A metal-based polymer nanoparticle antibacterial agent, its preparation method and application

Abstract

This invention discloses a metal-based polymer nanoparticle antibacterial agent, its preparation method, and its application. The preparation method involves dissolving a polymer peptide in a polar solvent, adding a metal salt or inorganic metal complex under stirring, heating to 25–160°C, reacting for 2–24 hours, and then continuing the pyrolysis reaction at 60–160°C for 1–18 hours. After the reaction, the product is collected, washed, and dried to obtain the metal-based polymer nanoparticle antibacterial agent. This invention synthesizes triphenylphosphine-modified metal-based polymer nanoparticles with an inorganic-organic polymer hybrid structure and a particle size of less than 10 nm. The inorganic-organic hybrid structure exhibits good stability. The prepared metal-based polymer nanoparticles possess bacterial targeting properties, can aggregate at the infection site, concentrate photothermal effects, and avoid excessive heat generation by the nanoparticles that could damage healthy cells and tissues. The prepared antibacterial wound dressing has good tensile strength and self-healing properties, which can further improve the healing efficiency of infected wounds and promote wound healing and skin tissue remodeling.

Description

Technical Field

[0001] This invention belongs to the field of antibacterial agents, specifically relating to a metal-based polymer nanoparticle antibacterial agent, its preparation method, and its application. Background Technology

[0002] As the body's first line of defense and one of its major organs, the skin plays a vital role in protection, absorption, regulation, sensation, and secretion. When the skin is damaged, it is highly susceptible to bacterial infection, leading to inflammatory responses and reduced quality of life for patients. Therefore, timely and effective treatment is crucial for wound healing. Furthermore, the moist environment of the wound surface facilitates bacterial growth and accelerates cross-infection within the affected area. Nanomaterials offer unique advantages in wound care, such as high reactivity, large specific surface area, and the ability to control conductivity and penetration depth by altering their size and shape. However, current technologies for nanomaterials suffer from slow bactericidal action and less than ideal bactericidal effects. Summary of the Invention

[0003] To address the problems existing in the prior art, this invention proposes a modified polyether thiourea antibacterial wound dressing, its preparation method, and its application.

[0004] This invention first discloses a method for preparing a metal-based polymer nanoparticle antibacterial agent. The steps are as follows: dissolve a polymer polypeptide in a polar solvent, add a metal salt or an inorganic metal complex under stirring, heat to 25-160°C and react for 2-24 hours, continue the pyrolysis reaction at 60-160°C for 1-18 hours, collect the product after the reaction, wash and dry to obtain the metal-based polymer nanoparticle antibacterial agent.

[0005] Furthermore, the obtained metal-based polymer nanoparticle antibacterial agent was modified using a modifier.

[0006] Furthermore, the modifier is triphenylphosphine.

[0007] Furthermore, the triphenylphosphine modifier is selected from one or more of the following: n-pentyltriphenylphosphine bromide, methyltriphenylphosphine bromide, ethyltriphenylphosphine bromide, n-heptyltriphenylphosphine bromide, benzyltriphenylphosphine bromide, or (3-carboxypropyl)triphenylphosphine bromide.

[0008] Furthermore, when the modifier is triphenylphosphine, the steps are as follows: the triphenylphosphine modifier is activated to obtain an activated triphenylphosphine solution, which is added dropwise to the metal-based polymer nanoparticle / aqueous dispersion. After the reaction is completed by stirring at room temperature in the dark, the product solution is dialyzed to remove unreacted raw materials, the product is collected, washed and dried to obtain triphenylphosphine-modified metal-based polymer nanoparticles.

[0009] Furthermore, the polymer polypeptide is made of substituent amino acids, wherein the amino acids are selected from one or more of the following: alanine, glutamic acid, glycine, leucine or valine, and the substituents are selected from one or more of the following: pyridyl, imidazole, carbazole, pyrrole or alkynyl.

[0010] The polymeric polypeptide contains segments of a polyethylene glycol modifier, which is selected from one or more of the following: methoxy polyethylene glycol amine, carboxylated polyethylene glycol amine, or amino-terminated polyethylene glycol, with a molecular weight of 1000, 2000, 5000, or 10000.

[0011] The degree of polymerization of the polymeric peptide is 50 to 1000, preferably 50 to 100.

[0012] Further, the metal salt is selected from one or more of the following: ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferrous nitrate, ferrous carbonate, or ferrous ammonium sulfate; and the inorganic metal complex is selected from one or more of the following: Fe(CO)5, Co2(CO)8, Ni(CO)4, V(CO)6, Mo(CO)6, W(CO)6, Ru(CO)5, or Mn2(CO). 10 .

[0013] Furthermore, the polar solvent is selected from one or more of the following: dimethyl sulfoxide, N,N-dimethylformamide, acetone, dioxane, tetrahydrofuran, methyl ethyl ketone, methanol, n-butanol, diethyl ether, chloroform, N-methylpyrrolidone, or o-dichlorobenzene.

[0014] The particles prepared according to the above method have a core-shell structure, with the core being a metal oxide particle and the shell being a polymer polypeptide. Optionally, a modified chain may be included.

[0015] The above-mentioned metal-based polymer nanoparticle antibacterial agent is applied by adding 0.1 to 0.3 parts by weight of the metal-based polymer nanoparticle antibacterial agent and 0 to 0.001 parts by weight of the cationic antibacterial agent to 100 parts by weight of the polyether thiourea dressing precursor, mechanically stirring and then transferring to a mold to form an antibacterial dressing.

[0016] Furthermore, the cationic antibacterial agent is selected from one or more of the following: dodecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, dodecyldimethylbenzylammonium bromide, tetradecyldimethylbenzylammonium chloride, hexadecylpyridine bromide, polyethyleneimine, or hexadecyltrimethylammonium bromide.

[0017] Compared with the prior art, the present invention has the following advantages and significant progress:

[0018] (1) The significant advantage of this invention is that it uses an intramolecular crosslinking method to synthesize in situ triphenylphosphine-modified metal-based polymer nanoparticles with a particle size of less than 10 nm through an inorganic-organic polymer hybrid. The hybrid nanoparticles have atomic-level mixing, which can precisely control the composition. Moreover, the nanoparticles form a shell by wrapping the polypeptide chain while the core is formed, and the two processes are carried out simultaneously, resulting in good inorganic-organic hybrid stability.

[0019] (2) The metal-based polymer nanoparticles prepared by this invention have bacterial targeting properties and can aggregate at the site of infection, so that the photothermal effect is concentrated and the nanoparticles do not generate too much heat to damage healthy cells and tissues. They have excellent wound healing and tissue repair capabilities.

[0020] (3) The composite doped polyether thiourea antibacterial wound dressing prepared by the present invention has high mechanical strength and self-healing properties. It has good tensile strength (about 200%) and self-healing properties, which solves the problem of the single function of nanoparticles in treating wound infection. It can further improve the healing efficiency of infected wounds and promote wound healing and skin tissue reconstruction. Attached Figure Description

[0021] Figure 1 The XPS fine spectrum of Example 1;

[0022] Figure 2 The XPS fine spectrum of Example 3;

[0023] Figure 3 For the morphological characterization of polyether thiourea dressings, (a) is a photograph of the dressing surface (from left to right: Comparative Examples 1-3, Example 6); (b) is a side photograph of the dressing of Comparative Example 1; (c) is a SEM image of Comparative Example 3; (d) is a SEM image of Example 6.

[0024] Figure 4 The stress-strain curves for Examples 4, 6, and Comparative Example 1 are shown below.

[0025] Figure 5 These are self-healing photographs of the antibacterial dressings in Comparative Example 1 and Example 6;

[0026] Figure 6 Under near-infrared light irradiation (0.75W / cm) 2 Photothermal properties of composite doped polyether thiourea antibacterial dressings (Examples 4-8);

[0027] Figure 7 The wound area of ​​different groups of wounds infected with Staphylococcus aureus;

[0028] Figure 8 HE staining microscopy of different groups of tissues from rats on day 9. Detailed Implementation

[0029] The technical solution of the present invention will be further described below with reference to the embodiments, but it is not limited thereto. Any modifications or equivalent substitutions to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be covered within the protection scope of the present invention.

[0030] This invention first discloses a method for preparing a metal-based polymer nanoparticle antibacterial agent. The steps are as follows: dissolving a polymer polypeptide in a polar solvent, adding a metal salt or an inorganic metal complex sequentially under stirring, heating to 25–160°C and reacting for 2–24 hours, followed by a pyrolysis reaction at 60–160°C for 1–18 hours, collecting the product after the reaction, washing and drying to obtain the metal-based polymer nanoparticle antibacterial agent. Optionally, the obtained metal-based polymer nanoparticle antibacterial agent is modified with a modifier. The modifier is triphenylphosphine. The triphenylphosphine modifier is selected from one or more of the following: n-pentyltriphenylphosphine bromide, methyltriphenylphosphine bromide, ethyltriphenylphosphine bromide, n-heptyltriphenylphosphine bromide, benzyltriphenylphosphine bromide, or (3-carboxypropyl)triphenylphosphine bromide.

[0031] The polymeric polypeptide is made from substituent amino acids, wherein the amino acids are selected from one or more of the following: alanine, glutamic acid, glycine, leucine, or valine; and the substituents are selected from one or more of the following: pyridyl, imidazole, carbazole, pyrrole, or alkynyl. The polymeric polypeptide contains segments of a polyethylene glycol modifier, wherein the polyethylene glycol modifier is selected from one or more of the following: methoxy polyethylene glycol amine, carboxylated polyethylene glycol amine, or amino-terminated polyethylene glycol, with a molecular weight of 1000, 2000, 5000, or 10000. The degree of polymerization of the polymeric polypeptide is 50–1000, preferably 50–100.

[0032] The metal salt is selected from one or more of the following: ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferrous nitrate, ferrous carbonate, or ferrous ammonium sulfate; the inorganic metal complex is selected from one or more of the following: Fe(CO)5, Co2(CO)8, Ni(CO)4, V(CO)6, Mo(CO)6, W(CO)6, Ru(CO)5, or Mn2(CO). 10 .

[0033] The polar solvent is selected from one or more of the following: dimethyl sulfoxide, N,N-dimethylformamide, acetone, dioxane, tetrahydrofuran, methyl ethyl ketone, methanol, n-butanol, diethyl ether, chloroform, N-methylpyrrolidone, or o-dichlorobenzene.

[0034] When the modifier is triphenylphosphine, the steps are as follows: the triphenylphosphine modifier is activated to obtain an activated triphenylphosphine solution, which is added dropwise to the metal-based polymer nanoparticle / aqueous dispersion. After the reaction is completed by stirring at room temperature in the dark, the product solution is dialyzed to remove unreacted raw materials, the product is collected, washed and dried to obtain triphenylphosphine-modified metal-based polymer nanoparticles.

[0035] The particles prepared according to the above method have a core-shell structure, with the core being a metal oxide particle and the shell being a polymer polypeptide. Optionally, a modified chain may be included.

[0036] The application of the aforementioned metal-based polymer nanoparticle antibacterial agent is specifically as follows: 0.1 to 0.3 parts by mass of the metal-based polymer nanoparticle antibacterial agent and 0 to 0.001 parts by mass of the cationic antibacterial agent are added to 100 parts by mass of the polyether thiourea dressing precursor, mechanically stirred, and then transferred to a mold to form an antibacterial dressing.

[0037] The cationic antibacterial agent is selected from one or more of the following: dodecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, dodecyldimethylbenzylammonium bromide, tetradecyldimethylbenzylammonium chloride, hexadecylpyridine bromide, polyethyleneimine, or hexadecyltrimethylammonium bromide.

[0038] Example 1:

[0039] 60 mg of alkyne-containing glycine polypeptide was dissolved in 60 mL of N,N-dimethylformamide. 0.72 g of FeCl3·6H2O and 0.48 g of FeCl2·4H2O were added sequentially with stirring. The mixture was heated to 85 °C and reacted for 2 h. After the reaction, the mixture was pyrolyzed for another 5 h at 85 °C. After the reaction was completed, the product was collected, washed, and dried to obtain an iron-based polymer nanoparticle antibacterial agent.

[0040] Example 2:

[0041] The iron-based polymer nanoparticle antibacterial agent obtained in Example 1 was modified. Specifically, 11.20 mg of triphenylphosphine modifier was activated to obtain 2 mL of activated triphenylphosphine solution, which was then added dropwise to 30 mL of iron-based polymer nanoparticle / aqueous dispersion. After the reaction was completed at room temperature in the dark, the product solution was dialyzed to remove unreacted raw materials. The product was collected, washed three times, and dried to obtain triphenylphosphine-modified iron-based polymer nanoparticles.

[0042] Example 3:

[0043] 40 mg of alkyne-containing glycine peptide was dissolved in 7 mL of o-dichlorobenzene, and 110 mg of cobalt octacarbonyl was added with stirring. After stirring at 25 °C for 18 h, the mixture was heated to 120 °C and pyrolyzed for 16 h. After the reaction was completed, the product was collected, washed and dried to obtain a cobalt-based polymer nanoparticle antibacterial agent.

[0044] Example 4:

[0045] Preparation of modified polyether thiourea wound dressing: The cationic antibacterial agent polyethyleneimine and the triphenylphosphine-modified iron-based polymer nanoparticles prepared in Example 2 were added to the polyether thiourea wound dressing precursor. After mechanical stirring, the mixture was transferred to a mold and vacuum dried at a temperature above 80°C to obtain the modified polyether thiourea antibacterial dressing. The mass ratio of triphenylphosphine-modified iron-based polymer nanoparticles, cationic antibacterial agent, and polyether thiourea wound dressing precursor was 0.1:0.001:100.

[0046] Example 5:

[0047] The mass ratio of triphenylphosphine-modified iron-based polymer nanoparticles, cationic antibacterial agent, and polyether thiourea wound dressing precursor was 0.15:0.001:100. The remaining steps were the same as in Example 4.

[0048] Example 6:

[0049] The mass ratio of triphenylphosphine-modified iron-based polymer nanoparticles, cationic antibacterial agent, and polyether thiourea wound dressing precursor was 0.2:0.001:100. The remaining steps were the same as in Example 4.

[0050] Example 7:

[0051] The mass ratio of triphenylphosphine-modified iron-based polymer nanoparticles, cationic antibacterial agent, and polyether thiourea wound dressing precursor was 0.25:0.001:100. The remaining steps were the same as in Example 4.

[0052] Example 8:

[0053] The mass ratio of triphenylphosphine-modified iron-based polymer nanoparticles, cationic antibacterial agent, and polyether thiourea wound dressing precursor was 0.3:0.001:100. The remaining steps were the same as in Example 4.

[0054] Example 9:

[0055] The mass ratio of triphenylphosphine-modified iron-based polymer nanoparticles, cationic antibacterial agent, and polyether thiourea wound dressing precursor was 0.1:0:100. The remaining steps were the same as in Example 4.

[0056] Comparative Example 1:

[0057] This comparative example contains only polyether thiourea wound dressing precursor, without the addition of cationic antibacterial agents and iron-based polymer nanoparticles. The remaining steps are the same as in Example 4.

[0058] Comparative Example 2:

[0059] The comparative example consists of a polyether thiourea wound dressing precursor with the addition of the cationic antibacterial agent cetyltrimethylammonium bromide. The mass ratio of the polyether thiourea wound dressing precursor to the cationic antibacterial agent is 100:0.001. The remaining steps are the same as in Example 4.

[0060] Comparative Example 3:

[0061] The comparative example consists of a polyether thiourea wound dressing precursor with the addition of a cationic antibacterial agent, polyethyleneimine. The mass ratio of the polyether thiourea wound dressing precursor to the cationic antibacterial agent is 100:0.001. The remaining steps are the same as in Example 4.

[0062] Testing and characterization analysis:

[0063] To determine the chemical valence state of iron within the iron-based polymer nanoparticles of Example 1, XPS analysis was performed. After peak fitting and processing using XPS Peak software, as shown... Figure 1 As shown, the XPS spectrum of Fe 2p3 / 2 shows four peaks at 709.5, 711.0, and 712.8 eV. The peaks at 711.0 eV and 712.8 eV correspond to oxygen-bonded Fe. 3+ (Fe(Ⅲ)-O). The peak at 709.5 eV can be attributed to oxygen-bonded Fe. 2+ (Fe(Ⅱ)-O).

[0064] To determine the chemical valence state of iron within the cobalt-based polymer nanoparticles of Example 3, XPS analysis was performed. After peak fitting and fractionation using XPS Peak software, as shown... Figure 2 As shown, the XPS spectrum of Co 2p3 / 2 can be divided into four peaks: 783.7 eV, 782.0 eV, 780.6 eV, and 779.1 eV, corresponding to Co-C, Co, and Co, respectively. 2+ Co 3+ And Co. This indicates that the pyrolysis products contain not only elemental cobalt but also a small amount of cobalt oxide.

[0065] By controlling the amounts of doped iron-based polymer nanoparticles and PEI, a series of composite doped PETU dressings were prepared, and their morphology was characterized as follows: Figure 3 As shown, from left to right: Comparative Examples 1-3, Example 6. Figure 3As can be seen from (a, b), the PETU dressing has a diameter of about 1.5 cm and a thickness of about 1 mm. It is orange-yellow. Adding 0.001% CTAB or PEI does not change the color of the dressing. However, adding iron-based polymer nanoparticles will turn the dressing into dark brown. Figure 3 (c) and 3(d) are SEM images of Comparative Example 3 and Example 6, respectively. As can be seen from the figures, the surfaces of the PETU dressing with single PEI doping in Comparative Example 3 and the composite doped PETU dressing in Example 6 are relatively smooth. The raised parts on the surface are due to the rapid increase in molecular weight due to high temperature crosslinking during the preparation process, which leads to a rapid increase in viscosity and the pores generated when the solvent evaporates.

[0066] Wound dressings require good mechanical properties when used. Therefore, comparative examples 3, 4, and 6 were subjected to tensile testing at a fixed speed of 10 mm / min using a universal testing machine at room temperature to verify their mechanical properties. Figure 4 As shown in the figure, the maximum tensile stress of Comparative Example 3 is approximately 0.3 MPa, and the maximum strain is approximately 200%, indicating that it has good tensile properties. Furthermore, with the increase in the doping amount of iron-based polymer nanoparticles, the tensile strength and elongation at break of the PETU dressing decrease, but they still meet the requirements for wound dressing applications.

[0067] Furthermore, the self-healing properties of the antibacterial dressing were tested, such as... Figure 5 As shown, the dressing was cut in half lengthwise, and the gaps were then joined together. After about 30 seconds, it was stretched to both sides, and obvious repair marks could be seen. This indicates that the prepared polyether thiourea dressing has excellent self-healing properties regardless of whether it is loaded with iron-based polymer nanoparticles.

[0068] To investigate the photothermal properties of composite-doped PETU antibacterial dressings in NIR-II, this invention first examined the photothermal performance at 0.75 W / cm². 2 The photothermal heating capacity of PETU antibacterial dressings with different loadings of iron-based polymer nanoparticles (i.e., Examples 4-8) at different power levels was investigated, and the results are as follows: Figure 6 As shown. By Figure 6 As can be seen, PETU antibacterial dressings loaded with iron-based polymer nanoparticles exhibit rapid and strong temperature-raising capabilities, with the effect becoming more significant with increasing concentration. Under 1064nm near-infrared laser irradiation, the temperatures of different composite-doped PETU antibacterial dressings increased from approximately 29.4℃ to 50.0, 53.4, 57.7, 60.3, and 61.7℃ (in ascending order of loading) within 10 minutes, indicating that PETU antibacterial dressings loaded with iron-based polymer nanoparticles possess significant photothermal temperature-raising capabilities. Since 50℃ is the critical value for bacterial death, the PETU-PEI-0.001%-NPs-0.2% antibacterial dressing was selected for subsequent wound treatment.

[0069] Antibacterial treatment of a rat model of Staphylococcus aureus infection in the skin

[0070] To observe the wound treatment in rats, infected rats were randomly divided into four groups for wound antibacterial experiments, as described in Examples 10-13. Purchased SD rats were housed for 7 days in a constant temperature and humidity environment with 12 hours of light / 12 hours of darkness before the experiment began. Rats were anesthetized using an air anesthesia machine, followed by intraperitoneal injection of sodium barbital (30 mg / kg). The hair on their backs was shaved and disinfected, and a complete dermal layer-free wound (1.5 cm in diameter) was created on the back of each rat. Injections containing Staphylococcus aureus (2 × 10⁻⁶) were applied to the wound. 8 A bacterial suspension of 100 μL (CFU / mL) was spread evenly and allowed to infect the rats for 30 minutes. Treatment was administered every other day for a total of three days. Wound healing was recorded daily for different treatment groups. Wound area was calculated using ImageJ. After 9 days, rats were euthanized, and relevant wound tissue was collected. The wound tissue was fixed, encapsulated in paraffin, and sectioned to appropriate sizes. Sections were then stained with hematoxylin and eosin and observed under a microscope.

[0071] Example 10:

[0072] This group was administered 100 μL of PBS solution.

[0073] Example 11:

[0074] The iron-based polymer nanoparticles prepared in Example 1 were dispersed in PBS solution at a ratio of 350 μg / mL. Rats were then irradiated with a 1064 nm NIR laser for 10 min (0.75 W / cm²) after each administration of 100 μL of the iron-based nanoparticle solution. 2 Then, 100 μL of 100 μM H2O2 was used at each site.

[0075] Example 12:

[0076] Rats were covered with the antibacterial dressing prepared in Comparative Example 3 on their infected wounds and wrapped with bandages for 12 hours before being discarded.

[0077] Example 13:

[0078] Rats were treated with 100 μL of 100 μM H2O2 at the site of an infected wound, followed by covering with the antibacterial dressing prepared in Example 6, and then irradiated with a 1064 nm NIR laser for 10 min (0.75 W / cm²). 2 After that, fix it with a bandage for 12 hours and then discard it.

[0079] Depend on Figure 7It can be seen that from day 0 to day 9, the wound area of ​​all four groups decreased to varying degrees; however, the wound in Example 13 healed the fastest. The difference in healing speed became apparent from day 3, with the wound healing rates for Examples 10-13 being 7.60%, 38.4%, 25.0%, and 41.3%, respectively. That is, by day 3, the average wound healing rate of Example 13 was already close to 50%, significantly higher than the other groups. Subsequently, from day 5 to day 9, the average wound healing rate of Example 13 was basically the same as that of Example 11. This demonstrates that Example 13 has the same effect on Staphylococcus aureus wound infection on the skin surface, and can save on the amount of iron-based polymer nanoparticles used.

[0080] HE staining was performed on skin tissue on the 9th day after surgery, and the results are as follows: Figure 8 As shown in the figures, in Example 10, the wound area showed extensive proliferation of connective tissue and infiltration of numerous lymphocytes, neutrophils, and macrophages, indicating epithelial erosion. In Example 11, new skin tissue regeneration was observed, accompanied by new skin appendages such as hair follicles, but some inflammatory cells remained. Although Example 12 did not show epithelial erosion, it still exhibited significant inflammatory cell infiltration. Example 13 showed that the epithelial tissue had recovered more regularly, indicating complete regeneration of the epidermis and dermis with fewer inflammatory cells. This demonstrates that Example 13 also exhibits superior wound healing promotion compared to Example 11.

[0081] The above description is only a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a metal-based polymer nanoparticle antibacterial agent, characterized in that, The steps are as follows: dissolve the polymer peptide in a polar solvent, add metal salt or inorganic metal complex under stirring, heat to 25-160℃ and react for 2-24 hours, continue the pyrolysis reaction after the reaction, the pyrolysis reaction temperature is 60-160℃ and the time is 1-18 hours, collect the product after the reaction is completed, wash and dry to obtain metal-based polymer nanoparticle antibacterial agent. The polymer polypeptide is made from substituent amino acids, wherein the amino acids are selected from one or more of the following: alanine, glutamic acid, glycine, leucine or valine, and the substituents are selected from one or more of the following: pyridyl, imidazole, carbazole, pyrrole or alkynyl; the degree of polymerization of the polymer polypeptide is 50 to 1000. The metal salt is selected from one or more of the following: ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferrous nitrate, ferrous carbonate, or ferrous ammonium sulfate; the inorganic metal complex is selected from one or more of the following: Fe(CO)5, Co2(CO)8, Ni(CO)4, V(CO)6, Mo(CO)6, W(CO)6, Ru(CO)5, or Mn2(CO). 10 .

2. The method for preparing a metal-based polymer nanoparticle antibacterial agent according to claim 1, characterized in that, The obtained metal-based polymer nanoparticle antibacterial agent was modified using a modifier.

3. The method for preparing a metal-based polymer nanoparticle antibacterial agent according to claim 2, characterized in that, The modifier is triphenylphosphine.

4. The method for preparing a metal-based polymer nanoparticle antibacterial agent according to claim 3, characterized in that, The triphenylphosphine modifier is selected from one or more of the following: n-pentyltriphenylphosphine bromide, methyltriphenylphosphine bromide, ethyltriphenylphosphine bromide, n-heptyltriphenylphosphine bromide, benzyltriphenylphosphine bromide, or (3-carboxypropyl)triphenylphosphine bromide.

5. The method for preparing a metal-based polymer nanoparticle antibacterial agent according to claim 3, characterized in that, When the modifier is triphenylphosphine, the steps are as follows: the triphenylphosphine modifier is activated to obtain an activated triphenylphosphine solution, which is added dropwise to the metal-based polymer nanoparticle / aqueous dispersion. After the reaction is completed by stirring at room temperature in the dark, the product solution is dialyzed to remove unreacted raw materials, the product is collected, washed and dried to obtain triphenylphosphine-modified metal-based polymer nanoparticles.

6. The method for preparing a metal-based polymer nanoparticle antibacterial agent according to claim 1, characterized in that, The polymeric polypeptide contains segments of a polyethylene glycol modifier, which is selected from one or more of the following: methoxy polyethylene glycol amine, carboxylated polyethylene glycol amine, or amino-terminated polyethylene glycol, with a molecular weight of 1000, 2000, 5000, or 10000.

7. The method for preparing a metal-based polymer nanoparticle antibacterial agent according to claim 1, characterized in that, The polar solvent is selected from one or more of the following: dimethyl sulfoxide, N,N-dimethylformamide, acetone, dioxane, tetrahydrofuran, methyl ethyl ketone, methanol, n-butanol, diethyl ether, chloroform, N-methylpyrrolidone, or o-dichlorobenzene.

8. The metal-based polymer nanoparticle antibacterial agent prepared by the preparation method of the metal-based polymer nanoparticle antibacterial agent according to any one of claims 1 to 7, characterized in that, The particles have a core-shell structure, with the core being a metal oxide particle and the shell being a polymer polypeptide.

9. The application of the metal-based polymer nanoparticle antibacterial agent as described in claim 8, characterized in that, 0.1 to 0.3 parts by weight of metal-based polymer nanoparticle antibacterial agent and 0 to 0.001 parts by weight of cationic antibacterial agent are added to 100 parts by weight of polyether thiourea dressing precursor. After mechanical stirring, the mixture is transferred to a mold to form an antibacterial dressing.

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