A dopamine surface self-polymer coating based on copper / hydrogen peroxide synergistic induction and a preparation method thereof

Abstract

This invention discloses a copper / hydrogen peroxide synergistic-induced dopamine surface self-polymerization coating and its preparation method, relating to the field of surface and interface modification technology. The specific preparation method is as follows: Buffer solution A is prepared using an organic amine buffer solution; copper salt is added and ultrasonically dispersed to obtain a copper-containing solution B; a substrate pretreated with acid washing is immersed in solution B; a dopamine precursor is added to obtain a mixed solution C; then an aqueous hydrogen peroxide solution is added, and the reaction is carried out under light-protected conditions to form a dopamine polymer coating in situ on the substrate surface. After washing and drying, a modified substrate with a copper / hydrogen peroxide synergistic-induced dopamine coating is obtained. 2+ It exhibits a significant synergistic effect with H2O2 in inducing oxidative polymerization, reflecting the combined effect of coordination site saturation and subsequent layer coverage. This invention achieves higher film-forming efficiency and interfacial stability through short-time impregnation and optimized reaction sequence, making it suitable for rapid modification of glass-like inert substrates.

Description

Technical Field

[0001] This invention relates to a copper / hydrogen peroxide synergistic-induced dopamine surface self-polymerization coating and its preparation method, belonging to the field of surface and interface modification technology. Background Technology

[0002] Inspired by the adhesion mechanism of mussels, dopamine surface coatings have become an important route for constructing functional surfaces due to their universal adhesion and post-modification properties. The catechol, amine, and imine groups in dopamine coatings (PDA) provide chemical sites for subsequent reduction of metal ions, induction of inorganic mineralization, and construction of antifouling / hydrophilic layers; however, traditional air oxidation methods usually require several hours to several days to form a film, and their stability in acids, alkalis, and strongly polar organic solvents is insufficient, and the coating is prone to agglomeration and inhomogeneity, which limits their application on smooth or micro / nanostructured surfaces.

[0003] To improve deposition rate and quality, previous studies have attempted to accelerate PDA formation through ultraviolet irradiation, external oxidants, and electrochemical methods. However, common problems still include slow coating thickness growth, excessively rapid increase in surface roughness, and easy detachment in polar solvents. To address these issues, some studies have proposed using a synergistic catalytic system of copper ions and hydrogen peroxide, which can significantly shorten coating preparation time. However, existing methods still face challenges in terms of film uniformity, adaptability to substrates with different wettability, and stable scale-up of process parameters.

[0004] Achieving uniform and controllable film formation on hydrophilic and hydrophobic substrates within a short time window (minutes) while simultaneously meeting the requirements of room temperature, aqueous phase, low feedstock addition, and repeatable scale-up of process parameters remains a challenge, and a systematic solution is still lacking. Therefore, it is necessary to provide a method for rapidly constructing a stable and uniform PDA intermediate layer on hydrophilic and hydrophobic substrates through synergistic oxidation of copper salts and hydrogen peroxide in an alkaline buffer system, to meet the needs of surface modification and subsequent functionalization of biomedical devices. Summary of the Invention

[0005] To address the shortcomings of related technologies, this invention provides a copper / hydrogen peroxide synergistic-induced dopamine surface self-polymerization coating and its preparation method, aiming to rapidly construct a stable and uniform PDA intermediate layer, thereby solving the challenges still faced by existing methods in terms of film uniformity, adaptability to substrates with different wettability, and stable scale-up of process parameters.

[0006] One objective of this invention is to provide a method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction, specifically including the following steps: (1) Prepare buffer solution A using organic amine buffer, add copper salt to buffer solution A to obtain copper-containing solution B, and then perform ultrasonic dispersion treatment on copper-containing solution B to obtain ultrasonically dispersed copper-containing solution B.

[0007] (2) The substrate is acid-washed to obtain a pretreated substrate, and the pretreated substrate is immersed in a copper-containing solution B after ultrasonic dispersion.

[0008] (3) Add dopamine precursor to copper-containing solution B from step (2) to obtain mixed solution C.

[0009] (4) Add an aqueous solution of hydrogen peroxide to the mixed solution C of step (3) and react under light-protected conditions to form a dopamine polymer coating on the substrate surface.

[0010] (5) The substrate with the dopamine polymer coating on the surface is removed, and after washing and drying, a modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction is obtained.

[0011] Preferably, the organic amine buffer in step (1) is Tris or its salt; the pH of the buffer solution A is 8.0~9.0; and the concentration of the organic amine buffer in the buffer solution A is 10~100 mmol / L.

[0012] Preferably, in step (1), the amount of copper salt added to the copper-containing solution B is 0.0001~0.02 g / mL; the copper salt is one of copper sulfate, copper nitrate or copper acetate.

[0013] More preferably, in step (1), the pH value of buffer solution A is 8.3~8.7; the concentration of organic amine buffer in buffer solution A is 40~60 mmol / L; and the ultrasonic dispersion treatment time is 10 min.

[0014] More preferably, the copper salt in step (1) is copper sulfate or copper sulfate pentahydrate.

[0015] More preferably, step (1) uses NaOH or HCl to adjust the pH of buffer solution A.

[0016] More preferably, in step (1), the amount of copper salt added to the copper-containing solution B is 0.0015~0.003 g / mL.

[0017] Preferably, the substrate in step (2) is an inorganic hydrophilic glass or an inorganic hydrophobic glass; the acid washing conditions are: immersing the substrate in a 1 mol / L hydrochloric acid aqueous solution and sonicating for 20 min, followed by rinsing and drying.

[0018] Preferably, the conditions for immersing the pretreated substrate in the ultrasonically dispersed copper-containing solution B in step (2) are: standing at 15~30℃ for 20~40 min or stirring at 100~600 rpm for 10~20 min.

[0019] More preferably, the inorganic hydrophobic glass in step (2) is formed by coating the glass surface with polydimethylsiloxane (PDMS) and curing it.

[0020] More preferably, in step (2), the conditions for immersing the pretreated substrate in the ultrasonically dispersed copper-containing solution B are: stirring at 100-600 rpm for 10-20 minutes at 15-30°C.

[0021] Preferably, the dopamine precursor in step (3) can be an aqueous solution of dopamine or solid dopamine; the amount of dopamine added in the mixed solution C is 0.5~2.5 g / L.

[0022] Preferably, in step (4), the content of hydrogen peroxide in the aqueous solution of hydrogen peroxide is 3-35% by mass; the aqueous solution of hydrogen peroxide is added to the mixed solution C at a molar ratio of hydrogen peroxide to dopamine of (0.5-20):1; the aqueous solution of hydrogen peroxide is added to the mixed solution C at a dropping rate of 1.5-6 mL / min.

[0023] More preferably, in step (4), the aqueous solution of hydrogen peroxide is added to the mixed solution C in a molar ratio of hydrogen peroxide to dopamine of (2~8):1.

[0024] Preferably, the reaction conditions in step (4) under light-protected conditions are: at 20~35℃, the reaction is carried out at a speed of 100~600rpm for 10~20min.

[0025] Another objective of this invention is to provide a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction prepared by the method of this invention.

[0026] Mechanism of the invention: This invention utilizes Cu 2+ Synergistic catalytic oxidation with H2O2 in alkaline Tris systems (Cu 2+ Complexation lowers the oxidation barrier, and H2O2 generates ROS to accelerate the chain reaction, enabling dopamine to rapidly self-polymerize and deposit a PDA coating within minutes. The coating growth mode and Cu dynamic distribution are regulated by the substrate wettability, ultimately forming a uniform and stable functional coating with Cu coordination crosslinking.

[0027] The beneficial effects of this invention are: (1) The preparation process of the dopamine surface self-polymerization coating (which can be called PDA antibacterial surface system) of the present invention does not use organic solvents and high temperature and pressure. It only uses a small amount of hydrogen peroxide and copper salt to trigger the self-polymerization of dopamine to generate the coating under aqueous phase and room temperature conditions. After thorough water washing, the free copper residue is controlled. The process is simple, safe and environmentally friendly. The resulting antibacterial surface can be used for surface modification of biomedical related devices, functional treatment of food packaging contact surfaces and daily chemical skin care contact interfaces.

[0028] (2) The PDA antibacterial surface system of the present invention achieves a balance between mild and long-lasting antibacterial efficacy and material compatibility through controlled copper-catechol coordination and the synergistic effect of PDA's intrinsic antioxidant capacity, thereby reducing the potential irritation and imbalance risks brought about by high-dose release antibacterial components.

[0029] (3) The PDA antibacterial surface system of the present invention has a controllable film formation rate and a wide window, and completes the construction of a dense and uniform hydrophilic coating in minutes; the coating has good dispersibility and adhesion, and is not easy to fall off or fail under long-term storage and cleaning conditions, making it easy to store and transport.

[0030] (4) The PDA antibacterial surface system of the present invention can show significant adhesion inhibition and killing trend against common pathogenic microorganisms (such as Escherichia coli and Staphylococcus aureus) under low working conditions, and can be used to reduce early adhesion and inhibit biofilm formation.

[0031] (5) The PDA antibacterial surface system of the present invention exhibits good biocompatibility and low cytotoxicity in routine in vitro evaluations, and is suitable for use with soft and hard substrates (including hydrophilic and hydrophobic surfaces) to meet the application requirements of medical-related surface modification.

[0032] (6) The PDA antibacterial surface system of the present invention has fewer steps, lower equipment requirements, and is easy to operate manually. Key parameters are easy to scale up and control online, making it suitable for large-scale continuous production and easy to industrialize. Attached Figure Description

[0033] Figure 1 Figure 1 shows the UV-Vis spectrum evolution curves of the reaction systems of Examples 1-4 and Comparative Examples 1-6 of this invention over time (0-20 min, monitored at 420 / 480 nm). Figure 2(a) shows the full spectrum evolution of the UV-Vis absorption spectrum of the reaction mixture at different reaction times (1, 3, 5, 10, 20 min); Figure 3(b) shows the trend of the absorbance of the reaction system at characteristic wavelengths of 420 nm and 480 nm with reaction time.

[0034] Figure 2 The images show AFM and roughness statistics of the coating surfaces prepared in Examples 1-4 and Comparative Examples 1-6 of this invention.

[0035] Figure 3Figure 1 shows the XPS chemical composition and bonding evolution results of the coatings prepared in this invention. Figure 2 shows the XPS full spectrum scans of the coatings on the hydrophobic glass substrate after deposition for 0 min, Comparative Example 3 (deposition for 3 min), Example 3 (deposition for 10 min), and Example 1 (deposition for 20 min). Figure 3 shows the XPS full spectrum scans of the coatings on the hydrophilic glass substrate after deposition for 0 min, Comparative Example 4 (deposition for 3 min), Example 4 (deposition for 10 min), and Example 2 (deposition for 20 min). Figure 4 shows the high-resolution photoelectron spectrum of Cu2p in the hydrophobic PDA coating of Example 1. Figure 5 shows the high-resolution photoelectron spectrum of Cu2p in the hydrophilic PDA coating of Example 2.

[0036] Figure 4 The figures show the antibacterial test results of the coatings prepared in Comparative Example 1 (hydrophobic substrate deposition for 1 min), Comparative Example 3 (hydrophobic substrate deposition for 3 min), Example 3 (hydrophobic substrate deposition for 10 min), and Example 1 (hydrophobic substrate deposition for 20 min) against Escherichia coli and Staphylococcus aureus.

[0037] Figure 5 The following are statistical charts verifying the evolution of surface wettability and antibacterial rate of the coatings prepared in this invention. Figure (a) shows the static water contact angle of Comparative Example 1 (hydrophobic substrate deposition for 1 min), Comparative Example 3 (hydrophobic substrate deposition for 3 min), Example 3 (hydrophobic substrate deposition for 10 min), and Example 1 (hydrophobic substrate deposition for 20 min). Figure (b) shows the static water contact angle of Comparative Example 2 (hydrophilic substrate deposition for 1 min), Comparative Example 4 (hydrophilic substrate deposition for 3 min), Example 4 (hydrophilic substrate deposition for 10 min), and Example 2 (hydrophilic substrate deposition for 20 min). Figure (c) shows the static water contact angle statistics for Comparative Example 1 (hydrophobic substrate deposition for 1 min), Comparative Example 3 (hydrophobic substrate deposition for 3 min), Example 3 (hydrophobic substrate deposition for 10 min), and Example 1 (hydrophobic substrate deposition for 20 min). Figure (d) shows the antibacterial rate statistics for the coatings of Comparative Example 2 (hydrophilic substrate deposition for 1 min), Comparative Example 4 (hydrophilic substrate deposition for 3 min), Example 4 (hydrophilic substrate deposition for 10 min), and Example 2 (hydrophilic substrate deposition for 20 min).

[0038] Figure 6 The graph shows the compatibility results of the coated cells prepared in Examples 1-4 and Comparative Examples 1-4 of this invention (relative proliferation rate RGR of L929 co-cultured for 24 h). Detailed Implementation

[0039] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below with reference to specific embodiments. In the embodiments and comparative examples of this invention, unless otherwise specified, all chemical reagents used in the experiments were commercially available analytical grade. The substrate described in this invention is an inorganic glass substrate with a smooth surface of various types. The inorganic glass substrate refers to a rigid amorphous solid whose main component is silicon dioxide (SiO2) and its network-modified oxides (such as Na2O, CaO, Al2O3, B2O3), including but not limited to soda-lime silicate glass, borosilicate glass, quartz glass, glass slides, and coverslips. The inorganic hydrophilic glass described in this invention refers to the above-mentioned glass substrate that has not undergone special hydrophobic modification and whose surface is rich in silanol groups (-Si-OH), thus possessing hydrophilicity, and whose initial water contact angle is typically less than 30°. The inorganic hydrophobic glass refers to modified glass with a hydrophobic surface formed by coating and curing a hydrophobic material (such as polydimethylsiloxane, PDMS) on the surface of the inorganic glass substrate, and whose surface water contact angle is typically greater than 90°. The hydrophobic modification of the inorganic glass matrix is ​​a routine procedure in the art.

[0040] Example 1 A method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction specifically includes the following steps: (1) Prepare a Tris buffer solution with pH 8.5 and concentration of 50 mmol / L using Tris and deionized water, namely buffer solution A (the pH of this solution is adjusted by NaOH and HCl). Add copper sulfate to buffer solution A to obtain copper-containing solution B, wherein the amount of copper sulfate added to copper-containing solution B is 0.00225 g / mL. Then, ultrasonically disperse copper-containing solution B for 10 min to obtain ultrasonically dispersed copper-containing solution B.

[0041] (2) PDMS is coated on the glass surface and then cured to obtain inorganic hydrophobic glass. The inorganic hydrophobic glass is immersed in 1 mol / L hydrochloric acid aqueous solution and sonicated for 20 min to remove inorganic salt ions, metal oxide particles or dust. Then, the inorganic hydrophobic glass is thoroughly rinsed with deionized water to remove residual acid. Finally, it is dried with nitrogen to obtain the pretreated substrate. The pretreated substrate is immersed in the ultrasonically dispersed copper-containing solution B and stirred at 25°C and 300 rpm for 15 min.

[0042] (3) Add dopamine precursor to copper-containing solution B in step (2) and stir until it is dissolved evenly to obtain mixed solution C, wherein the amount of dopamine added in mixed solution C is 2g / L.

[0043] (4) Add an aqueous solution of hydrogen peroxide with a mass percentage concentration of 30% to the mixed solution C in step (3) at a ratio of 3.7:1 to hydrogen peroxide. React at 25°C and 200 rpm for 20 min under light-protected conditions to form a dopamine polymer coating on the substrate surface.

[0044] (5) The substrate with the dopamine polymer coating on the surface is taken out, washed with deionized water, and then vacuum dried at room temperature to remove moisture, so as to obtain a brown modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction.

[0045] The oxidative polymerization process of the dopamine reaction solution in the bulk phase in this embodiment is as follows: Figure 1 As shown, the surface morphology comparison AFM and roughness statistics of the coating prepared in this embodiment are as follows. Figure 2 As shown in the figure, the XPS chemical composition and bonding evolution results are as follows: Figure 3 As shown, the antibacterial test results of the coating against Escherichia coli and Staphylococcus aureus are as follows: Figure 4 As shown in the figure, the surface wettability evolution verification and antibacterial rate statistics are as follows: Figure 5 As shown in the figure, the coating cell compatibility results are as follows: Figure 6 As shown.

[0046] Example 2 A method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction specifically includes the following steps: (1) Prepare a Tris buffer solution with pH 8.5 and concentration of 50 mmol / L using Tris and deionized water, namely buffer solution A (the pH of this solution is adjusted by NaOH and HCl). Add copper sulfate to buffer solution A to obtain copper-containing solution B, wherein the amount of copper sulfate added to copper-containing solution B is 0.00225 g / mL. Then, ultrasonically disperse copper-containing solution B for 10 min to obtain ultrasonically dispersed copper-containing solution B.

[0047] (2) Immerse the inorganic hydrophilic glass in a 1 mol / L hydrochloric acid aqueous solution and sonicate for 20 min to remove inorganic salt ions, metal oxide particles or dust. Then rinse the inorganic hydrophilic glass thoroughly with deionized water to remove residual acid. Finally, blow it dry with nitrogen to obtain the pretreated substrate. Immerse the pretreated substrate in the ultrasonically dispersed copper-containing solution B and stir at 25°C and 300 rpm for 15 min.

[0048] (3) Add dopamine precursor to copper-containing solution B in step (2) and stir until it is dissolved evenly to obtain mixed solution C, wherein the amount of dopamine added in mixed solution C is 2g / L.

[0049] (4) Add an aqueous solution of hydrogen peroxide with a mass percentage concentration of 30% to the mixed solution C in step (3) at a ratio of 3.7:1 to hydrogen peroxide. React at 25°C and 200 rpm for 20 min under light-protected conditions to form a dopamine polymer coating on the substrate surface.

[0050] (5) The substrate with the dopamine polymer coating on the surface is taken out, washed with deionized water, and then vacuum dried at room temperature to remove moisture, so as to obtain a brown modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction.

[0051] The surface morphology comparison AFM and roughness statistics of the coating prepared in this embodiment are shown in the following figures. Figure 2 As shown in the figure, the XPS chemical composition and bonding evolution results are as follows: Figure 3 As shown in the figure, the surface wettability evolution verification and antibacterial rate statistics are as follows: Figure 5 As shown in the figure, the coating cell compatibility results are as follows: Figure 6 As shown.

[0052] Example 3 A method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction specifically includes the following steps: (1) Prepare a Tris buffer solution with pH 8.5 and concentration of 50 mmol / L using Tris and deionized water, namely buffer solution A (the pH of this solution is adjusted by NaOH and HCl). Add copper sulfate to buffer solution A to obtain copper-containing solution B, wherein the amount of copper sulfate added to copper-containing solution B is 0.00225 g / mL. Then, ultrasonically disperse copper-containing solution B for 10 min to obtain ultrasonically dispersed copper-containing solution B.

[0053] (2) PDMS is coated on the glass surface and then cured to obtain inorganic hydrophobic glass. The inorganic hydrophobic glass is immersed in 1 mol / L hydrochloric acid aqueous solution and sonicated for 20 min to remove inorganic salt ions, metal oxide particles or dust. Then, the inorganic hydrophobic glass is thoroughly rinsed with deionized water to remove residual acid. Finally, it is dried with nitrogen to obtain the pretreated substrate. The pretreated substrate is immersed in the ultrasonically dispersed copper-containing solution B and stirred at 25°C and 300 rpm for 15 min.

[0054] (3) Add dopamine precursor to copper-containing solution B in step (2) and stir until it is dissolved evenly to obtain mixed solution C, wherein the amount of dopamine added in mixed solution C is 2g / L.

[0055] (4) Add an aqueous solution of hydrogen peroxide with a mass percentage concentration of 30% to the mixed solution C in step (3) at a rate of 3 mL / min according to the molar ratio of hydrogen peroxide to dopamine of 3.7:1. React at 25°C and 200 rpm for 10 min under light-protected conditions to form a dopamine polymer coating on the substrate surface.

[0056] (5) The substrate with the dopamine polymer coating on the surface is taken out, washed with deionized water, and then vacuum dried at room temperature to remove moisture, so as to obtain a brown modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction.

[0057] The surface morphology comparison AFM and roughness statistics of the coating prepared in this embodiment are shown in the following figures. Figure 2 As shown in the figure, the XPS chemical composition and bonding evolution results are as follows: Figure 3 As shown, the antibacterial test results of the coating against Escherichia coli and Staphylococcus aureus are as follows: Figure 4 As shown in the figure, the surface wettability evolution verification and antibacterial rate statistics are as follows: Figure 5 As shown in the figure, the coating cell compatibility results are as follows: Figure 6 As shown.

[0058] Example 4 A method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction specifically includes the following steps: (1) Prepare a Tris buffer solution with pH 8.5 and concentration of 50 mmol / L using Tris and deionized water, namely buffer solution A (the pH of this solution is adjusted by NaOH and HCl). Add copper sulfate to buffer solution A to obtain copper-containing solution B, wherein the amount of copper sulfate added to copper-containing solution B is 0.00225 g / mL. Then, ultrasonically disperse copper-containing solution B for 10 min to obtain ultrasonically dispersed copper-containing solution B.

[0059] (2) Immerse the inorganic hydrophilic glass in a 1 mol / L hydrochloric acid aqueous solution and sonicate for 20 min to remove inorganic salt ions, metal oxide particles or dust. Then rinse the inorganic hydrophilic glass thoroughly with deionized water to remove residual acid. Finally, blow it dry with nitrogen to obtain the pretreated substrate. Immerse the pretreated substrate in the ultrasonically dispersed copper-containing solution B and stir at 25°C and 300 rpm for 15 min.

[0060] (3) Add dopamine precursor to copper-containing solution B in step (2) and stir until it is dissolved evenly to obtain mixed solution C, wherein the amount of dopamine added in mixed solution C is 2g / L.

[0061] (4) Add an aqueous solution of hydrogen peroxide with a mass percentage concentration of 30% to the mixed solution C in step (3) at a rate of 3 mL / min according to the molar ratio of hydrogen peroxide to dopamine of 3.7:1. React at 25°C and 200 rpm for 10 min under light-protected conditions to form a dopamine polymer coating on the substrate surface.

[0062] (5) The substrate with the dopamine polymer coating on the surface is taken out, washed with deionized water, and then vacuum dried at room temperature to remove moisture, so as to obtain a brown modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction.

[0063] The surface morphology comparison AFM and roughness statistics of the coating prepared in this embodiment are shown in the following figures. Figure 2 As shown in the figure, the XPS chemical composition and bonding evolution results are as follows: Figure 3 As shown in the figure, the surface wettability evolution verification and antibacterial rate statistics are as follows: Figure 5 As shown in the figure, the coating cell compatibility results are as follows: Figure 6 As shown.

[0064] Example 5 A method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction specifically includes the following steps: (1) Prepare a buffer solution with pH 8.0 and concentration of 40 mmol / L using Tris-HCl and deionized water, namely buffer solution A (the pH of this solution is adjusted by NaOH and HCl). Add copper acetate to buffer solution A to obtain copper-containing solution B, wherein the amount of copper acetate added to copper-containing solution B is 0.0001 g / mL. Then, ultrasonically disperse copper-containing solution B for 10 min to obtain ultrasonically dispersed copper-containing solution B.

[0065] (2) PDMS is coated on the glass surface and then cured to obtain inorganic hydrophobic glass. The inorganic hydrophobic glass is immersed in 1 mol / L hydrochloric acid aqueous solution and sonicated for 20 min to remove inorganic salt ions, metal oxide particles or dust. Then, the inorganic hydrophobic glass is thoroughly rinsed with deionized water to remove residual acid. Finally, it is dried with nitrogen to obtain the pretreated substrate. The pretreated substrate is immersed in the ultrasonically dispersed copper-containing solution B and stirred at 15°C and 600 rpm for 10 min.

[0066] (3) Add the aqueous solution of dopamine to the copper-containing solution B in step (2) and stir until it is dissolved evenly to obtain a mixed solution C, wherein the amount of dopamine added in the mixed solution C is 0.5 g / L.

[0067] (4) Add an aqueous solution of hydrogen peroxide with a mass percentage concentration of 3% to the mixed solution C in step (3) at a rate of 1.5 mL / min according to the molar ratio of hydrogen peroxide to dopamine of 0.5:1. React at 20°C and 100 rpm for 15 min under light-protected conditions to form a dopamine polymer coating on the substrate surface.

[0068] (5) The substrate with the dopamine polymer coating on the surface is taken out, washed with deionized water, and then vacuum dried at room temperature to remove moisture, so as to obtain a brown modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction.

[0069] Example 6 A method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction specifically includes the following steps: (1) Prepare a Tris buffer solution with pH 9.0 and concentration of 60 mmol / L using Tris and deionized water, namely buffer solution A (the pH of this solution is adjusted by NaOH and HCl). Add copper nitrate to buffer solution A to obtain copper-containing solution B, wherein the amount of copper nitrate added to copper-containing solution B is 0.02 g / mL. Then, ultrasonically disperse copper-containing solution B for 10 min to obtain ultrasonically dispersed copper-containing solution B.

[0070] (2) PDMS is coated on the glass surface and then cured to obtain inorganic hydrophobic glass. The inorganic hydrophobic glass is immersed in 1 mol / L hydrochloric acid aqueous solution and sonicated for 20 min to remove inorganic salt ions, metal oxide particles or dust. Then, the inorganic hydrophobic glass is thoroughly rinsed with deionized water to remove residual acid. Finally, it is dried with nitrogen to obtain the pretreated substrate. The pretreated substrate is immersed in the ultrasonically dispersed copper-containing solution B and stirred at 30℃ and 600 rpm for 20 min.

[0071] (3) Add dopamine to the copper-containing solution B in step (2) and stir until it is dissolved evenly to obtain a mixed solution C, wherein the amount of dopamine added in the mixed solution C is 2.5 g / L.

[0072] (4) Add an aqueous solution of hydrogen peroxide with a mass percentage concentration of 35% to the mixed solution C in step (3) at a rate of 6 mL / min according to the molar ratio of hydrogen peroxide to dopamine of 20:1. React at 35°C and 600 rpm for 15 min under light-protected conditions to form a dopamine polymer coating on the substrate surface.

[0073] (5) The substrate with the dopamine polymer coating on the surface is taken out, washed with deionized water, and then vacuum dried at room temperature to remove moisture, so as to obtain a brown modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction.

[0074] Comparative Example 1 A method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction specifically includes the following steps: (1) Prepare a Tris buffer solution with pH 8.5 and concentration of 50 mmol / L using Tris and deionized water, namely buffer solution A (the pH of this solution is adjusted by NaOH and HCl). Add copper sulfate to buffer solution A to obtain copper-containing solution B, wherein the amount of copper sulfate added to copper-containing solution B is 0.00225 g / mL. Then, ultrasonically disperse copper-containing solution B for 10 min to obtain ultrasonically dispersed copper-containing solution B.

[0075] (2) PDMS is coated on the glass surface and then cured to obtain inorganic hydrophobic glass. The inorganic hydrophobic glass is immersed in 1 mol / L hydrochloric acid aqueous solution and sonicated for 20 min to remove inorganic salt ions, metal oxide particles or dust. Then, the inorganic hydrophobic glass is thoroughly rinsed with deionized water to remove residual acid. Finally, it is dried with nitrogen to obtain the pretreated substrate. The pretreated substrate is immersed in the ultrasonically dispersed copper-containing solution B and stirred at 25°C and 300 rpm for 15 min.

[0076] (3) Add dopamine precursor to copper-containing solution B in step (2) and stir until it is dissolved evenly to obtain mixed solution C, wherein the amount of dopamine added in mixed solution C is 2g / L.

[0077] (4) Add an aqueous solution of hydrogen peroxide with a mass percentage concentration of 30% to the mixed solution C in step (3) at a rate of 3 mL / min according to the molar ratio of hydrogen peroxide to dopamine of 3.7:1. React at 25°C and 200 rpm for 1 min under light-protected conditions to form a dopamine polymer coating on the substrate surface.

[0078] (5) The substrate with the dopamine polymer coating on the surface is taken out, washed with deionized water, and then vacuum dried at room temperature to remove moisture, so as to obtain a brown modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction.

[0079] The surface morphology comparison AFM and roughness statistics of the coating prepared in this comparative example are shown in the figure below. Figure 2 As shown in the figure, the XPS chemical composition and bonding evolution results are as follows: Figure 3 As shown, the antibacterial test results of the coating against Escherichia coli and Staphylococcus aureus are as follows: Figure 4 As shown in the figure, the surface wettability evolution verification and antibacterial rate statistics are as follows: Figure 5 As shown in the figure, the coating cell compatibility results are as follows: Figure 6 As shown.

[0080] Comparative Example 2 A method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction specifically includes the following steps: (1) Prepare a Tris buffer solution with pH 8.5 and concentration of 50 mmol / L using Tris and deionized water, namely buffer solution A (the pH of this solution is adjusted by NaOH and HCl). Add copper sulfate to buffer solution A to obtain copper-containing solution B, wherein the amount of copper sulfate added to copper-containing solution B is 0.00225 g / mL. Then, ultrasonically disperse copper-containing solution B for 10 min to obtain ultrasonically dispersed copper-containing solution B.

[0081] (2) Immerse the inorganic hydrophilic glass in a 1 mol / L hydrochloric acid aqueous solution and sonicate for 20 min to remove inorganic salt ions, metal oxide particles or dust. Then rinse the inorganic hydrophilic glass thoroughly with deionized water to remove residual acid. Finally, blow it dry with nitrogen to obtain the pretreated substrate. Immerse the pretreated substrate in the ultrasonically dispersed copper-containing solution B and stir at 25°C and 300 rpm for 15 min.

[0082] (3) Add dopamine precursor to copper-containing solution B in step (2) and stir until it is dissolved evenly to obtain mixed solution C, wherein the amount of dopamine added in mixed solution C is 2g / L.

[0083] (4) Add an aqueous solution of hydrogen peroxide with a mass percentage concentration of 30% to the mixed solution C in step (3) at a rate of 3 mL / min according to the molar ratio of hydrogen peroxide to dopamine of 3.7:1. React at 25°C and 200 rpm for 1 min under light-protected conditions to form a dopamine polymer coating on the substrate surface.

[0084] (5) The substrate with the dopamine polymer coating on the surface is taken out, washed with deionized water, and then vacuum dried at room temperature to remove moisture, so as to obtain a brown modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction.

[0085] The surface morphology comparison AFM and roughness statistics of the coating prepared in this comparative example are shown in the figure below. Figure 2 As shown in the figure, the XPS chemical composition and bonding evolution results are as follows: Figure 3 As shown in the figure, the surface wettability evolution verification and antibacterial rate statistics are as follows: Figure 5 As shown in the figure, the coating cell compatibility results are as follows: Figure 6 As shown.

[0086] Comparative Example 3 A method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction specifically includes the following steps: (1) Prepare a Tris buffer solution with pH 8.5 and concentration of 50 mmol / L using Tris and deionized water, namely buffer solution A (the pH of this solution is adjusted by NaOH and HCl). Add copper sulfate to buffer solution A to obtain copper-containing solution B, wherein the amount of copper sulfate added to copper-containing solution B is 0.00225 g / mL. Then, ultrasonically disperse copper-containing solution B for 10 min to obtain ultrasonically dispersed copper-containing solution B.

[0087] (2) PDMS is coated on the glass surface and then cured to obtain inorganic hydrophobic glass. The inorganic hydrophobic glass is immersed in 1 mol / L hydrochloric acid aqueous solution and sonicated for 20 min to remove inorganic salt ions, metal oxide particles or dust. Then, the inorganic hydrophobic glass is thoroughly rinsed with deionized water to remove residual acid. Finally, it is dried with nitrogen to obtain the pretreated substrate. The pretreated substrate is immersed in the ultrasonically dispersed copper-containing solution B and stirred at 25°C and 300 rpm for 15 min.

[0088] (3) Add dopamine precursor to copper-containing solution B in step (2) and stir until it is dissolved evenly to obtain mixed solution C, wherein the amount of dopamine added in mixed solution C is 2g / L.

[0089] (4) Add an aqueous solution of hydrogen peroxide with a mass percentage concentration of 30% to the mixed solution C in step (3) at a rate of 3 mL / min according to the molar ratio of hydrogen peroxide to dopamine of 3.7:1. React at 25°C and 200 rpm for 3 min under light-protected conditions to form a dopamine polymer coating on the substrate surface.

[0090] (5) The substrate with the dopamine polymer coating on the surface is taken out, washed with deionized water, and then vacuum dried at room temperature to remove moisture, so as to obtain a brown modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction.

[0091] The surface morphology comparison AFM and roughness statistics of the coating prepared in this comparative example are shown in the figure below. Figure 2 As shown in the figure, the XPS chemical composition and bonding evolution results are as follows: Figure 3 As shown, the antibacterial test results of the coating against Escherichia coli and Staphylococcus aureus are as follows: Figure 4 As shown in the figure, the surface wettability evolution verification and antibacterial rate statistics are as follows: Figure 5 As shown in the figure, the coating cell compatibility results are as follows: Figure 6 As shown.

[0092] Comparative Example 4 A method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction specifically includes the following steps: (1) Prepare a Tris buffer solution with pH 8.5 and concentration of 50 mmol / L using Tris and deionized water, namely buffer solution A (the pH of this solution is adjusted by NaOH and HCl). Add copper sulfate to buffer solution A to obtain copper-containing solution B, wherein the amount of copper sulfate added to copper-containing solution B is 0.00225 g / mL. Then, ultrasonically disperse copper-containing solution B for 10 min to obtain ultrasonically dispersed copper-containing solution B.

[0093] (2) Immerse the inorganic hydrophilic glass in a 1 mol / L hydrochloric acid aqueous solution and sonicate for 20 min to remove inorganic salt ions, metal oxide particles or dust. Then rinse the inorganic hydrophilic glass thoroughly with deionized water to remove residual acid. Finally, blow it dry with nitrogen to obtain the pretreated substrate. Immerse the pretreated substrate in the ultrasonically dispersed copper-containing solution B and stir at 25°C and 300 rpm for 15 min.

[0094] (3) Add dopamine precursor to copper-containing solution B in step (2) and stir until it is dissolved evenly to obtain mixed solution C, wherein the amount of dopamine added in mixed solution C is 2g / L.

[0095] (4) Add an aqueous solution of hydrogen peroxide with a mass percentage concentration of 30% to the mixed solution C in step (3) at a rate of 3 mL / min according to the molar ratio of hydrogen peroxide to dopamine of 3.7:1. React at 25°C and 200 rpm for 3 min under light-protected conditions to form a dopamine polymer coating on the substrate surface.

[0096] (5) The substrate with the dopamine polymer coating on the surface is taken out, washed with deionized water, and then vacuum dried at room temperature to remove moisture, so as to obtain a brown modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction.

[0097] The surface morphology comparison AFM and roughness statistics of the coating prepared in this comparative example are shown in the figure below. Figure 2 As shown in the figure, the XPS chemical composition and bonding evolution results are as follows: Figure 3 As shown in the figure, the surface wettability evolution verification and antibacterial rate statistics are as follows: Figure 5 As shown in the figure, the coating cell compatibility results are as follows: Figure 6 As shown.

[0098] Comparative Example 5 A method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction specifically includes the following steps: (1) Prepare a Tris buffer solution with pH 8.5 and concentration of 50 mmol / L using Tris and deionized water, namely buffer solution A (the pH of this solution is adjusted by NaOH and HCl). Add copper sulfate to buffer solution A to obtain copper-containing solution B, wherein the amount of copper sulfate added to copper-containing solution B is 0.00225 g / mL. Then, ultrasonically disperse copper-containing solution B for 10 min to obtain ultrasonically dispersed copper-containing solution B.

[0099] (2) PDMS is coated on the glass surface and then cured to obtain inorganic hydrophobic glass. The inorganic hydrophobic glass is immersed in 1 mol / L hydrochloric acid aqueous solution and sonicated for 20 min to remove inorganic salt ions, metal oxide particles or dust. Then, the inorganic hydrophobic glass is thoroughly rinsed with deionized water to remove residual acid. Finally, it is dried with nitrogen to obtain the pretreated substrate. The pretreated substrate is immersed in the ultrasonically dispersed copper-containing solution B and stirred at 25°C and 300 rpm for 15 min.

[0100] (3) Add dopamine precursor to copper-containing solution B in step (2) and stir until it is dissolved evenly to obtain mixed solution C, wherein the amount of dopamine added in mixed solution C is 2g / L.

[0101] (4) Add an aqueous solution of hydrogen peroxide with a mass percentage concentration of 30% to the mixed solution C in step (3) at a rate of 3 mL / min according to the molar ratio of hydrogen peroxide to dopamine of 3.7:1. React at 25°C and 200 rpm for 5 min under light-protected conditions to form a dopamine polymer coating on the substrate surface.

[0102] (5) The substrate with the dopamine polymer coating on the surface is taken out, washed with deionized water, and then vacuum dried at room temperature to remove moisture, so as to obtain a brown modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction.

[0103] The surface morphology comparison AFM and roughness statistics of the coating prepared in this comparative example are shown in the figure below. Figure 2 As shown.

[0104] Comparative Example 6 A method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction specifically includes the following steps: (1) Prepare a Tris buffer solution with pH 8.5 and concentration of 50 mmol / L using Tris and deionized water, namely buffer solution A (the pH of this solution is adjusted by NaOH and HCl). Add copper sulfate to buffer solution A to obtain copper-containing solution B, wherein the amount of copper sulfate added to copper-containing solution B is 0.00225 g / mL. Then, ultrasonically disperse copper-containing solution B for 10 min to obtain ultrasonically dispersed copper-containing solution B.

[0105] (2) Immerse the inorganic hydrophilic glass in a 1 mol / L hydrochloric acid aqueous solution and sonicate for 20 min to remove inorganic salt ions, metal oxide particles or dust. Then rinse the inorganic hydrophilic glass thoroughly with deionized water to remove residual acid. Finally, blow it dry with nitrogen to obtain the pretreated substrate. Immerse the pretreated substrate in the ultrasonically dispersed copper-containing solution B and stir at 25°C and 300 rpm for 15 min.

[0106] (3) Add dopamine precursor to copper-containing solution B in step (2) and stir until it is dissolved evenly to obtain mixed solution C, wherein the amount of dopamine added in mixed solution C is 2g / L.

[0107] (4) Add an aqueous solution of hydrogen peroxide with a mass percentage concentration of 30% to the mixed solution C in step (3) at a rate of 3 mL / min according to the molar ratio of hydrogen peroxide to dopamine of 3.7:1. React at 25°C and 200 rpm for 5 min under light-protected conditions to form a dopamine polymer coating on the substrate surface.

[0108] (5) The substrate with the dopamine polymer coating on the surface is taken out, washed with deionized water, and then vacuum dried at room temperature to remove moisture, so as to obtain a brown modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction.

[0109] The surface morphology comparison AFM and roughness statistics of the coating prepared in this comparative example are shown in the figure below. Figure 2 As shown.

[0110] This invention uses a UV-Vis spectrophotometer to monitor changes in absorption peaks in solution in real time, paying particular attention to the increase in absorption at 420 nm as an indicator of reaction completion. The test results are as follows: Figure 1 As shown, based on the changes in UV absorption in the reaction solution, the absorption intensity at 420 nm continuously increases over time, indicating that the oxidative polymerization process of dopamine was successfully completed and the coating is uniform. The final film thickness is 30-50 nm, and the surface roughness Ra measured by AFM is 3.2 nm, indicating that the coating has good uniformity and a smooth surface.

[0111] AFM was used to analyze the surface morphology of the coating at different reaction times, observing the coating thickening process and changes in surface roughness. The test results are as follows: Figure 2 As shown in the results, tests revealed that the coating on the hydrophobic substrate formed a continuous PDA film after 20 minutes, starting from uniform nucleation and gradually thickening. The deposition process on the hydrophilic substrate was slower, accelerating only after about 10 minutes, and gradually forming a denser film layer after 10-20 minutes. The surface roughness (Ra) of the coating changed significantly with time, thus affecting its antibacterial properties.

[0112] The chemical composition and surface functional group changes of the PDA coating were observed by XPS, especially the changes in C1s, N1s, and Cu2p peaks. The degree of oxidation and crosslinking of the coating was analyzed. The test results are as follows: Figure 3 As shown, tests revealed that the proportion of C=O components in the coating increased significantly with increasing reaction time, indicating a deeper degree of oxidation in the coating; N1s N + The increase in the (~402eV) ratio indicates that the amine groups in the coating are further converted into the oxidized state, which has high chemical stability. At the same time, the appearance of Cu-catechol coordination signal proves that copper ions and PDA form a stable coordination structure, thereby enhancing the compactness and antibacterial properties of the film.

[0113] Staphylococcus aureus and Escherichia coli were inoculated separately onto nutrient agar plates and incubated overnight at 37°C. Single colonies were picked and suspended in sterile physiological saline, and the bacterial concentration was adjusted to 0.5 McFarland standard (approximately 1.5 × 10⁻⁶). 8 (CFU / mL), then diluted 100-fold with sterile physiological saline to obtain a concentration of approximately 1.5 × 10⁻⁶ CFU / mL. 6 CFU / mL working bacterial suspension was used for antibacterial experiments. The sterilized coated sample and a blank glass substrate (control group) were placed in sterile petri dishes. 100 μL of the working bacterial suspension was added dropwise to the sample surface, ensuring even coverage. The mixture was allowed to stand for 24 hours under normal light conditions at room temperature. After the reaction, the sample surface was thoroughly rinsed with sterile physiological saline to recover bacteria. The recovered solution was then serially diluted (e.g., 100-fold). 100 μL of the diluted solution was spread onto nutrient agar plates and incubated at 37°C for 24 hours. Plate counts were then performed, and the antibacterial rate was calculated. The test results are as follows: Figure 4 As shown in the test results, the PDA coating exhibits a significant inhibitory effect on both E. coli and S. aureus. In particular, at reaction times of 10 minutes or more, the coating can effectively reduce the initial adhesion formation of bacteria, demonstrating excellent antibacterial effect.

[0114] The stability and durability of the coating were evaluated through contact angle testing and antibacterial retention rate. The test results are as follows: Figure 5 As shown, tests revealed that the coating maintained good antibacterial properties even after multiple water washes and ultrasonic treatments, and the contact angle change was less than 5°, indicating that the coating has good stability and wash resistance.

[0115] Mouse osteogenic progenitor cells (MC3T3-E1) were used for cell culture. Cells were purchased from Pronosei Corporation. MC3T3-E1 cells in the logarithmic growth phase were harvested, counted, and the cell concentration was adjusted to 6 × 10⁶ cells / year. 3The culture medium was seeded into 96-well plates and incubated in a 5% CO2, 37°C incubator. Following the above grouping and treatment, the plates were incubated for 24 hours in a 5% CO2, 37°C incubator. The culture medium was removed, and each well was washed three times with PBS. 100 μL of medium containing 10% CCK8 was added to each well, and the plates were incubated in a 5% CO2, 37°C incubator for 2 hours. The absorbance at 450 nm was measured using a microplate reader. The test results are as follows: Figure 6 As shown, tests revealed that the PDA coating extract maintained a relative proliferation rate of MC3T3-E1 cells within the range of 95.5% to 100%, indicating that the coating has no significant cytotoxicity and is suitable for medical-related surface modification.

[0116] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or improvement of the technology in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction, characterized in that, Specifically, the following steps are included: (1) Prepare buffer solution A using organic amine buffer, add copper salt to buffer solution A to obtain copper-containing solution B, and then perform ultrasonic dispersion treatment on copper-containing solution B to obtain ultrasonically dispersed copper-containing solution B; (2) The substrate is acid-washed to obtain a pretreated substrate, and the pretreated substrate is immersed in a copper-containing solution B after ultrasonic dispersion. (3) Add dopamine precursor to copper-containing solution B from step (2) to obtain mixed solution C; (4) Add an aqueous solution of hydrogen peroxide to the mixed solution C in step (3), react under light-protected conditions, and form a dopamine polymer coating on the substrate surface; (5) The substrate with the dopamine polymer coating on the surface is removed, and after washing and drying, a modified substrate with a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction is obtained.

2. The method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction according to claim 1, characterized in that, In step (1), the organic amine buffer is Tris or its salt; the pH of the buffer solution A is 8.0~9.0; and the concentration of the organic amine buffer in the buffer solution A is 10~100 mmol / L.

3. The method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction according to claim 1, characterized in that, In step (1), the amount of copper salt added to copper solution B is 0.0001~0.02 g / mL; the copper salt is one or more of copper sulfate, copper nitrate or copper acetate.

4. The method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction according to claim 1, characterized in that, The substrate in step (2) is an inorganic hydrophilic glass or an inorganic hydrophobic glass; the acid washing conditions are: immerse the substrate in a 1 mol / L hydrochloric acid aqueous solution and sonicate for 20 min, then rinse and dry.

5. The method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction according to claim 1, characterized in that, The conditions for immersing the pretreated substrate in the ultrasonically dispersed copper-containing solution B in step (2) are: standing at 15~30℃ for 20~40 min or stirring at 100~600 rpm for 10~20 min.

6. The method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction according to claim 1, characterized in that, In step (3), the dopamine precursor can be an aqueous solution of dopamine or solid dopamine; the amount of dopamine added in the mixed solution C is 0.5~2.5 g / L.

7. The method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction according to claim 1, characterized in that, In step (4), the hydrogen peroxide content in the aqueous solution is 3-35% by mass; the aqueous solution of hydrogen peroxide is added to the mixed solution C at a ratio of (0.5-20):1 of hydrogen peroxide to dopamine; the aqueous solution of hydrogen peroxide is added to the mixed solution C at a dropping rate of 1.5-6 mL / min.

8. The method for preparing a dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction according to claim 1, characterized in that, The reaction conditions in step (4) under light-protected conditions are: at 20~35℃, the reaction is carried out at a speed of 100~600rpm for 10~20min.

9. The dopamine surface self-polymerization coating based on copper / hydrogen peroxide synergistic induction prepared by the method of any one of claims 1 to 8.

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