20 parts of water, constant temperature oscillation reaction at 40℃ for 10h, then added to the prepolymer solution obtained in step one, 0.08 parts of chitosan (CS) was added, 70℃ stirring reaction for 50min, poured into the mold, and the reaction was formed into a conductive gel by standing.

[0076] Example 9

[0077] The present embodiment gives a preparation method of a ginkgo biloba natural extract copolymer antibacterial conductive gel, comprising the following steps:

[0078] Step one, 8 parts of N-(p-hydroxyphenyl)-N-(imidazolyl) acrylamide and 1 part of γ-methacryloyloxypropyl trimethoxysilane were successively dissolved in 12 parts of methanol, 0.2 parts of Span-80 was added, stirred uniformly to obtain a prepolymer solution;

[0079] Step two, 0.3 parts of Swern oxidation system was dissolved in 10 parts of acetone, 10 parts of alginic acid was added, stirred at room temperature for 48h under nitrogen protection, then the reaction solution was centrifuged to separate the supernatant, and the solid product was collected by suction filtration and washed with ethanol for 3 times, and dried to obtain oxidized alginic acid;

[0080] Step three, 5 parts of p-hydroxyphenyl guanidine sulfate, 10 parts of ginkgo lactone, and the oxidized alginic acid prepared in step two were dissolved in 30 parts of water, constant temperature oscillation reaction at 40℃ for 10h, then added to the prepolymer solution obtained in step one, 0.1 parts of polyethylene glycol (PEG) was added, 70℃ stirring reaction for 60min, poured into the mold, and the reaction was formed into a conductive gel by standing.

[0081] Comparative example 1

[0082] Step one, 2 parts of polyacrylic acid (PAA) and 1 part of vinyl tributyl ketoxime silane were successively dissolved in 20 parts of ethanol, 0.1 parts of SDS was added, stirred uniformly to obtain a prepolymer solution;

[0083] Step two, 3 parts of alginic acid was dissolved in 30 parts of water respectively to obtain an alginic acid solution;

[0084] Step three, 2 parts of the alginic acid solution obtained in step two was added to the prepolymer solution obtained in step one, 0.1 parts of gelatin was added, 65℃ stirring reaction for 60min, poured into the mold, and the reaction was formed into a comparative example hydrogel 1 by standing.

[0085] Comparative example 2

[0086] Step one, 2 parts of polyacrylic acid (PAA) and 1 part of vinyl tributyl ketoxime silane were successively dissolved in 20 parts of ethanol, 0.1 parts of SDS was added, stirred uniformly to obtain a prepolymer solution;

[0087] Step two, 3 parts of oxidized gelatin were dissolved in 30 parts of water respectively to obtain oxidized gelatin solution;

[0088] Step three, 2 parts of the oxidized gelatin solution obtained in step two were added to the prepolymer solution obtained in step one, 0.1 part of gelatin was added, and stirring reaction was carried out at 65°C for 60 min, and then the mixture was poured into a mold to form a comparative hydrogel 2.

[0089] Comparative example 3

[0090] Step one, 2 parts of polyacrylic acid (PAA) and 1 part of vinyl tributyl ketoxime silane were sequentially dissolved in 20 parts of ethanol, 0.1 part of SDS was added, and stirring was carried out until uniform, to obtain a prepolymer solution;

[0091] Step two, 3 parts of oxidized hyaluronic acid were dissolved in 30 parts of water respectively to obtain oxidized hyaluronic acid solution;

[0092] Step three, 2 parts of the oxidized hyaluronic acid solution obtained in step two were added to the prepolymer solution obtained in step one, 0.1 part of gelatin was added, and stirring reaction was carried out at 65°C for 60 min, and then the mixture was poured into a mold to form a comparative hydrogel 3.

[0093] Antibacterial test

[0094] A sterile culture dish containing agar medium was added with E. coli bacterial suspension and S. aureus bacterial suspension respectively, and after uniform oscillation, phosphate buffer solution was added, and the gel samples of examples 1-9 and comparative examples 1-3 were cut into thin slices of the same size and placed in the sterile culture dish, and the culture dishes containing examples 1-9 and comparative examples 1-3 were placed in a constant temperature and humidity incubator, and cultured at 37°C for 24h and 48h, and the antibacterial rate was calculated.

[0095] The test results are shown in Table 1:

[0096] Table 1 Inhibition effect of conductive gel on E. coli and S. aureus

[0097]

[0098] From the above table, it can be seen that in examples 1-9, the natural polysaccharide polymerized hydrogel modified by the modifier has a significant inhibition effect on the measured E. coli and S. aureus. The antibacterial rate of comparative example 1 is the lowest, and the possible reason is that sodium alginate without any treatment has no inhibition effect on bacteria, but may provide a suitable environment for bacterial growth, and after comprehensive consideration of other components, the antibacterial rate is lower. Comparative examples 2 and 3 show that the natural polysaccharide polymerized hydrogel without modification by the modifier has a much lower inhibition effect on the measured E. coli and S. aureus than examples 1-9.

[0099] In summary, the guanidine salt is used to graft the monomer containing aldehyde group with guanidine group, which greatly improves the antibacterial ability of the hydrogel.

[0100] Conductive performance test

[0101] The conductive performance of the ginkgo biloba natural extract copolymerized antibacterial conductive gel of the present application was tested as follows:

[0102] The conductivity of the material was tested by an electrochemical workstation. The conductive hydrogel was cut into a sample of 50 mm x 5 mm x 3 mm, which was fixed and clamped between the two ends of the electrode clamp, and the voltage was set to 1.5 V. The conductivity (σ) of the hydrogel sample was calculated as follows:

[0103] σ = d / (R x A)

[0104] d: distance between adjacent electrodes (mm);

[0105] R: resistance of the hydrogel sample (Ω);

[0106] A: cross-sectional area of the hydrogel sample (mm 2 ).

[0107] The conductive performance test results are shown in Table 2.

[0108] Table 2 Conductive performance test results

[0109]

[0110] As can be seen from Table 2, the conductive gel of the copolymerized ginkgo biloba antibacterial extract prepared by the method of the present application has reliable conductive performance, and can effectively and accurately transmit bioelectric signals when applied to a biological strain sensor.

[0111] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application and not to limit it, although the present application has been described in detail with reference to the above examples, those skilled in the art should understand that: the specific embodiments of the present application can be modified or replaced, without departing from the spirit and scope of the present application, any modification or equivalent replacement, which should be covered within the protection scope of the claims of the present application.

Claims

1. A conductive gel copolymerized with natural extracts of the Ginkgoaceae family, characterized in that, The raw materials comprise the following components by mass: 1–10 parts of Ginkgo biloba natural extract, 1–8 parts of imidazolyl alkenyl amino acid compound, 0.02–0.1 parts of stabilizer, 0.01–0.2 parts of emulsifier, 0.5–1 parts of organosilicon crosslinking agent, 1–5 parts of modifier, 0.05–0.3 parts of organic oxidant, 1–10 parts of natural polysaccharide, 15–25 parts of organic solvent, and 10–30 parts of water.

2. The conductive gel copolymerized with Ginkgo biloba natural extracts for antibacterial properties as described in claim 1, characterized in that, The natural extracts of the Ginkgoaceae family include one or more of ginkgolide, total ginkgo flavonoids, and ginkgo lactone. The extraction method for the Ginkgo biloba natural extract includes: The dried ginkgo leaves were pulverized to 20-40 mesh, dissolved in acetone solution, and ultrasonically treated at room temperature for 3-5 hours. After eluting three times with distilled water, the product was eluted with 30%-50% ethanol solution. The products were collected separately, dried, and then the natural extract of Ginkgoaceae was obtained.

3. The conductive gel copolymerized with Ginkgo biloba natural extracts for antibacterial properties as described in claim 1, characterized in that, The imidazolyl alkenyl ammonium acid compounds include any one of N-benzimidazolylacrylamide, N-(p-hydroxyphenyl)-N-(imidazolyl)acrylamide, and benzimidazolyl acrylate.

4. The conductive gel copolymerized with Ginkgo biloba natural extracts for antibacterial properties as described in claim 1, characterized in that, The stabilizer includes any one of polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose, polyethylene glycol, and chitosan.

5. The conductive gel copolymerized with Ginkgo biloba natural extracts for antibacterial properties as described in claim 1, characterized in that, The emulsifier includes any one or a mixture of several of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium stearate, Tween-80, Tween-60, Span-60 and Span-80 in any proportion.

6. The conductive gel copolymerized with Ginkgo biloba natural extracts for antibacterial properties as described in claim 1, characterized in that, The organosilicon crosslinking agent includes any one of vinyltributylone oxime silane, γ-methacryloyloxypropyltrimethoxysilane, and vinyltriethoxysilane.

7. The conductive gel copolymerized with Ginkgo biloba natural extracts for antibacterial properties as described in claim 1, characterized in that, The modifiers include any one or more of lysine, arginine, 1H-imidazolium-1-formamidinium hydrochloride, tetramethylguanidine lactate, 1,3-di-o-tolylguanidine salt, methylguanidine glycinate, and p-hydroxyphenylguanidine sulfate; The organic oxidant includes any one of pyridine chlorochromate, pyridine dichromate, the Swern oxidation system, or aluminum alkoxide.

8. The conductive gel copolymerized with Ginkgo biloba natural extracts for antibacterial properties as described in claim 1, characterized in that, The natural polysaccharides mentioned include any one of cellulose, starch, and alginic acid; The organic solvent includes any one of methanol, ethanol, acetone, and dimethyl sulfoxide.

9. A method for preparing a conductive gel copolymerized with Ginkgo biloba natural extracts for antibacterial properties as described in any one of claims 1 to 8, characterized in that, Includes the following steps: Step 1: Take the raw materials according to the mass fraction, dissolve 1-8 parts of imidazolyl alkenyl ammonium acid compound and 0.5-1 parts of organosilicon crosslinking agent in 10-15 parts of organic solvent, add 0.01-0.2 parts of emulsifier, stir evenly to obtain a prepolymer solution; Step 2: Dissolve 0.05-0.3 parts of organic oxidant in 5-10 parts of organic solvent, add 1-10 parts of natural polysaccharide, stir and react at room temperature for 24-48 hours under nitrogen protection, then centrifuge to collect the solid product, wash with ethanol 3 times, and dry to obtain oxidized natural polysaccharide. Step 3: Dissolve 1-5 parts of modifier, 1-10 parts of natural Ginkgo biloba plant, and the oxidized natural polysaccharide prepared in Step 2 in 10-30 parts of water, and react at a constant temperature of 30-40℃ with shaking for 8-12 hours. Then add it to the prepolymer solution obtained in Step 1, add 0.02-0.1 parts of stabilizer, stir at 50-70℃ for 30-60 minutes, pour into a mold, and let it stand to react and form a conductive gel.

10. The application of a conductive gel copolymerized with natural Ginkgo biloba extracts as described in any one of claims 1 to 8 as a flexible electronic sensor or a bioelectric stimulation antibacterial dressing.

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