Nano-silver dressing solution with efficient sterilization and stable dispersion and preparation method of nano-silver dressing solution
By preparing triangular morphology nanosilver dressing solution in terminal amino hyperbranched polymers, the nanosilver surface charge is regulated by amino acids, the problem of insufficient dispersion and antibacterial ability of the nanosilver dressing solution is solved, and stability and biological phase are achieved Improvement of capacities.
Patent Information
- Application Number
- CN202411379524.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-29
- Publication Date
- 2024-12-27
AI Technical Summary
The existing nanosilver dressing solutions have poor dispersion and weak antibacterial ability, resulting in reduced stability and reduced antibacterial properties, and commonly used surfactants may bring risks of biotoxicity.
The nanosilver dressing solution with triangular morphology was prepared by reducing silver ions by amino acids with isoelectric point greater than 7 to ensure its stable dispersion and efficient antibacterial ability.
The stable dispersion and efficient antibacterial ability of nano-silver dressing solution are achieved, while avoiding biotoxicity problems and ensuring good biocompatibility.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the preparation of nanomaterial dressings with antibacterial efficacy, and specifically relates to a preparation of nanosilver with triangular morphology based on hyperbranched polymers, wherein the surface charge of the triangular nanosilver is adjusted by amino acids to achieve a triangular nanosilver dressing solution with high stability, good dispersibility and high bactericidal ability. Background Art
[0002] The skin isolates the human body from the internal and external environment, avoiding physical, chemical and microbial invasions, thereby protecting the human body. Since the skin is easily affected by external factors such as mechanical, thermal and chemical agents, different types of wounds are caused. If you encounter deep wounds or burns, the skin's self-healing ability is far from enough. If these difficult-to-heal wounds are infected with bacteria, they may have very serious consequences, such as amputation or death. In order to promote wound healing, a variety of wound dressings have been gradually developed, including gauze, cotton wool, hydrogel polymer films, materials alginate, and collagen. These wound dressings can protect and promote wound healing.
[0003] As antibacterial solutions, the metal ions used more often are silver, copper and zinc, among which silver-containing antibacterial agents have the best antibacterial effect. Its mechanism of action is mainly that the metal ions attached to the carrier or the surface will be slowly released during use, and then penetrate into the peptidoglycan layer or bacterial wall of the bacteria, destroying DNA and bacterial proteins. This damage will affect the key metabolic processes of bacteria, destroy the normal life activities of bacteria, and eventually cause the death of bacteria.
[0004] The antibacterial activity of nanosilver is related to many factors, such as action time, dosage, temperature, type of bacteria or cells, etc. It is also related to many properties of nanosilver itself, such as size, shape, surface coating, and hydrophilicity / hydrophobicity of nanosilver. The size of nanosilver particles is one of the most important physical and chemical characteristics that determine the antibacterial efficacy of nanosilver and its cytotoxicity to mammalian cells. Compared with larger nanosilver particles, smaller nanosilver particles have a larger specific surface area, which leads to a higher adhesion rate on the bacterial cell membrane, higher permeability, stronger ability to penetrate biological barriers, and stronger ability to be taken up by cells, thus having better antibacterial effect and greater cytotoxicity. Thilini Silva et al. [1] used silver nitrate as a precursor to prepare nanosilver with three different particle sizes of 10nm, 56nm, and 72nm. The results showed that at the same action concentration, 10nm nanosilver particles were the most toxic to both, followed by 56nm silver particles, and 72nm silver particles were the least toxic. Usually, nanosilver particles are very easy to aggregate, which leads to the decrease of the stability of nanosilver solution, and the antibacterial property and cytotoxicity of nanosilver will also decrease. This is because the active surface of aggregated nanosilver particles is reduced, and the possibility of them attaching to the surface of bacteria or cells is reduced. Therefore, the preparation of dispersed and stable nanosilver solution is the prerequisite for obtaining high-quality antibacterial silver dressings.
[0005] There are many methods for reducing silver ions to nano silver, and the nano silver solutions formed by most methods are extremely unstable, which is caused by the aforementioned nano silver particles being very easy to reunite. In order to obtain a stable nano silver dispersion solution, Chen Ling used methyl acrylate, diethylenetriamine, etc. as raw materials, and methanol as solvent to prepare a series of amino-terminated hyperbranched polymers. Since the amino-terminated hyperbranched polymer surface contains a large amount of amino and imino groups, the prepared hyperbranched polymers not only have a certain reducibility, but also can reduce silver ions. At the same time, due to its weaker reducibility, silver nano particles with smaller particle size can be obtained. The surface charge of nano silver particles has a great influence on the antibacterial activity of nano silver particles and cell compatibility. This is not only reflected in the fact that positively charged nano silver is easy to adsorb with negatively charged fungi by electrostatic attraction, but also because positively charged nano silver is not easy to reunite, the antibacterial activity of silver nano particles is maintained. Although there are many studies on maintaining the stability of silver nanoparticles by adding surfactants, these solutions maintain the activity of nanosilver, but do not effectively regulate the charge of nanosilver. It should be pointed out that since the present invention is to prepare an antibacterial dressing for skin injury, the primary condition is that the added substance cannot have biological toxicity. Therefore, how to prepare a nanosilver dressing with good dispersibility and high antibacterial ability under the condition of good biocompatibility is a technical problem to be solved by the present invention. Summary of the invention
[0006] In view of a series of problems such as poor dispersion stability and weak antibacterial ability of the currently prepared nanosilver dressing solutions, the present invention is based on the reduction of silver ions by hyperbranched polymers, the regulation of the morphology of nanosilver by organic acid ligands, and the further adjustment of the surface charge of silver nanoparticles by amino acids, thereby successfully preparing a nanosilver hyperbranched polymer dressing solution with stable dispersion and high antibacterial ability.
[0007] In order to solve the above problems, the technical solution adopted by the present invention is:
[0008] Triangular silver nanoparticles (AgNPs-HP) were obtained in a hyperbranched polymer containing terminal amino groups, and the nanoparticles were then surface-modified with amino acids having an isoelectric point greater than 7 to obtain stably dispersed hyperbranched polymer triangular silver nanoparticles ( + H3N-R / AgNPs-HP) solution, i.e., nanosilver dressing solution.
[0009] The specific preparation steps are as follows:
[0010] (1) Preparation of hyperbranched polymer containing terminal amino groups: Place a polyamino monomer solution in a reaction vessel, add a monomer solution containing carboxyl or ester groups dropwise under ice-water cooling, and continue to stir the mixture system in the reaction vessel at room temperature and pressure for 4-5 hours after the addition is complete. Remove the solvent from the mixture under reduced pressure, then heat the mixture to 150°C and continue to react for 1-1.5 hours, then cool to 120°C to preliminarily obtain a hyperbranched polymer containing terminal amino groups. Then add the prepared polyacid to the reaction vessel, and react under constant temperature and reduced pressure for 2 hours to obtain a hyperbranched polymer rich in terminal amino groups. The final mass concentration of the hyperbranched polymer containing terminal amino groups is about 0.1-2%.
[0011] (2) adding the prepared hyperbranched polymer containing terminal amino groups to deionized water to prepare a polymer aqueous solution of a certain concentration, then adding an aqueous silver nitrate solution to the polymer aqueous solution, and continuing to stir the reaction for about 60 minutes to obtain a solution of triangular silver nanoparticles (AgNPs-HP) dispersed in the hyperbranched polymer containing terminal amino groups;
[0012] (3) Surface modification of silver nanoparticles with amino acids having an isoelectric point greater than pH 7: Specifically, an ethanol solution of amino acids having an isoelectric point greater than pH 7.0 and a concentration of 0.1 to 1 mM is added to a dispersion of silver nanoparticles containing a terminal amino hyperbranched polymer, and stirred at room temperature for 8 hours. The silver nanoparticles can be stably dispersed in an aqueous solution of the terminal amino hyperbranched polymer without agglomeration. Figure 2 A), triangular-shaped silver nanoparticles with positive surface charges ( + H3N-R / AgNPs-HP) particles.
[0013] Wherein, the polyamino monomer solution in step (1) is a methanol solution of any one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or hexaethyleneheptamine;
[0014] The monomer solution containing carboxyl or ester group is any one or more methanol solutions of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate and methyl methacrylate, and the mass concentration is 40-50%.
[0015] The molar ratio of the polyamino monomer to the monomer containing a carboxyl group or an ester group is 1:1.
[0016] Wherein, the polyacid selected in step (1) is any one or two of sebacic acid, undecane dicarboxylic acid, dodecanedioic acid, pentadecane dicarboxylic acid, and triazine polycarboxylic acid. The principle of selecting the polyacid is that it can neutralize the pH of the reaction system to near neutrality, and can complex with silver ions to increase the stability of the nano silver particles after the reaction, but it cannot have too strong complexing ability with silver ions, such as complexing agents such as citric acid, because the complexing ability of citric acid with silver ions is too strong, which inhibits the reduction of silver ions and makes it difficult to obtain a nano silver solution in a hyperbranched polymer.
[0017] The amount of polyacid added is preferably such that the pH value of the hyperbranched polymer containing terminal amino groups is between 6.5 and 7.5. Because it is a dressing solution, the pH should be kept as neutral as possible. If the pH is adjusted to 7.5 or higher, the charge of the silver nanoparticles changes due to the further dissociation of the amino groups on the amino acids. If the pH is lower than 6.5, the positive charge of the silver nanoparticles can be guaranteed, but it will cause irritation and damage to the skin.
[0018] In order to effectively improve the antibacterial ability of silver nanoparticles, the present invention adds a polyacid, a morphology regulator of silver nanoparticles, to the above-mentioned hyperbranched polymer containing terminal amino groups. In order to prevent the dressing solution from causing strong irritation to the skin, after the polyacid is added, the morphology of the silver nanoparticles (AgNPs-HP) becomes a triangle ( Figure 1 B). If no polyacid is added, the initially obtained hyperbranched polymer containing terminal amino groups is used to reduce silver ions to obtain spherical silver nanoparticles ( Figure 1 A).
[0019] The concentration of the silver nitrate aqueous solution in step (2) is 0.01-0.10 mol / L, and the volume ratio of the aqueous solution of the hyperbranched polymer containing terminal amino groups to the silver nitrate aqueous solution is 1:1. The mass concentration of the nanosilver in the triangular nanosilver (AgNPs-HP) solution dispersed in the hyperbranched polymer containing terminal amino groups is 0.1-2%.
[0020] Wherein, in step (3), the amino acid with an isoelectric point greater than 7 is one or more of lysine, arginine or histidine.
[0021] The concentration of the amino acid solution with an isoelectric point greater than 7 is 0.1-1 mM; the volume ratio of the amino acid solution with an isoelectric point greater than 7 to the silver solution is 0.1-0.2:10.
[0022] In order to further adjust the surface charge of the silver nanoparticles, the surface of the silver nanoparticles of the present invention is modified with positively charged amino acids, thereby improving the antibacterial ability of the silver nanoparticles and further improving the dispersion stability of the nanosilver particles. Finally, a nanosilver dressing solution is prepared.
[0023] Beneficial effects of the present invention
[0024] The invention successfully prepares nano silver particles by reducing silver ions with hyperbranched polymers. The invention is significantly different from the nano silver solution prepared in the past in that, in order to achieve the ability of efficient antibacterial, the shape of nano silver is successfully regulated to be triangular by adding organic acid ligands in the hyperbranched polymers. In order to effectively improve the defects of the nano silver solution that is difficult to solve at present, such as easy agglomeration and instability, the stable dispersion of the nano silver solution is achieved by regulating the surface charge of the nano silver, and the antibacterial ability of the nano silver particles is effectively improved due to the presence of positive charges on the surface of the silver nano particles. Since the surface charge regulator is an amino acid, the nano silver is used as a dressing solution, which ingeniously solves the problem of biological toxicity of the nano silver particles prepared in general, and achieves a nano silver dressing solution with good biocompatibility, efficient antibacterial and good stability.
[0025] The present invention solves the biological toxicity problem ingeniously by adding amino acids with isoelectric points higher than the pH of the hyperbranched polymer system. Since silver ions are easily complexed with amino acids, and the isoelectric points of amino acids such as lysine, arginine and histidine are higher than the pH of the hyperbranched polymer aqueous solution system, the amino acid molecules complexed with silver ions present a positive charge as a whole. The triangular nanosilver ( + H3N-R / AgNPs-HP) particles and preparation of stably dispersed hyperbranched polymer aqueous solutions. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 The electron microscope images are of nanosilver (A) obtained by reducing silver ions with a hyperbranched polymer containing terminal amino groups and nanosilver (B) obtained by adding a polyacid to a hyperbranched polymer containing terminal amino groups to reduce silver ions.
[0027] Figure 2 The absorbance value change diagram of nanosilver particles after 72 hours of storage; A is +H3N-R / AgNPs-HP, B is spherical AgNPs-HP, C is triangular AgNPs-HP; 1 is the absorbance value of the nanosilver solution after synthesis, and 2 is the absorbance value of the nanosilver after being placed for 72 hours. DETAILED DESCRIPTION
[0028] The stability and antibacterial effect of the nano-silver dressing solution of the present invention are further illustrated by the following examples. In order to effectively illustrate the stability effect and antibacterial principle of the nano-silver of the present invention, spherical nano-silver, triangular nano-silver and positively charged silver nano-silver with the same silver particle concentration dispersed in the amino-terminated hyperbranched polymer were prepared. + H3N-R / AgNPs-HP particles.
[0029] The following are several specific examples and comparative examples to illustrate the characteristics of the nano-silver dressing solution of the present invention. The claims of the present invention are not limited to the reaction conditions and raw material concentrations listed in the following examples.
[0030] Example 1
[0031] Place 73.1 mL of triethylenetetramine in a 250 mL two-necked flask, cool in an ice-water bath, and stir at a constant speed. Slowly add a mixed solution of 43.0 mL of methyl acrylate and 50 mL of methanol using a constant pressure funnel. After the addition is complete, continue to stir and react at room temperature for 4 hours. Then transfer the mixture to a rotary evaporator, remove the methanol under reduced pressure, heat to 150° C. under reduced pressure and react for 1 hour, then cool to 120° C., add 2.75 g of ground dodecane dicarboxylic acid, and continue to distill under reduced pressure for 2 hours to obtain a hyperbranched polymer containing terminal amino groups with a pH of 6.5.
[0032] 50mL mass percent is 0.5% of the above-mentioned aqueous solution containing rich terminal amino hyperbranched polymer, mixed with 50mL mass molar concentration of 0.02mol / L silver nitrate aqueous solution, stirred for about 60min, obtained the silver solution (particle diameter is about 210nm) dispersed in the hyperbranched polymer containing terminal amino. 0.5mL mass molar concentration is that the ethanolic solution of 0.1mmol / L lysine is added to the above-mentioned solution, stirred for 8h in dark, can obtain the nano silver dispersion liquid with positive charge on the surface modification, and the shape is a triangle. And investigate the stability and antibacterial ability of this nano silver dispersion liquid after 72 hours, the results are listed in Table 1.
[0033] Example 2
[0034] Place 75.7 mL of tetraethylenepentamine in a 250 mL two-necked flask, cool in an ice-water bath, and stir at a constant speed. Slowly add 40.0 mL of a mixed solution of methyl methacrylate and 40 mL of methanol using a constant pressure funnel. After the addition is complete, continue stirring and react at room temperature for 4.5 hours. Then transfer the mixture to a rotary evaporator, remove the methanol under reduced pressure, heat to 150°C under reduced pressure and react for 1.5 hours, then cool to 120°C, add 2.97 g of ground triazine polycarboxylic acid, and continue to distill under reduced pressure for 2 hours to obtain a hyperbranched polymer containing rich terminal amino groups with a pH of 6.7.
[0035] 50mL mass percent is 0.3% of the above-mentioned aqueous solution containing rich terminal amino hyperbranched polymer, mixed with 50mL mass molar concentration of 0.01mol / L silver nitrate aqueous solution, stirring reaction for about 50min, obtains the silver solution (particle diameter is about 220nm) dispersed in the hyperbranched polymer containing terminal amino. 1mL mass molar concentration is that the arginine ethanol solution of 0.18mmol / L is added to the reaction, stirred for 8h in dark, can obtain the nano silver dispersion liquid with positive charge on the surface modification, and morphology is a triangle. Investigate the stability and antibacterial ability of this nano silver dispersion liquid after 72 hours, and the results are listed in Table 1.
[0036] Example 3
[0037] Place 69.7 mL of pentaethylenehexamine in a 250 mL two-necked flask, cool in an ice-water bath, and stir at a constant speed. Slowly add 30.0 mL of a mixed solution of ethyl acrylate and 40 mL of methanol using a constant pressure funnel. After the addition is complete, continue to stir and react at room temperature for 4 hours. Then transfer the mixture to a rotary evaporator, remove the methanol under reduced pressure, heat to 150° C. under reduced pressure and react for 1.5 hours, then cool to 120° C., add 1.88 g of ground sebacic acid and undecane dicarboxylic acid in a molar mass ratio of 1:1, and continue to distill under reduced pressure for 1.5 hours to obtain a hyperbranched polymer rich in terminal amino groups with a pH of 6.8.
[0038] 50mL of the aqueous solution containing the above-mentioned rich terminal amino hyperbranched polymer with a mass percentage of 0.6% was mixed with 50mL of the silver nitrate aqueous solution with a mass molar concentration of 0.03mol / L, and the reaction was stirred for about 55min to obtain a silver solution with a particle size of about 200nm dispersed in the terminal amino hyperbranched polymer. 0.5mL of the ethanol solution of histidine with a mass molar concentration of 0.23mmol / L was added to the reaction, stirred for 8h in dark, and a nano silver dispersion with a positive charge on the surface and a triangular shape was obtained. The stability and antibacterial ability of the nano silver dispersion after 72 hours were investigated, and the results are listed in Table 1.
[0039] Comparative Example 1
[0040] Place 73.1 mL of triethylenetetramine in a 250 mL two-necked flask, cool in an ice-water bath, and stir at a constant speed. Slowly add a mixed solution of 43.0 mL of methyl acrylate and 50 mL of methanol using a constant pressure funnel. After the addition is complete, continue stirring and react at room temperature for 4 hours. Then transfer the mixture to a rotary evaporator, remove methanol under reduced pressure, and heat to 150°C under reduced pressure to react for 1 hour to obtain a hyperbranched polymer containing terminal amino groups.
[0041] 50 mL of the aqueous solution containing the amino-terminated hyperbranched polymer with a mass percentage of 0.5% was mixed with 50 mL of an aqueous solution of silver nitrate with a mass molar concentration of 0.02 mol / L, and stirred for reaction for about 60 min to obtain a silver solution with a particle size of about 150 nm and a spherical morphology dispersed in the amino-terminated hyperbranched polymer ( Figure 1 A). 0.5 mL of ethanol solution with a mass molar concentration of 0.1 mmol / L lysine was added to the above spherical silver solution, and stirred for 8 hours in the dark to obtain a nanosilver dispersion with a surface modified with positive charges and a spherical morphology. The stability and antibacterial ability of the nanosilver dispersion were investigated after 72 hours, and the results are listed in Table 1.
[0042] Comparative Example 2
[0043] Place 73.1 mL of triethylenetetramine in a 250 mL two-necked flask, cool in an ice-water bath, and stir at a constant speed. Slowly add a mixed solution of 43.0 mL of methyl acrylate and 50 mL of methanol using a constant pressure funnel. After the addition is complete, continue to stir and react at room temperature for 4 hours. Then transfer the mixture to a rotary evaporator, remove the methanol under reduced pressure, heat to 150° C. under reduced pressure and react for 1 hour, then cool to 120° C., add 2.75 g of ground dodecane dicarboxylic acid, and continue to distill under reduced pressure for 2 hours to obtain a hyperbranched polymer containing terminal amino groups with a pH of 6.5.
[0044] 50 mL of the aqueous solution containing the terminal amino group-rich hyperbranched polymer with a mass percentage of 0.5% was mixed with 50 mL of a silver nitrate aqueous solution with a mass molar concentration of 0.02 mol / L, and stirred for reaction for about 60 minutes to obtain a nanosilver solution with a particle size of about 200 nm and a triangular morphology dispersed in the terminal amino group-containing hyperbranched polymer ( Figure 1 B). The stability and antibacterial ability of the nanosilver dispersion were investigated after 72 hours. The results are listed in Table 1.
[0045] In order to evaluate the stability of the silver nanoparticle solution containing terminal amino hyperbranched polymer, the absorbance value of the silver nanoparticle solution of the terminal amino hyperbranched polymer was measured by a spectrophotometer, and the stability of the silver nanoparticle solution was evaluated based on the change of the absorbance value of the silver nanoparticle solution. In the embodiments and comparative examples, the preparation methods of the silver nanoparticle solution in the terminal amino hyperbranched polymer are slightly different, but as shown in FIG. Figure 2As shown in the figure, due to the same concentration of nanosilver, the absorbance values of the nanosilver solutions shown are almost the same. However, after 72 hours, due to different preparation methods, the absorbance values of the nanosilver solutions shown will change greatly, which means that the silver particles in the nanosilver solution are easy to agglomerate and the nanosilver solution is unstable. In order to effectively describe the stability of the nanosilver solution, the present invention uses the rate of change of the absorbance value after 72 hours to describe the stability of the nanosilver solution, that is, It can be seen that the smaller the value of ΔA%, the more stable the dispersibility of the nanosilver solution is, and the nanosilver particles are less likely to agglomerate.
[0046] In order to investigate the antibacterial ability of nanosilver solution, Escherichia coli was selected as the analysis object. First, the filter paper was immersed in the nanosilver solution with the same silver concentration (the silver concentration was 50ppm), and the filter paper was taken out and pasted on the surface of the agar medium coated with Escherichia coli, and cultured in a constant temperature incubator at 37℃ for 24h, and then the diameter of the antibacterial circle was measured with a ruler to measure the antibacterial effect of different nanosilver dispersions.
[0047] Table 1 Stability and antibacterial ability of nanosilver dispersions in Examples and Comparative Examples
[0048]
[0049] From the results in Table 1, it can be seen that the triangular and positively charged nanosilver particles dispersed in the amino-terminated hyperbranched polymer of the present invention have good stability and high antibacterial ability.
[0050] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A highly efficient bactericidal and stably dispersed nano-silver dressing solution, characterized in that: Triangular nanosilver was prepared based on the reduction of silver ions by hyperbranched polymers containing polyacids. The nanosilver was surface-modified with amino acids with an isoelectric point greater than 7 to obtain a stably dispersed hyperbranched polymer triangular nanosilver solution.
2. The method for preparing the highly efficient bactericidal and stably dispersed nano-silver dressing solution according to claim 1, characterized in that: (1) placing a polyamino monomer solution in a reaction vessel, and dropping a monomer solution containing a carboxyl group or an ester group in an ice-water bath, stirring the mixture in the reaction vessel for 4-5 hours at room temperature and pressure after the dropping is completed, removing the solvent under reduced pressure, and then heating to 150° C. to continue reacting for 1-1.5 hours, and then cooling to 120° C. to preliminarily obtain a hyperbranched polymer containing terminal amino groups; then adding a polyacid to the reaction vessel, and reacting at a constant temperature and reduced pressure for 2 hours to obtain a hyperbranched polymer rich in terminal amino groups; (2) adding deionized water to the prepared hyperbranched polymer rich in terminal amino groups to prepare a polymer aqueous solution, adding an aqueous silver nitrate solution to the polymer aqueous solution, stirring the reaction, and obtaining a triangular nanosilver solution dispersed in the hyperbranched polymer containing terminal amino groups; (3) The triangular silver nanoparticles dispersed in the hyperbranched polymer containing terminal amino groups are surface modified with an amino acid solution having an isoelectric point greater than 7 to obtain a stably dispersed triangular silver nanoparticle solution of the hyperbranched polymer.
3. The method for preparing the highly efficient bactericidal and stably dispersed nano-silver dressing solution according to claim 2, characterized in that: The polyamino monomer in step (1) is any one or more combinations of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine.
4. The method for preparing the highly effective bactericidal and stably dispersed nano-silver dressing solution according to claim 2, characterized in that: The monomer containing a carboxyl group or an ester group is any one or more combinations of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, and methyl methacrylate; the molar ratio of the polyamino monomer to the monomer containing a carboxyl group or an ester group is 1:
1.
5. The method for preparing the highly effective bactericidal and stably dispersed nano-silver dressing solution according to claim 2, characterized in that: The polyacid is any one or a combination of two of sebacic acid, undecanedioic acid, dodecanedioic acid, pentadecane dicarboxylic acid and triazine polycarboxylic acid; the amount of the polyacid added is such that the pH value of the hyperbranched polymer containing terminal amino groups is between 6.5 and 7.
5.
6. The method for preparing the highly effective bactericidal and stably dispersed nano-silver dressing solution according to claim 2, characterized in that: The mass concentration of the triangular nano silver solution dispersed in the hyperbranched polymer containing terminal amino groups is 0.1-2%.
7. The method for preparing the highly effective bactericidal and stably dispersed nano-silver dressing solution according to claim 2, characterized in that: The amino acids with an isoelectric point greater than 7 are one or more combinations of lysine, arginine and histidine.
8. The method for preparing the highly effective bactericidal and stably dispersed nano-silver dressing solution according to claim 2, characterized in that: The concentration of the amino acid solution with an isoelectric point greater than 7 is 0.1-1 mM; the volume ratio of the amino acid solution with an isoelectric point greater than 7 to the triangular nanosilver solution dispersed in the hyperbranched polymer containing terminal amino groups is 1:50-100.