A photothermal responsive multifunctional composite coating, its preparation method, and its application.

Abstract

This invention discloses a photothermal responsive multifunctional composite coating, its preparation method, and its application, relating to the field of antibacterial nanomaterials technology. The composite coating comprises an electrophoretic deposition onto a substrate using an electrophoretic solution formulated with chitosan and electrospun short fibers. The electrospun short fibers are prepared by electrospinning a spinning solution formulated with polylactic acid and a core-shell composite material, followed by plasma treatment and fluffing. The core-shell composite material is a composite material with a silver nanorod core and a mesoporous silica shell; wherein the silver nanorods encapsulate gold bipyramidal seeds. The core-shell structured silver nanoparticle antibacterial agent provided by this invention significantly alleviates the problems of cytotoxicity of silver nanoparticles and limited functionality as a surface modification material for bone implants.

Description

Technical Field

[0001] This invention relates to the field of antibacterial nanomaterials technology, specifically to a photothermal responsive multifunctional composite coating, its preparation method, and its application. Background Technology

[0002] With the increasing aging of the population, more and more patients are suffering from bone injuries due to osteoporosis, external force injuries, accidents, and other reasons. In clinical practice, when encountering bone injuries that cannot heal on their own, bone implants are usually required to help patients restore function at the affected site. Bone implantation surgery places extremely stringent requirements on the materials used in the implants. Titanium and its alloys are among the most widely used metal materials for bone implants, but they still have many problems, such as poor biocompatibility and a high risk of postoperative infection. Currently, researchers are focusing on surface modification of titanium and titanium alloys to improve their biocompatibility and impart antibacterial properties. Multi-material composites and multifunctional surface modification are the development directions for bone implant materials. Surface modification technology can greatly promote the clinical application of titanium alloy bone implants. Surface-modified titanium alloy implants can possess both antibacterial properties and good biocompatibility. Polylactic acid (PLA) is a polymer material with good biocompatibility, biodegradability, and processability, and has been approved by the U.S. Food and Drug Administration for human use. PLA is completely degradable in the human body, and its degradation products can be absorbed by the body without irritation or toxic side effects, making it highly safe for human use and eliminating the need for secondary surgery for removal. Compared to traditional medical metals such as stainless steel and titanium alloys, PLA's elastic modulus is closer to that of human bone tissue, reducing stress shielding effects.

[0003] Nano-silver, as an antibacterial agent, possesses advantages such as high efficiency, long-lasting antibacterial activity, broad-spectrum antibacterial properties, and a tendency to induce drug resistance, and is widely used in research on antibacterial modification of titanium material surfaces. In recent years, research on using silver as an antibacterial agent to improve the antibacterial ability of materials has gradually increased, but all methods have some shortcomings. Existing technologies use a melt method to prepare silver-loaded glass antibacterial agents, but this preparation method usually requires high-temperature reactions, making the process complex, demanding high-quality equipment, and incurring high maintenance costs. Silver-doped porous antibacterial ceramic materials have also been disclosed, but the preparation method is complex and has a long cycle, making practical operation difficult. Similarly, a method for preparing spherical zinc-silver materials has been disclosed, but this method does not involve silver ion release control, which may cause strong toxic side effects.

[0004] In summary, current silver antibacterial agents and titanium surface antibacterial modification technologies suffer from high costs, complex preparation processes, and the fact that the antibacterial properties of silver nanoparticles are closely related to their shape—only silver nanorods (AgNRs) with a specific aspect ratio exhibit photothermal responsive antibacterial properties. Furthermore, silver nanoparticles have drawbacks such as easy accumulation in vivo leading to strong toxic side effects, limited functionality when applied to bone implant surface modification, and poor bioactivity that can easily cause rejection reactions. Therefore, it is necessary to develop a simple method for constructing a bioactive coating on the surface of titanium implants that is uniformly deposited, has strong adhesion, and offers controllable antibacterial capabilities, thereby promoting the practical clinical application of titanium implants. Summary of the Invention

[0005] To address the shortcomings of the aforementioned background technologies, this invention primarily targets the problems of poor bioactivity of titanium matrices leading to rejection reactions, the tendency of silver nanoparticles to accumulate in vivo and generate strong toxic side effects, and limited functionality when applied to bone implant surface modification. This invention provides a photothermal-responsive multifunctional composite coating, its preparation method, and its applications. This composite coating possesses a core-shell structured silver nanoparticle antibacterial agent, significantly mitigating the cytotoxicity of silver nanoparticles and addressing the limitations of its limited functionality as a surface modification material for bone implants. Furthermore, the preparation method provides a novel method for preparing electrospun short fibers, simplifying the electrospun short fiber manufacturing process and reducing costs.

[0006] The first objective of this invention is to provide a photothermal responsive multifunctional composite coating, wherein the composite coating comprises an electrophoretic solution prepared with chitosan and electrospun short fibers, which is electrophoretically deposited onto a substrate to form a coating.

[0007] The electrospun short fiber is obtained by electrospinning a spinning solution formulated with polylactic acid and a core-shell composite material, and then the spinning product is successively subjected to plasma treatment and fluffing treatment.

[0008] The core-shell composite material is a composite material with a core-shell structure formed by silver nanorods as the core and mesoporous silica as the shell.

[0009] The silver nanorods are encapsulated with gold bipyramidal seeds.

[0010] Preferably, the molar ratio of the silver nanorods to mesoporous silica is 1:3~7;

[0011] The silver nanorods have a length of 60-150 nm and an aspect ratio of 3-5:1.

[0012] The thickness of the mesoporous silica shell is 10–80 nm.

[0013] Preferably, the plasma treatment involves placing the spun product in a plasma treatment machine, and after the vacuum level reaches the required level, turning on the plasma treatment machine to treat the sample with plasma for ten minutes. The purpose of the plasma treatment is to change the hydrophilicity of the fiber membrane so that it can be dispersed in the sodium borohydride solution in subsequent processing.

[0014] Preferably, the fluffing treatment involves immersing the spun product in a sodium borohydride solution after plasma treatment to fluff it up.

[0015] The concentration of the sodium borohydride solution is 1.5~3M.

[0016] Preferably, the core-shell composite material is prepared according to the following steps:

[0017] Silver nanorods were prepared using the gold seed method;

[0018] The prepared silver nanorods were dispersed in a chloroform solution and then added to an aqueous solution of CTAB to obtain a homogeneous oil-in-water microemulsion. The chloroform in the microemulsion was evaporated to obtain an AgNR@CTAB solution.

[0019] AgNR@CTAB solution and tetraethyl orthosilicate solution doped with metal ions are added to an alkaline aqueous solution containing CTAB. After the reaction is complete, a core-shell structured composite material is obtained.

[0020] Preferably, the composite coating is capable of photothermal conversion of near-infrared light with a wavelength of 780–850 nm.

[0021] Preferably, the coating obtained by electrophoretic deposition on the substrate has a thickness of 5-20 μm.

[0022] The second objective of this invention is to provide a method for preparing a photothermal responsive multifunctional composite coating, comprising the following steps:

[0023] The electrospun short fibers were frozen at -85~-75℃ for 24~48h;

[0024] A certain amount of deionized water, anhydrous ethanol, chitosan, and acetic acid are mixed evenly to obtain an electrophoresis solution.

[0025] The frozen electrospun short fibers are uniformly dispersed in the electrophoresis solution to obtain the short fiber electrophoresis solution;

[0026] In a short fiber electrophoresis solution, a stainless steel sheet is used as the anode and a titanium substrate is used as the cathode. A photothermal responsive multifunctional composite coating is prepared on the surface of the titanium sheet by electrophoretic deposition.

[0027] Preferably, the ratio of deionized water, anhydrous ethanol, and acetic acid is 10~89:10~89:1;

[0028] The concentration of electrospun short fibers in the short fiber electrophoresis solution is 0.5~5 mg / mL; the concentration of chitosan in the short fiber electrophoresis solution is 0.5~5 mg / mL.

[0029] The third objective of this invention is to provide an application of a photothermal responsive multifunctional composite coating in bone implant substrates.

[0030] Compared with the prior art, the beneficial effects of the present invention are:

[0031] This invention provides a photothermal responsive multifunctional composite coating, its preparation method, and its application. The composite coating provided by this invention includes chitosan and electrospun short fibers. The electrospun short fibers include polylactic acid and a core-shell structure composite material mounted thereon. The composite material has a core-shell structure formed by silver nanorods as the core and mesoporous silica coated on the surface of the silver nanorods as the shell. The silver nanorods contain gold bipyramidal seeds.

[0032] The preparation method provided by this invention includes shredding an electrospun fiber membrane after plasma treatment, soaking it in a sodium borohydride solution for a period of time to fluff it up, and then freezing it overnight to obtain electrospun short fibers. The electrospun short fibers are then added to a chitosan electrophoresis solution, and a composite coating is deposited on the surface of a titanium sheet using electrophoretic deposition. This invention obtains composite coatings with different surface morphologies by controlling the ratio of chitosan to short fibers in the electrophoresis solution and the voltage, current, and deposition time during the electrophoretic deposition process. Ultimately, a uniform, photothermally responsive, multifunctional composite coating is obtained on the surface of the titanium sheet, which is expected to be applied in the surface modification of titanium-based bone implant materials.

[0033] The preparation method of the uniform electrospinning short fiber electrophoresis solution provided by the present invention is simple, requires little equipment, has strong applicability, can meet the needs of short fiber preparation of different electrospinning fibers, and is easy to put into industrial production.

[0034] This invention yields a composite coating with photothermal response, which alleviates the cytotoxicity of AgNR@MSN and the limited functionality of AgNR@MSN as a surface modification material for bone implants through photothermal assistance.

[0035] The process of this invention is simple, the required equipment is simple, and the coating process is highly applicable, which can meet the preparation of different functionalized nano-silver-based antibacterial coatings and is easy to put into industrial production.

[0036] Silver nanorods were prepared using the gold seed method, and a silver nanorod composite material encapsulated in ion-doped mesoporous silica was prepared using the sol-gel method. Using CTAB as a template agent and TEOS as a silicon source, a core-shell structure was formed. The core-shell structured silver nanorods can slowly release silver ions through mesoporous channels, avoiding the toxic side effects of sudden silver ion release.

[0037] By adjusting the electrophoretic deposition parameters, the surface morphology and thickness of the coating can be controlled as needed, thereby controlling the content of antibacterial agents and cell adhesion behavior in the coating. Attached Figure Description

[0038] Figure 1 This is a scanning electron microscope image of the AgNR@MSN / PLA fiber membrane described in this invention.

[0039] Figure 2 This is a scanning electron microscope image of the short fibers obtained by shortening an electrospun fiber membrane using the method described in this invention.

[0040] Figure 3 This is a scanning electron microscope image showing the thickness of the composite coating described in this invention.

[0041] Figure 4 This is a scanning electron microscope image of the composite coatings prepared with different fiber membrane contents in the electrophoretic solution described in this invention.

[0042] Figure 5 The photothermal performance of the composite coating described in this invention was tested under NIR (near-infrared) light irradiation.

[0043] Figure 6 This is a qualitative antibacterial performance inhibition zone test of the composite coating described in this invention.

[0044] Figure 7 This is a quantitative antibacterial performance test of the composite coating described in this invention. Detailed Implementation

[0045] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific embodiments and accompanying drawings. However, the embodiments described are not intended to limit the present invention.

[0046] The purpose of this invention is to address the shortcomings of titanium matrices, such as poor bioactivity leading to rejection reactions, the tendency of silver nanoparticles to accumulate in vivo and produce strong toxic side effects, and their limited functionality when used for surface modification of bone implants. This invention provides a photothermal-responsive multifunctional composite coating, its preparation method, and its applications. This composite coating contains a core-shell structured silver nanoparticle antibacterial agent, which greatly alleviates the cytotoxicity of silver nanoparticles and the limited functionality as a surface modification material for bone implants. Furthermore, the preparation method provides a novel method for preparing electrospun short fibers, simplifying the electrospun short fiber manufacturing process and reducing costs.

[0047] To achieve the above objectives, the first aspect of the present invention provides a photothermal responsive multifunctional composite coating, the composite coating comprising an electrophoretic solution prepared with chitosan and electrospun short fibers, which is electrophoretically deposited onto a substrate to obtain the coating.

[0048] The electrospun short fiber is obtained by electrospinning a spinning solution formulated with polylactic acid and a core-shell composite material, and then the spinning product is successively subjected to plasma treatment and fluffing treatment.

[0049] The core-shell composite material is a composite material with a core-shell structure formed by silver nanorods as the core and mesoporous silica as the shell.

[0050] The silver nanorods are encapsulated with gold bipyramidal seeds.

[0051] The coating contains PLA / AgNR@MSN short fibers. The silver nanorods in AgNR@MSN exhibit a plasmon resonance effect, enabling photothermal conversion of near-infrared light with wavelengths of 780–850 nm. Irradiating the composite coating with near-infrared light of 780–850 nm triggers the photothermal effect of the coating and promotes the release of silver ions, achieving a synergistic antibacterial effect of silver ions and photothermal interaction.

[0052] The molar ratio of the silver nanorods to mesoporous silica is 1:3~7;

[0053] The silver nanorods have a length of 60-150 nm and an aspect ratio of 3-5:1.

[0054] The thickness of the mesoporous silica shell is 10–80 nm.

[0055] The plasma treatment involves placing the spun product inside a plasma treatment machine. Once the required vacuum level is reached, the machine is turned on to treat the sample with plasma for ten minutes. The purpose of the plasma treatment is to alter the hydrophilicity of the fiber membrane, allowing it to disperse in the sodium borohydride solution during subsequent processing.

[0056] The fluffing treatment involves immersing the spun product in a sodium borohydride solution after plasma treatment to fluff it up.

[0057] The concentration of the sodium borohydride solution is 1.5~3M.

[0058] The core-shell structured composite material is prepared according to the following steps:

[0059] Silver nanorods were prepared using the gold seed method;

[0060] The prepared silver nanorods were dispersed in a chloroform solution and then added to an aqueous solution of CTAB to obtain a homogeneous oil-in-water microemulsion. The chloroform in the microemulsion was evaporated to obtain an AgNR@CTAB solution.

[0061] AgNR@CTAB solution and tetraethyl orthosilicate solution doped with metal ions are added to an alkaline aqueous solution containing CTAB. After the reaction is completed, the core-shell composite material (AgNR@MSN) is obtained.

[0062] The molar ratio of silver nanorods to CTAB is 1:3~6.

[0063] The method for preparing silver nanorods via gold seeding includes:

[0064] Preparation of gold seed solution;

[0065] The gold seed solution was added to a growth aqueous solution containing CTAB, HAuCl4, AgNO3, HCl and AA. After standing and reacting, a metal cone was obtained.

[0066] A solution of AgNO3 and AA was added to a solution of gold bipyramidal compounds containing CTAC to obtain silver nanorods encapsulated with gold bipyramidal compounds; wherein, in the reaction solution, AA and Ag... + The molar ratio is 3~5:1.

[0067] In one embodiment, the specific preparation method of the silver nanorods encapsulating gold bipyramidal structures is as follows:

[0068] 1.1) At room temperature, CTAC (50 mM, 8.95 mL), citric acid (5 mM, 1 mL), and HAuCl4 (50 mM, 0.05 mL) were added sequentially to the solution. Then, HAuCl4 was rapidly reduced using sodium borohydride (25 mM, 0.25 mL) to prepare gold seeds. After 2 min, the bottle was capped, and the seed solution was heated at 80 °C with gentle stirring for 90 min to obtain the gold seed solution. Finally, the seed solution was stored at room temperature. The gold seed solution was used to grow small gold bipyramidal structures.

[0069] 1.2) Under vigorous stirring, equal portions (1 mL) of the gold seed solution were added to a growth aqueous solution containing CTAB (20 mL, 100 mM), HAuCl4 (0.2 mL, 50 mM), AgNO3 (0.2 mL, 10 mM), HCl (0.4 mL, 1 M), and ascorbic acid (AA) (0.16 mL, 100 mM). The mixture was allowed to stand at 30 °C for 4 h to obtain gold bipyramids. After 4 h of reaction, the solution was centrifuged (10000 rpm, 30 min) to remove excess reagents and redispersed in CTAC (10 mM, 1 mL).

[0070] 1.3) Under vigorous stirring, a solution of AgNO3 (10 mM) and AA (100 mM) was added to a solution of gold bipyramidal powder (10 mL) containing CTAC (10 mM) at room temperature. Throughout the addition process, the molar ratio of [AA]:[AgNO3] was maintained. + The concentration of 4 was kept constant. After the addition was complete, the mixture was stirred vigorously at 60°C for 2 h. Finally, the resulting solution was centrifuged (10,000 rpm, 30 min) and redispersed in water to obtain silver nanorods.

[0071] It should be noted that the length and aspect ratio of the bipyramidal silver nitrate can be changed by altering the concentration ratio of the two components to meet different requirements.

[0072] In one embodiment, the preparation steps of electrospun short fibers include:

[0073] 2.1) At room temperature, weigh 2 g of PLA powder (molecular weight 160,000) and dissolve it in 12 mL of DCM solution. Stir magnetically until completely dissolved and the solution becomes transparent. Simultaneously, add 0.1 g of AgNR@MSN powder to 8 mL of DMF solution and stir to disperse it evenly. After both solutions are evenly dispersed, mix them and continue stirring for 6 hours to prepare a co-spinning electrospinning solution.

[0074] 2.2) Inject the prepared electrospinning solution into two 5 mL syringes. After correctly installing the syringes and connecting the circuit, turn on the equipment. Specific electrospinning process parameters are set as follows: voltage 18 kV, feed rate 1 mL / h, distance between the syringe needle and the roller collector 15 cm. Spinning ambient temperature 25 ± 2℃, relative humidity 45 ± 2%. The resulting spun product is a polylactic acid fiber membrane (PLA / AgNR@MSN).

[0075] 2.3) Weigh 0.1g of the prepared PLA / AgNR@MSN fiber membrane, ionize it for 10min and then take it out for later use.

[0076] 2.4) Cut the plasma-treated fiber membrane into 1mm×1mm fragments.

[0077] 2.5) Weigh 3.783 g of NaBH4 and dissolve it in 50 ml of 4 °C deionized water to prepare a 2 M NaBH4 solution.

[0078] 2.6) Add the fiber membrane fragments to the prepared NaBH4 solution and soak for 30 minutes, during which time sonication and stirring are used to make it fluffy.

[0079] 2.7) Filter the mixed solution of fiber and sodium borohydride, and wash the fiber on the filter paper three times with deionized water to remove residual sodium borohydride. Then place the washed fiber in a freezer at -80°C overnight.

[0080] This yields electrospun short fibers.

[0081] The composite coating is capable of photothermal conversion of near-infrared light with a wavelength of 780–850 nm.

[0082] The coating, which is deposited on the substrate by electrophoretic deposition, has a thickness of 5-20 μm.

[0083] In one embodiment, the method for preparing the core-shell composite material (AgNR@MSN) includes:

[0084] The prepared silver nanorods were dispersed in a chloroform solution and then added to an aqueous solution of CTAB to obtain a homogeneous oil-in-water microemulsion. The chloroform in the microemulsion was evaporated to obtain an AgNR@CTAB solution.

[0085] AgNR@CTAB solution and tetraethyl orthosilicate solution doped with metal ions are added to an alkaline aqueous solution containing CTAB. After the reaction is complete, a core-shell structured composite material is obtained.

[0086] A second aspect of this invention provides a method for preparing a photothermal responsive multifunctional composite coating, comprising the following steps:

[0087] The electrospun short fibers were frozen at -85~-75℃ for 24~48h;

[0088] A certain amount of deionized water, anhydrous ethanol, chitosan, and acetic acid are mixed evenly to obtain an electrophoresis solution.

[0089] The frozen electrospun short fibers are uniformly dispersed in the electrophoresis solution to obtain the short fiber electrophoresis solution;

[0090] In a short fiber electrophoresis solution, a stainless steel sheet is used as the anode and a titanium substrate is used as the cathode. A photothermal responsive multifunctional composite coating is prepared on the surface of the titanium sheet by electrophoretic deposition.

[0091] Preferably, the ratio of deionized water, anhydrous ethanol, and acetic acid is 10~89:10~89:1;

[0092] The concentration of electrospun short fibers in the short fiber electrophoresis solution is 0.5~5 mg / mL; the concentration of chitosan in the short fiber electrophoresis solution is 0.5~5 mg / mL.

[0093] In one embodiment, the method for preparing a photothermal responsive multifunctional composite coating includes the following steps:

[0094] At room temperature, 50 ml of deionized water, 49 ml of anhydrous ethanol and 1 ml of acetic acid were mixed evenly, and 0.5 g of chitosan was added and stirred to dissolve, thus obtaining the electrophoresis solution.

[0095] The electrospun short fibers that have been frozen overnight are added to the prepared electrophoresis solution and ultrasonically stirred to disperse them evenly in the electrophoresis solution, thus obtaining a uniformly dispersed short fiber electrophoresis solution.

[0096] At room temperature, a stainless steel sheet is used as the anode and a titanium sheet as the cathode. A photothermal responsive short fiber coating is prepared on the surface of the titanium sheet by electrophoretic deposition. The morphology of the coating on the surface of the titanium sheet is changed by changing the electrophoretic deposition parameters.

[0097] The process of freezing the fluffed fibers overnight at -80°C before adding them to the electrophoresis solution is to make the fiber membrane more dispersed in the electrophoresis solution.

[0098] A third aspect of the present invention provides the application of a photothermal responsive multifunctional composite coating in bone implant substrates.

[0099] It should be noted that this invention provides the application of photothermal responsive multifunctional composite coatings in the surface modification of titanium implants with antibacterial / osteogenic functions. This invention also provides the application of core-shell structured photothermal responsive multifunctional ion-doped composite materials in the preparation of antibacterial agents with pro-angiogenic / osteogenic functions.

[0100] It should be noted that, unless otherwise specified, the experimental methods used in this invention are all conventional methods; and the reagents and materials used, unless otherwise specified, are all commercially available.

[0101] Example 1

[0102] A method for preparing a photothermal responsive multifunctional composite coating includes the following steps:

[0103] Step 1: Prepare silver nanorods using the gold seed method described above;

[0104] Step 2: The prepared silver nanorods were dispersed in a chloroform (CHCl3) solution to prepare a 3.0 mL (5 mg / mL) mixed solution. The mixed solution was added to 10 mL of an aqueous solution containing 0.2 g CTAB, and the mixture was stirred vigorously to obtain a homogeneous oil-in-water microemulsion. The resulting microemulsion was heated at 65 °C for 20 min to evaporate the CHCl3, yielding an AgNR@CTAB solution.

[0105] Step 3: Dissolve 0.05 g CTAB in 86 mL of water at room temperature with stirring, and add NaOH (0.7 mL, 2 M). Then add the AgNR@CTAB solution obtained in Step 2, and heat the mixture to 60°C. While stirring vigorously, add 0.75 mL of TEOS to the reaction solution. After the addition is complete, allow the reaction to proceed for 2 h. After the reaction is complete, centrifuge at 10000 rpm for 5 min and collect the product.

[0106] Step 4: Extract with an ethanol solution containing ammonium nitrate (6 g / L) and reflux for 24 h to remove the template agent. After obtaining the sample, wash and dry it. The sample is labeled as AgNR@MSN.

[0107] Step 5: At room temperature, weigh 2 g of PLA powder (molecular weight 160,000) and dissolve it in 12 mL of DCM solution. Stir magnetically until completely dissolved and the solution becomes transparent. Simultaneously, add 0.4 g of AgNR@MSN powder to 8 mL of DMF solution and stir to disperse it evenly. After both solutions are evenly dispersed, mix them and continue stirring for 6 hours to prepare a co-spinning electrospinning solution.

[0108] Step 6: Inject the prepared electrospinning solution into two 5 mL syringes. After correctly installing the syringes and connecting the circuit, turn on the equipment. Specific electrospinning process parameters are set as follows: voltage 18 kV, feed rate 1 mL / h, distance between the syringe needle and the roller collector 15 cm. Spinning ambient temperature 25 ± 2℃, relative humidity 45 ± 2%. Label the collected electrospinned fiber membrane as 20%AgNR@MSN / PLA.

[0109] Step 7: Weigh 3.783g of NaBH4 and dissolve it in 50ml of 4℃ deionized water to prepare a 2M NaBH4 solution. Weigh 100mg of 20% AgNR@MSN / PLA fiber membrane, cut it into 1mm×1mm fragments, and soak them in the NaBH4 solution for 30min, ultrasonically stirring during the process to disperse and fluff the fiber membrane. Filter the mixed solution of fiber and sodium borohydride, and wash the fiber on the filter paper three times with deionized water to remove residual sodium borohydride. Then place the washed fiber in a -80℃ freezer overnight.

[0110] Step 8: At room temperature, measure 50 ml of deionized water, 49 ml of anhydrous ethanol, and 1 ml of acetic acid and mix them thoroughly. Add 0.5 g of chitosan and stir to dissolve, obtaining an electrophoresis buffer. Add the overnight frozen fiber membrane to the prepared electrophoresis buffer and sonicate to disperse it evenly in the electrophoresis buffer, obtaining a uniformly dispersed short fiber electrophoresis buffer.

[0111] Step 9: At room temperature, a 1cm wide stainless steel sheet is used as the anode, and a 1cm wide titanium sheet is used as the cathode. The distance between the anode and cathode is 1cm, and the length of each anode and cathode immersed in the electrophoretic solution is 2cm. Electrophoretic deposition is performed on the surface of the titanium sheet at a constant current of 0.03A for 3 minutes. After drying, a photothermal responsive multifunctional composite coating is obtained.

[0112] Example 2

[0113] A method for preparing a photothermal responsive multifunctional composite coating includes the following steps:

[0114] Step 1: Prepare silver nanorods using the gold seed method described above;

[0115] Step 2: The prepared silver nanorods were dispersed in a chloroform (CHCl3) solution to prepare a 3.0 mL (5 mg / mL) mixed solution. The mixed solution was added to 10 mL of an aqueous solution containing 0.2 g CTAB, and the mixture was stirred vigorously to obtain a homogeneous oil-in-water microemulsion. The resulting microemulsion was heated at 65 °C for 20 min to evaporate the CHCl3, yielding an AgNR@CTAB solution.

[0116] Step 3: Dissolve 0.05 g CTAB in 86 mL of water at room temperature with stirring, and add NaOH (0.7 mL, 2 M). Then add the AgNR@CTAB solution obtained in Step 2, and heat the mixture to 60°C. While stirring vigorously, add 0.75 mL of TEOS to the reaction solution. After the addition is complete, allow the reaction to proceed for 2 h. After the reaction is complete, centrifuge at 10000 rpm for 5 min and collect the product.

[0117] Step 4: Extract with an ethanol solution containing ammonium nitrate (6 g / L) and reflux for 24 h to remove the template agent. After obtaining the sample, wash and dry it. The sample is labeled as AgNR@MSN.

[0118] Step 5: At room temperature, weigh 2 g of PLA powder (molecular weight 160,000) and dissolve it in 12 mL of DCM solution. Stir magnetically until completely dissolved and the solution becomes transparent. Simultaneously, add 0.6 g of AgNR@MSN powder to 8 mL of DMF solution and stir to disperse it evenly. After both solutions are evenly dispersed, mix them and continue stirring for 6 hours to prepare a co-spinning electrospinning solution.

[0119] Step 6: Inject the prepared electrospinning solution into two 5 mL syringes. After correctly installing the syringes and connecting the circuit, turn on the equipment. Specific electrospinning process parameters are set as follows: voltage 18 kV, feed rate 1 mL / h, distance between syringe needle and roller collector 15 cm. Spinning ambient temperature 25 ± 2℃, relative humidity 45 ± 2%. Label the collected electrospinned fiber membrane as 30%AgNR@MSN / PLA.

[0120] Step 7: Weigh 3.783g of NaBH4 and dissolve it in 50ml of 4℃ deionized water to prepare a 2M NaBH4 solution. Weigh 100mg of 30% AgNR@MSN / PLA fiber membrane, cut it into 1mm×1mm fragments, and soak them in the NaBH4 solution for 30min, ultrasonically stirring during the process to disperse and fluff the fiber membrane. Filter the mixed solution of fiber and sodium borohydride, and wash the fiber on the filter paper three times with deionized water to remove residual sodium borohydride. Then place the washed fiber in a -80℃ freezer overnight.

[0121] Step 8: At room temperature, measure 50 ml of deionized water, 49 ml of anhydrous ethanol, and 1 ml of acetic acid and mix them thoroughly. Add 0.5 g of chitosan and stir to dissolve, obtaining an electrophoresis buffer. Add the overnight frozen fiber membrane to the prepared electrophoresis buffer and sonicate to disperse it evenly in the electrophoresis buffer, obtaining a uniformly dispersed short fiber electrophoresis buffer.

[0122] Step 9: At room temperature, a 1cm wide stainless steel sheet is used as the anode, and a 1cm wide titanium sheet is used as the cathode. The distance between the anode and cathode is 1cm, and the length of each anode and cathode immersed in the electrophoretic solution is 2cm. Electrophoretic deposition is performed on the surface of the titanium sheet at a constant current of 0.03A for 3 minutes. After drying, a photothermal responsive multifunctional composite coating is obtained.

[0123] Example 2 differs from Example 1 only in the amount of AgNR@MSN added during electrospinning.

[0124] Example 3

[0125] Step 1: Prepare silver nanorods using the gold seed method described above;

[0126] Step 2: The prepared silver nanorods were dispersed in a chloroform (CHCl3) solution to prepare a 3.0 mL (5 mg / mL) mixed solution. The mixed solution was added to 10 mL of an aqueous solution containing 0.2 g CTAB, and the mixture was stirred vigorously to obtain a homogeneous oil-in-water microemulsion. The resulting microemulsion was heated at 65 °C for 20 min to evaporate the CHCl3, yielding an AgNR@CTAB solution.

[0127] Step 3: Dissolve 0.05 g CTAB in 86 mL of water at room temperature with stirring, and add NaOH (0.7 mL, 2 M). Then add the AgNR@CTAB solution obtained in Step 2, and heat the mixture to 60°C. While stirring vigorously, add 0.75 mL of TEOS to the reaction solution. After the addition is complete, allow the reaction to proceed for 2 h. After the reaction is complete, centrifuge at 10000 rpm for 5 min and collect the product.

[0128] Step 4: Extract with an ethanol solution containing ammonium nitrate (6 g / L) and reflux for 24 h to remove the template agent. After obtaining the sample, wash and dry it. The sample is labeled as AgNR@MSN.

[0129] Step 5: At room temperature, weigh 2 g of PLA powder (molecular weight 160,000) and dissolve it in 12 mL of DCM solution. Stir magnetically until completely dissolved and the solution becomes transparent. Simultaneously, add 0.4 g of AgNR@MSN powder to 8 mL of DMF solution and stir to disperse it evenly. After both solutions are evenly dispersed, mix them and continue stirring for 6 hours to prepare a co-spinning electrospinning solution.

[0130] Step 6: Inject the prepared electrospinning solution into two 5 mL syringes. After correctly installing the syringes and connecting the circuit, turn on the equipment. Specific electrospinning process parameters are set as follows: voltage 18 kV, feed rate 1 mL / h, distance between the syringe needle and the roller collector 15 cm. Spinning ambient temperature 25 ± 2℃, relative humidity 45 ± 2%. Label the collected electrospinned fiber membrane as 20%AgNR@MSN / PLA.

[0131] Step 7: Weigh 3.783 g of NaBH4 and dissolve it in 50 ml of 4°C deionized water to prepare a 2M NaBH4 solution. Weigh 150 mg of 20% AgNR@MSN / PLA fiber membrane, cut it into 1 mm × 1 mm fragments, and soak them in the NaBH4 solution for 30 min, stirring ultrasonically during the process to disperse and fluff the fiber membrane. Filter the mixed solution of fiber and sodium borohydride, and wash the fiber on the filter paper three times with deionized water to remove residual sodium borohydride. Then, freeze the washed fiber overnight at -80°C.

[0132] Step 8: At room temperature, measure 50 ml of deionized water, 49 ml of anhydrous ethanol, and 1 ml of acetic acid and mix them thoroughly. Add 0.5 g of chitosan and stir to dissolve, obtaining an electrophoresis buffer. Add the overnight frozen fiber membrane to the prepared electrophoresis buffer and sonicate to disperse it evenly in the electrophoresis buffer, obtaining a uniformly dispersed short fiber electrophoresis buffer.

[0133] Step 9: At room temperature, a 1cm wide stainless steel sheet is used as the anode, and a 1cm wide titanium sheet is used as the cathode. The distance between the anode and cathode is 1cm, and the length of each anode and cathode immersed in the electrophoretic solution is 2cm. Electrophoretic deposition is performed on the surface of the titanium sheet at a constant current of 0.03A for 3 minutes. After drying, a photothermal responsive multifunctional composite coating is obtained.

[0134] Example 3 differs from Example 1 only in the mass of the fibers in the electrophoresis solution.

[0135] Example 4

[0136] A method for preparing a photothermal responsive multifunctional composite coating includes the following steps:

[0137] Step 1: Prepare silver nanorods using the gold seed method described above;

[0138] Step 2: The prepared silver nanorods were dispersed in a chloroform (CHCl3) solution to prepare a 3.0 mL (5 mg / mL) mixed solution. The mixed solution was added to 10 mL of an aqueous solution containing 0.2 g CTAB, and the mixture was stirred vigorously to obtain a homogeneous oil-in-water microemulsion. The resulting microemulsion was heated at 65 °C for 20 min to evaporate the CHCl3, yielding an AgNR@CTAB solution.

[0139] Step 3: Dissolve 0.05 g CTAB in 86 mL of water at room temperature with stirring, and add NaOH (0.7 mL, 2 M). Then add the AgNR@CTAB solution obtained in Step 2, and heat the mixture to 60°C. While stirring vigorously, add 0.75 mL of TEOS to the reaction solution. After the addition is complete, allow the reaction to proceed for 2 h. After the reaction is complete, centrifuge at 10000 rpm for 5 min and collect the product.

[0140] Step 4: Extract with an ethanol solution containing ammonium nitrate (6 g / L) and reflux for 24 h to remove the template agent. After obtaining the sample, wash and dry it. The sample is labeled as AgNR@MSN.

[0141] Step 5: At room temperature, weigh 2 g of PLA powder (molecular weight 160,000) and dissolve it in 12 mL of DCM solution. Stir magnetically until completely dissolved and the solution becomes transparent. Simultaneously, add 0.6 g of AgNR@MSN powder to 8 mL of DMF solution and stir to disperse it evenly. After both solutions are evenly dispersed, mix them and continue stirring for 6 hours to prepare a co-spinning electrospinning solution.

[0142] Step 6: Inject the prepared electrospinning solution into two 5 mL syringes. After correctly installing the syringes and connecting the circuit, turn on the equipment. Specific electrospinning process parameters are set as follows: voltage 18 kV, feed rate 1 mL / h, distance between syringe needle and roller collector 15 cm. Spinning ambient temperature 25 ± 2℃, relative humidity 45 ± 2%. Label the collected electrospinned fiber membrane as 30%AgNR@MSN / PLA.

[0143] Step 7: Weigh 3.783 g of NaBH4 and dissolve it in 50 ml of 4°C deionized water to prepare a 2M NaBH4 solution. Weigh 150 mg of 30% AgNR@MSN / PLA fiber membrane, cut it into 1 mm × 1 mm fragments, and soak them in the NaBH4 solution for 30 min, stirring ultrasonically during the process to disperse and fluff the fiber membrane. Filter the mixed solution of fiber and sodium borohydride, and wash the fiber on the filter paper three times with deionized water to remove residual sodium borohydride. Then, freeze the washed fiber overnight at -80°C.

[0144] Step 8: At room temperature, measure 50 ml of deionized water, 49 ml of anhydrous ethanol, and 1 ml of acetic acid and mix them thoroughly. Add 0.5 g of chitosan and stir to dissolve, obtaining an electrophoresis buffer. Add the overnight frozen fiber membrane to the prepared electrophoresis buffer and sonicate to disperse it evenly in the electrophoresis buffer, obtaining a uniformly dispersed short fiber electrophoresis buffer.

[0145] Step 9: At room temperature, a 1cm wide stainless steel sheet is used as the anode, and a 1cm wide titanium sheet is used as the cathode. The distance between the anode and cathode is 1cm, and the length of each anode and cathode immersed in the electrophoretic solution is 2cm. Electrophoretic deposition is performed on the surface of the titanium sheet at a constant current of 0.03A for 3 minutes. After drying, a photothermal responsive multifunctional composite coating is obtained.

[0146] Example 4 differs from Example 2 only in the mass of the fibers in the electrophoresis solution.

[0147] Example 5

[0148] A method for preparing a photothermal responsive multifunctional composite coating includes the following steps:

[0149] Step 1: Prepare silver nanorods using the gold seed method described above;

[0150] Step 2: The prepared silver nanorods were dispersed in a chloroform (CHCl3) solution to prepare a 3.0 mL (5 mg / mL) mixed solution. The mixed solution was added to 10 mL of an aqueous solution containing 0.2 g CTAB, and the mixture was stirred vigorously to obtain a homogeneous oil-in-water microemulsion. The resulting microemulsion was heated at 65 °C for 20 min to evaporate the CHCl3, yielding an AgNR@CTAB solution.

[0151] Step 3: Dissolve 0.05 g CTAB in 86 mL of water at room temperature with stirring, and add NaOH (0.7 mL, 2 M). Then add the AgNR@CTAB solution obtained in Step 2, and heat the mixture to 60°C. While stirring vigorously, add 0.75 mL of TEOS to the reaction solution. After the addition is complete, allow the reaction to proceed for 2 h. After the reaction is complete, centrifuge at 10000 rpm for 5 min and collect the product.

[0152] Step 4: Extract with an ethanol solution containing ammonium nitrate (6 g / L) and reflux for 24 h to remove the template agent. After obtaining the sample, wash and dry it. The sample is labeled as AgNR@MSN.

[0153] Step 5: At room temperature, weigh 2 g of PLA powder (molecular weight 160,000) and dissolve it in 12 mL of DCM solution. Stir magnetically until completely dissolved and the solution becomes transparent. Simultaneously, add 0.4 g of AgNR@MSN powder to 8 mL of DMF solution and stir to disperse it evenly. After both solutions are evenly dispersed, mix them and continue stirring for 6 hours to prepare a co-spinning electrospinning solution.

[0154] Step 6: Inject the prepared electrospinning solution into two 5 mL syringes. After correctly installing the syringes and connecting the circuit, turn on the equipment. Specific electrospinning process parameters are set as follows: voltage 18 kV, feed rate 1 mL / h, distance between the syringe needle and the roller collector 15 cm. Spinning ambient temperature 25 ± 2℃, relative humidity 45 ± 2%. Label the collected electrospinned fiber membrane as 20%AgNR@MSN / PLA.

[0155] Step 7: Weigh 3.783 g of NaBH4 and dissolve it in 50 ml of 4°C deionized water to prepare a 2M NaBH4 solution. Weigh 150 mg of 20% AgNR@MSN / PLA fiber membrane, cut it into 1 mm × 1 mm fragments, and soak them in the NaBH4 solution for 30 min, stirring ultrasonically during the process to disperse and fluff the fiber membrane. Filter the mixed solution of fiber and sodium borohydride, and wash the fiber on the filter paper three times with deionized water to remove residual sodium borohydride. Then, freeze the washed fiber overnight at -80°C.

[0156] Step 8: At room temperature, measure 50 ml of deionized water, 49 ml of anhydrous ethanol, and 1 ml of acetic acid and mix them thoroughly. Add 0.5 g of chitosan and stir to dissolve, obtaining an electrophoresis buffer. Add the overnight frozen fiber membrane to the prepared electrophoresis buffer and sonicate to disperse it evenly in the electrophoresis buffer, obtaining a uniformly dispersed short fiber electrophoresis buffer.

[0157] Step 9: At room temperature, a 1cm wide stainless steel sheet is used as the anode, and a 1cm wide titanium sheet is used as the cathode. The distance between the anode and cathode is 1cm, and the length of each anode immersed in the electrophoretic solution is 2cm. Electrophoretic deposition is performed on the surface of the titanium sheet at a constant current of 0.02A for 3 minutes. After drying, a photothermal responsive multifunctional composite coating is obtained.

[0158] Example 5 differs from Example 3 only in the voltage and current of electrophoretic deposition.

[0159] Example 6

[0160] A method for preparing a photothermal responsive multifunctional composite coating includes the following steps:

[0161] Step 1: Prepare silver nanorods using the gold seed method described above;

[0162] Step 2: The prepared silver nanorods were dispersed in a chloroform (CHCl3) solution to prepare a 3.0 mL (5 mg / mL) mixed solution. The mixed solution was added to 10 mL of an aqueous solution containing 0.2 g CTAB, and the mixture was stirred vigorously to obtain a homogeneous oil-in-water microemulsion. The resulting microemulsion was heated at 65 °C for 20 min to evaporate the CHCl3, yielding an AgNR@CTAB solution.

[0163] Step 3: Dissolve 0.05 g CTAB in 86 mL of water at room temperature with stirring, and add NaOH (0.7 mL, 2 M). Then add the AgNR@CTAB solution obtained in Step 2, and heat the mixture to 60°C. While stirring vigorously, add 0.75 mL of TEOS to the reaction solution. After the addition is complete, allow the reaction to proceed for 2 h. After the reaction is complete, centrifuge at 10000 rpm for 5 min and collect the product.

[0164] Step 4: Extract with an ethanol solution containing ammonium nitrate (6 g / L) and reflux for 24 h to remove the template agent. After obtaining the sample, wash and dry it. The sample is labeled as AgNR@MSN.

[0165] Step 5: At room temperature, weigh 2 g of PLA powder (molecular weight 160,000) and dissolve it in 12 mL of DCM solution. Stir magnetically until completely dissolved and the solution becomes transparent. Simultaneously, add 0.4 g of AgNR@MSN powder to 8 mL of DMF solution and stir to disperse it evenly. After both solutions are evenly dispersed, mix them and continue stirring for 6 hours to prepare a co-spinning electrospinning solution.

[0166] Step 6: Inject the prepared electrospinning solution into two 5 mL syringes. After correctly installing the syringes and connecting the circuit, turn on the equipment. Specific electrospinning process parameters are set as follows: voltage 18 kV, feed rate 1 mL / h, distance between syringe needle and roller collector 15 cm. Spinning ambient temperature 25 ± 2℃, relative humidity 45 ± 2%. Label the collected electrospinned fiber membrane as 30%AgNR@MSN / PLA.

[0167] Step 7: Weigh 3.783 g of NaBH4 and dissolve it in 50 ml of 4°C deionized water to prepare a 2 M NaBH4 solution. Weigh 150 mg of 30% AgNR@MSN / PLA fiber membrane, cut it into 1 mm × 1 mm fragments, and soak them in the NaBH4 solution for 30 min, stirring ultrasonically during the process to disperse and fluff the fiber membrane. Filter the mixed solution of fiber and sodium borohydride, and wash the fiber on the filter paper three times with deionized water to remove residual sodium borohydride. Then, freeze the washed fiber overnight at -80°C.

[0168] Step 8: At room temperature, measure 50 ml of deionized water, 49 ml of anhydrous ethanol, and 1 ml of acetic acid and mix them thoroughly. Add 0.5 g of chitosan and stir to dissolve, obtaining an electrophoresis buffer. Add the overnight frozen fiber membrane to the prepared electrophoresis buffer and sonicate to disperse it evenly in the electrophoresis buffer, obtaining a uniformly dispersed short fiber electrophoresis buffer.

[0169] Step 9: At room temperature, a 1cm wide stainless steel sheet is used as the anode, and a 1cm wide titanium sheet is used as the cathode. The distance between the anode and cathode is 1cm, and the length of each anode immersed in the electrophoretic solution is 2cm. Electrophoretic deposition is performed on the surface of the titanium sheet at a constant current of 0.02A for 3 minutes. After drying, a photothermal responsive multifunctional composite coating is obtained.

[0170] Example 6 differs from Example 4 only in the voltage and current of electrophoretic deposition.

[0171] To illustrate the relevant properties of the composite material provided by this invention, see [link / reference]. Figures 1-7 As shown, an explanation will be provided.

[0172] Figure 1This is a scanning electron microscope (SEM) image of the AgNR@MSN / PLA fiber membrane described in Embodiment 1 of the present invention. From... Figure 1 As can be seen, the core-shell structured AgNR@MSN is uniformly dispersed in PLA fibers, and the fiber membrane successfully carries the photothermally responsive core-shell composite material. This invention realizes the preparation of an electrospun fiber membrane carrying a photothermally responsive core-shell composite material.

[0173] Figure 2 The image shown is a scanning electron microscope (SEM) image of the short fibers obtained by immersing the electrospun fiber membrane in sodium borohydride, freezing, and then thawing as described in Example 1. The SEM image shows that the electrospun short fibers prepared by this method are well dispersed and do not exhibit entanglement or aggregation. The method for preparing electrospun short fibers in this invention is simple and effective.

[0174] Figure 3 This is a cross-sectional scanning electron microscope image of the composite coating described in Example 1 of the present invention. The thickness of the composite coating obtained by the present invention is 8-10 μm.

[0175] Figure 4 These are scanning electron microscope (SEM) images of the surface morphology of the composite coatings described in Examples 1(a) and 3(b) of the present invention. Figure 4 As can be seen, the surface morphology of the coating can be changed by altering the content of the fiber membrane in the electrophoresis solution.

[0176] To illustrate the performance of the composite coating provided by this invention, the photothermal and antibacterial properties of the composite coating provided in Example 2 are tested, as shown below. Figure 5-6 As shown.

[0177] Figure 5 The photothermal performance of the composite coating provided in Example 2 was tested under irradiation with NIR light of different powers. The results show that near-infrared light can effectively promote the photothermal effect of the coating, and the temperature increases with the increase of NIR light irradiation power and irradiation time. The coating prepared by this invention has significant photothermal response performance.

[0178] In subsequent antibacterial performance experiments, the irradiation power and irradiation time of NIR near-infrared light were 2W / cm² and 3min.

[0179] Figure 6 and Figure 7 All results are test results of the antibacterial performance of the composite coating provided in Example 2. Figure 6 The composite coating showed inhibition zone tests against Staphylococcus aureus and Escherichia coli. Figure 7 The number of colonies after co-culturing Staphylococcus aureus and Escherichia coli with the composite coating shows that the composite coating has good antibacterial properties after being irradiated with NIR light.

[0180] This invention describes preferred embodiments and their effects. However, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to include both the preferred embodiments and all changes and modifications falling within the scope of this invention.

[0181] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A photothermal responsive multifunctional composite coating, characterized in that, The composite coating comprises an electrophoretic solution prepared with chitosan and electrospun short fibers, which is electrophoretically deposited onto a substrate to form a coating. The electrospun short fiber is obtained by electrospinning a spinning solution formulated with polylactic acid and a core-shell composite material, and then the spinning product is successively subjected to plasma treatment and fluffing treatment. The core-shell composite material is a composite material with a core-shell structure formed by silver nanorods as the core and mesoporous silica as the shell. The silver nanorods are encapsulated with gold bipyramidal seeds; The molar ratio of the silver nanorods to mesoporous silica is 1:3~7; The silver nanorods have a length of 60-150 nm and an aspect ratio of 3-5:

1. The thickness of the mesoporous silica shell is 10–80 nm; The plasma treatment involves placing the spinning product inside a plasma treatment machine, and after the vacuum level reaches the required level, turning on the plasma treatment machine to treat the sample with plasma for ten minutes. The fluffing treatment involves immersing the spun product in a sodium borohydride solution after plasma treatment to fluff it up. The concentration of the sodium borohydride solution is 1.5~3M; The core-shell structured composite material is prepared according to the following steps: Silver nanorods were prepared using the gold seed method; The prepared silver nanorods were dispersed in a chloroform solution and then added to an aqueous solution of CTAB to obtain a homogeneous oil-in-water microemulsion. The chloroform in the microemulsion was evaporated to obtain an AgNR@CTAB solution. AgNR@CTAB solution and tetraethyl orthosilicate solution are added to an alkaline aqueous solution containing CTAB. After the reaction is complete, a core-shell composite material is obtained.

2. The photothermal responsive multifunctional composite coating according to claim 1, characterized in that, The composite coating is capable of photothermal conversion of near-infrared light with wavelengths of 780–850 nm.

3. The photothermal responsive multifunctional composite coating according to claim 1, characterized in that, The coating, which is deposited on the substrate by electrophoretic deposition, has a thickness of 5-20 μm.

4. A method for preparing a photothermal responsive multifunctional composite coating according to any one of claims 1 to 3, characterized in that, Includes the following steps: The electrospun short fibers were frozen at -85~-75℃ for 24~48h; A certain amount of deionized water, anhydrous ethanol, chitosan, and acetic acid are mixed evenly to obtain an electrophoresis solution. The frozen electrospun short fibers are uniformly dispersed in the electrophoresis solution to obtain the short fiber electrophoresis solution; In a short fiber electrophoresis solution, a stainless steel sheet is used as the anode and a titanium substrate is used as the cathode. A photothermal responsive multifunctional composite coating is prepared on the surface of the titanium sheet by electrophoretic deposition.

5. The method for preparing the photothermal responsive multifunctional composite coating according to claim 4, characterized in that, The ratio of deionized water, anhydrous ethanol, and acetic acid is 10~89:10~89:1; The concentration of electrospun short fibers in the short fiber electrophoresis solution is 0.5~5 mg / mL; the concentration of chitosan in the short fiber electrophoresis solution is 0.5~5 mg / mL.

6. The application of the photothermal responsive multifunctional composite coating according to any one of claims 1 to 3 in bone implant matrix.

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