Hydroxyapatite super-long nanowire / poly(methyl methacrylate) composite bone cement, and preparation method and application thereof

Abstract

The application relates to a hydroxyapatite super-long nanowire / polymethyl methacrylate composite bone cement as well as a preparation method and application thereof. The hydroxyapatite super-long nanowire / polymethyl methacrylate composite bone cement comprises two parts of a powder and a liquid; the powder is composed of modified hydroxyapatite super-long nanowires, polymethyl methacrylate and an initiator; the liquid is composed of methyl methacrylate and a curing accelerator; and the modified hydroxyapatite super-long nanowires are hydroxyapatite super-long nanowires modified by an antibacterial agent and acrylated pamidronate disodium in sequence. The composite bone cement provided by the application not only has low curing heat effect, excellent mechanical properties and good biological activity, but also has long-term antibacterial performance, so that infection of a bone defect part is avoided.

Description

Technical Field

[0001] This invention belongs to the field of biomedical material preparation and application, and relates to a hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement, its preparation method and application. Background Technology

[0002] With an aging population, fractures, bone defects, and osteoporosis have become significant public health challenges. For example, patients with osteoporosis are prone to fragility fractures, with vertebral compression fractures (OVCFs) being particularly common and prevalent in the elderly and postmenopausal women. Bone cement, a commonly used repair material in orthopedic surgery, is implanted or injected into bone defects to promote rapid repair.

[0003] Polymethyl methacrylate (PMMA) bone cement has been widely used in orthopedic surgeries, including total hip / knee replacement, treatment of vertebral compression fractures, and bone defect filling. PMMA bone cement offers advantages such as short curing time, high plasticity, high support strength, low cost, significant pain relief, and the ability to allow patients to ambulate early. However, PMMA bone cement also has some drawbacks, such as excessively high curing temperatures that can cause thermal damage or even necrosis of surrounding normal tissues, nerves, and blood vessels; its bioinertness, lack of activity in inducing new bone formation, and poor biocompatibility with surrounding bone tissue; and its excessively high elastic modulus, which can cause stress concentration in the vertebral body and increase the incidence of adjacent vertebral fractures. Researchers have conducted modification studies on PMMA bone cement. For example, Yin Jun et al. reported a composite bone cement of sodium alginate and polyethyleneimine modified hydroxyapatite, hydroxyapatite modified with hydroxyl functionalized drugs, and PMMA (application number 202310204560.8); Yang Dicheng et al. reported a PMMA bone cement modified with porous hydroxyapatite microspheres (application number 202311741934.6); and Shao Gaohai et al. reported a composite PMMA bone cement of calcium phosphate and mesoporous bioglass (application number 202511206813.0). Although these methods can improve the bioactivity of PMMA bone cement to some extent, the inorganic components that provide bioactivity are combined with PMMA through mechanical mixing. The interfacial bonding force between the inorganic components and PMMA is weak, resulting in poor overall mechanical properties of the organic-inorganic composite bone cement, and the inorganic components are prone to disintegration in the body fluid environment.

[0004] To treat infected bone defects, antibiotics are typically incorporated into PMMA bone cement to create antibiotic-loaded bone cement. However, antibiotic-loaded PMMA bone cement releases antibiotics explosively in a short period, followed by very low release levels, limiting its use. Therefore, there is an urgent need to develop a bone cement material with low thermosetting effect, excellent mechanical properties, good bioactivity, and long-lasting antibacterial activity. Summary of the Invention

[0005] To address the key issues of high curing temperature, high elastic modulus, lack of osteogenic activity, and lack of antibacterial activity in polymethyl methacrylate (PMMA) bone cement, this invention provides a hydroxyapatite ultralong nanowire / PMMA composite bone cement, its preparation method, and its applications. This composite bone cement exhibits low curing heat effect, excellent mechanical properties, good bioactivity, and long-lasting antibacterial properties, preventing infection at bone defect sites.

[0006] In a first aspect, the present invention provides a hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement, comprising two parts: a powder and a liquid; the powder is composed of modified hydroxyapatite ultralong nanowires, polymethyl methacrylate, and an initiator; the liquid is composed of methyl methacrylate and a curing accelerator; the modified hydroxyapatite ultralong nanowires are hydroxyapatite ultralong nanowires modified sequentially with an antibacterial agent and disodium pamidronate acrylate.

[0007] Preferably, the modified hydroxyapatite ultralong nanowires have a length of 10–1000 micrometers, a diameter of 10–100 nanometers, and an aspect ratio greater than 100.

[0008] Preferably, the modified hydroxyapatite ultralong nanowires in the powder contain 0.1% to 70% by mass, more preferably 10% to 50% by mass, the polymethyl methacrylate contains 29.8% to 99.7% by mass, and the initiator contains 0.2% to 2% by mass.

[0009] Preferably, the content of the curing accelerator in the liquid is 1 to 5% by mass percentage.

[0010] Preferably, the mass-to-volume ratio of the powder to the liquid is (1.0–4.0) g: 1 mL, and more preferably (1.5–3.0) g: 1 mL.

[0011] Preferably, the antibacterial agent includes at least one of nano-copper, nano-silver, zinc oxide, gentamicin, vancomycin, ciprofloxacin, chlorhexidine hydrochloride, chitosan, carboxymethyl chitosan, and antimicrobial peptides.

[0012] Preferably, when the antibacterial agent is at least one of nano-copper, nano-silver, and zinc oxide, the antibacterial agent formation process is as follows: copper ions, silver ions, and zinc ions are loaded onto the surface of hydroxyapatite ultralong nanowires through ion exchange, reduction / precipitation methods. When the antibacterial agent is at least one of gentamicin, vancomycin, ciprofloxacin, chlorhexidine hydrochloride, chitosan, carboxymethyl chitosan, and antimicrobial peptide, the antibacterial agent is loaded onto the surface of hydroxyapatite ultralong nanowires through an electrostatic adsorption process.

[0013] Preferably, the disodium pamidronate acrylate is loaded onto the surface of hydroxyapatite ultralong nanowires via an electrostatic adsorption process.

[0014] Preferably, the initiator is selected from at least one of benzoyl peroxide, lauroyl peroxide, and dimethyl azobisisobutyrate.

[0015] Preferably, the curing accelerator is selected from at least one of N,N-dimethyl-p-toluidine, N,N-dimethylaniline, and N-methyl-N-2-hydroxyethyl-p-toluidine.

[0016] Secondly, the present invention provides a method for preparing the above-mentioned hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement, comprising the following steps: mixing modified hydroxyapatite ultralong nanowires, polymethyl methacrylate and an initiator to obtain a solid powder; subsequently adding a mixed liquid containing a curing accelerator and methyl methacrylate to the mixture, stirring to obtain a mixture; filling the obtained mixture into a mold for curing and molding, and obtaining the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement after demolding.

[0017] Preferably, the modified hydroxyapatite ultralong nanowires account for 0.1% to 70% of the mass of the solid powder, more preferably 10% to 50%.

[0018] Preferably, the solid-liquid ratio of the solid powder to the mixed liquid is (1.0-4.0) g: 1 mL, more preferably (1.5-3.0) g: 1 mL.

[0019] Preferably, the antibacterial agent is at least one of nano-copper, nano-silver, and zinc oxide; the preparation method of the modified hydroxyapatite ultralong nanowires includes: (1) When the antibacterial agent is at least one of nano copper and nano silver, hydroxyapatite ultralong nanowires are mixed with an aqueous solution containing copper ions or silver ions, and a reducing agent is added to reduce the copper ions or silver ions. The resulting nano copper or nano silver is loaded on the surface of the hydroxyapatite ultralong nanowires. After centrifugation and washing, antibacterial agent modified hydroxyapatite ultralong nanowires are obtained. When the antibacterial agent is zinc oxide, hydroxyapatite ultralong nanowires are mixed with an aqueous solution containing zinc ions, and an alkaline substance is added to cause the zinc ions to precipitate. The resulting zinc oxide is loaded onto the surface of the hydroxyapatite ultralong nanowires. After centrifugation and washing, antibacterial agent modified hydroxyapatite ultralong nanowires are obtained. (2) Disperse the antibacterial agent-modified hydroxyapatite ultralong nanowires and disodium pamidronate acrylate in deionized water, adjust the pH to neutral, and then stir, centrifuge, wash and dry to obtain the antibacterial agent and disodium pamidronate acrylate-modified hydroxyapatite ultralong nanowires.

[0020] Preferably, the antibacterial agent is at least one of gentamicin, vancomycin, ciprofloxacin, chlorhexidine hydrochloride, chitosan, carboxymethyl chitosan, and antimicrobial peptides; The method for preparing the modified hydroxyapatite ultralong nanowires includes: dispersing hydroxyapatite ultralong nanowires with an antibacterial agent and disodium pamidronate acrylate in deionized water, adjusting the pH to neutral, and then stirring, centrifuging, washing, and drying to obtain hydroxyapatite ultralong nanowires modified with the antibacterial agent and disodium pamidronate acrylate.

[0021] Preferably, the mass ratio of the antibacterial agent to the hydroxyapatite ultralong nanowires is (0.001-1):1, more preferably (0.005-0.5):1; the mass ratio of the disodium pamidronate acrylate to the hydroxyapatite ultralong nanowires is (0.01-1):1, more preferably (0.1-0.6):1.

[0022] Thirdly, the present invention provides an application of the above-mentioned hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement in the preparation of bone defect repair materials, osteoporosis treatment materials, and bone-related disease treatment materials. Beneficial effects

[0023] (1) In the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement of the present invention, the acrylic groups on the surface of the modified hydroxyapatite ultralong nanowire undergo a polymerization reaction with the methyl methacrylate monomer, and the hydroxyapatite ultralong nanowire forms a stable organic-inorganic interface bond with the polymethyl methacrylate. The hydroxyapatite ultralong nanowire is assembled and interwoven to form a three-dimensional network structure, forming a structure similar to "reinforced concrete", which significantly improves the mechanical properties and structural stability of the composite bone cement, and effectively solves the key problem of poor mechanical properties of traditional PMMA bone cement after adding high content of inorganic components; (2) In the hydroxyapatite ultra-long nanowire / polymethyl methacrylate composite bone cement of the present invention, the modified hydroxyapatite ultra-long nanowire has a high mass ratio, which effectively reduces the mass ratio of polymethyl methacrylate and can significantly reduce the curing temperature, thus effectively solving the key problem of high curing temperature of traditional PMMA bone cement. (3) In the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement of the present invention, each functional component can effectively promote bone defect repair, bone regeneration and prevent bacterial infection through a multi-level synergistic mechanism: hydroxyapatite ultralong nanowire slowly releases calcium ions and phosphate ions, which have excellent biocompatibility, osteoconduction and osteoinduction activities, and can promote the adhesion, proliferation and differentiation of bone marrow mesenchymal stem cells and improve osteogenic performance; the antibacterial agent stably loaded on the hydroxyapatite ultralong nanowire can slowly release antibacterial components (copper ions, silver ions, zinc ions, gentamicin, vancomycin, etc.) for a long time, which have long-lasting antibacterial activity and can effectively fight bacteria or prevent bacterial infection. Attached Figure Description

[0024] Figure 1 (a) is a schematic diagram of the modification of hydroxyapatite ultralong nanowires using antibacterial agents and disodium pamidronate acrylate in this invention; Figure 1 (b) is a flowchart of the preparation process of hydroxyapatite ultralong nanowires / polymethyl methacrylate composite bone cement in this invention; Figure 2 Digital photographs of hydroxyapatite ultralong nanowires / polymethyl methacrylate composite bone cement prepared using different molds in Example 1 of this invention; Figure 3 This refers to the highest curing temperature of the samples prepared in Examples 1-6 and Comparative Examples 1-6 of this invention; Figure 4 The curing time refers to the time of the samples prepared in Examples 1-6 and Comparative Examples 1-6 of this invention. Figure 5 The compressive strength and elastic modulus of the samples prepared in Examples 1-6 and Comparative Examples 1-6 of this invention; Figure 6 The flexural strength and elastic modulus of the samples prepared in Examples 1-6 and Comparative Examples 1-6 of this invention; Figure 7 The growth of samples prepared in Examples 1-5 and Comparative Example 1 of this invention, after being cultured in liquid culture medium with Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus, was measured by coating a portion of the liquid onto a solid culture medium. Detailed Implementation

[0025] To further illustrate the invention's content, features, and practical effects, the invention will be described in detail below with reference to embodiments. It should be noted that the modification methods of the invention are not limited to these specific implementation methods. Equivalent substitutions and modifications made by those skilled in the art based on their reading of the invention, without departing from its spirit and essence, are also within the scope of protection claimed by the invention. Unless otherwise specified, percentage content refers to mass percentage content.

[0026] First, this invention provides a hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement, comprising two parts: a powder and a liquid. The powder consists of modified hydroxyapatite ultralong nanowires, polymethyl methacrylate, and an initiator. The liquid consists of methyl methacrylate and a curing accelerator. The modified hydroxyapatite ultralong nanowires are hydroxyapatite ultralong nanowires modified sequentially with an antibacterial agent and disodium pamidronate acrylate (e.g., ...). Figure 1 (a) shows the antibacterial agent. The antibacterial agent includes at least one of the following: nano copper, nano silver, zinc oxide, gentamicin, vancomycin, ciprofloxacin, chlorhexidine hydrochloride, chitosan, carboxymethyl chitosan, and antimicrobial peptides.

[0027] In an optional embodiment, the modified hydroxyapatite ultralong nanowires have a length of 10–1000 micrometers, a diameter of 10–100 nanometers, and an aspect ratio greater than 100. By mass percentage, the modified hydroxyapatite ultralong nanowires in the powder comprise 0.1–70%, preferably 10–50%, the polymethyl methacrylate comprises 29.8–99.7%, and the initiator comprises 0.2–2%. Excessive content of the modified hydroxyapatite ultralong nanowires in the powder will increase porosity in the composite bone cement, reducing its mechanical properties.

[0028] In an optional embodiment, the initiator is selected from at least one of benzoyl peroxide, lauroyl peroxide, and dimethyl azobisisobutyrate.

[0029] In an optional embodiment, the curing accelerator is selected from at least one of N,N-dimethyl-p-toluidine, N,N-dimethylaniline, and N-methyl-N-2-hydroxyethyl-p-toluidine. The content of the curing accelerator in the liquid is 1-5% by mass percentage.

[0030] In this invention, hydroxyapatite ultralong nanowires are first modified using an antibacterial agent and disodium pamidronate acrylate. When the antibacterial agent is at least one of nano-copper, nano-silver, or zinc oxide, the antibacterial agent is formed by loading copper, silver, and zinc ions onto the surface of the hydroxyapatite ultralong nanowires via ion exchange and reduction / precipitation. When the antibacterial agent is at least one of gentamicin, vancomycin, ciprofloxacin, chlorhexidine hydrochloride, chitosan, carboxymethyl chitosan, or antimicrobial peptides, the antibacterial agent is loaded onto the surface of the hydroxyapatite ultralong nanowires via electrostatic adsorption. Disodium pamidronate acrylate is loaded onto the surface of the hydroxyapatite ultralong nanowires via electrostatic adsorption. The acrylic groups modified on the surface of the hydroxyapatite ultralong nanowires undergo a thermal polymerization reaction with polymethyl methacrylate under the action of an initiator and a curing accelerator, forming a stable organic-inorganic interfacial bond between the hydroxyapatite ultralong nanowires and polymethyl methacrylate. On the one hand, hydroxyapatite ultralong nanowires possess a high aspect ratio, forming abundant organic-inorganic interface binding sites with polymethyl methacrylate (PMMA), thus constructing a robust organic-inorganic network structure. The hydroxyapatite ultralong nanowires assemble and interweave to form a three-dimensional network structure, forming a "reinforced concrete" structure with PMMA (such as...). Figure 1 (b) As shown, the composite of high-content hydroxyapatite ultralong nanowires maintains good mechanical properties, meeting the mechanical performance requirements of composite bone cement. Furthermore, hydroxyapatite has a higher thermal conductivity than polymethyl methacrylate (PMMA), effectively transferring the heat generated by the polymerization reaction to the surface and dissipating it promptly, achieving a lower thermosetting effect and reducing thermal damage to biological tissues. The antibacterial agent stably loaded on the surface of the modified hydroxyapatite ultralong nanowires is released slowly, significantly prolonging the release time and providing long-lasting antibacterial efficacy, effectively preventing bacterial infection. In addition, the slow release of calcium and phosphate ions from the hydroxyapatite ultralong nanowires promotes the adhesion, proliferation, and differentiation of bone marrow mesenchymal stem cells, improving the osteoconductivity, osteoinduction, and osteogenic properties of the composite bone cement, thus promoting bone defect repair and functional recovery.

[0031] The key technical challenges in preparing hydroxyapatite ultralong nanowire / polymethyl methacrylate (PMMA) composite bone cement according to this invention include: the interfacial bonding between hydroxyapatite ultralong nanowires and PMMA, and the loading and release of antibacterial agents. This invention modifies hydroxyapatite ultralong nanowires with disodium pamidronate acrylate, subsequently forming a stable organic-inorganic interfacial bond with PMMA, overcoming the problem of weak interfacial bonding. Antibacterial agents are stably loaded onto the surface of the hydroxyapatite ultralong nanowires using methods such as ion exchange, reduction / precipitation, and electrostatic adsorption, enabling the hydroxyapatite ultralong nanowire / PMMA composite bone cement to exhibit slow-release antibacterial agent properties, overcoming the problem of explosive antibacterial agent release.

[0032] The following exemplarily illustrates the preparation method of the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement provided by the present invention (e.g. Figure 1 (b) shown).

[0033] Preparation of hydroxyapatite ultralong nanowires. In this invention, hydroxyapatite ultralong nanowires are prepared using a solvothermal method or a hydrothermal method with calcium oleate precursors. Methods reported in published patents and literature can be referenced, such as: Zhu Yingjie, Lu Bingqiang, Chen Feng, High-flexibility, high-temperature resistant, non-flammable hydroxyapatite paper and its preparation method, patent number ZL201310687363.2; Ceramics International, 41, 6098-6102 (2015); Materials Letters, 144, 135-137 (2015). Other suitable preparation methods can also be used, as long as the method can produce the aforementioned hydroxyapatite ultralong nanowires.

[0034] Preparation of disodium pamidronate acrylate. As an example, 8.37 g of disodium pamidronate and 12.56 g of N-acryloyloxysuccinimide were added to 50 mL of deionized water. The pH of the mixture was adjusted to 8.0 using an aqueous sodium hydroxide solution. After stirring at room temperature for 24 hours, cold ethanol was added to precipitate the mixture. The precipitate was washed with cold ethanol, the product was collected, and dried at 50 °C to obtain disodium pamidronate acrylate.

[0035] Hydroxyapatite ultralong nanowires were modified sequentially using an antibacterial agent and disodium pamidronate acrylate. It is important to note that the modification order of these two agents cannot be reversed. If disodium pamidronate acrylate is modified first, followed by the antibacterial agent modification, the loading of disodium pamidronate acrylate on the surface of the hydroxyapatite ultralong nanowires will be reduced, further affecting the mechanical properties of the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement. Therefore, this invention uses an antibacterial agent and disodium pamidronate acrylate sequentially to modify the hydroxyapatite ultralong nanowires, ensuring that disodium pamidronate acrylate is stably loaded on the surface of the hydroxyapatite ultralong nanowires and achieving excellent mechanical properties.

[0036] In an optional embodiment, the antibacterial agent includes at least one selected from nano-copper, nano-silver, zinc oxide, gentamicin, vancomycin, ciprofloxacin, chlorhexidine hydrochloride, chitosan, carboxymethyl chitosan, and antimicrobial peptides. The mass ratio of the antibacterial agent to the hydroxyapatite ultralong nanowires is (0.001–1):1, preferably (0.005–0.5):1; the mass ratio of disodium pamidronate acrylate to the hydroxyapatite ultralong nanowires is (0.01–1):1, preferably (0.1–0.6):1. The antibacterial agent and disodium pamidronate acrylate are stably loaded onto the surface of the hydroxyapatite ultralong nanowires through methods such as ion exchange, reduction / precipitation, and electrostatic adsorption. When the antibacterial agent is at least one of nano-copper, nano-silver, and zinc oxide, the preparation method of the modified hydroxyapatite ultralong nanowires includes: (1) mixing hydroxyapatite ultralong nanowires with an aqueous solution containing copper or silver ions, adding a reducing agent to reduce the copper or silver ions, and the resulting nano-copper or nano-silver is loaded on the surface of the hydroxyapatite ultralong nanowires. After centrifugation and washing, antibacterial agent modified hydroxyapatite ultralong nanowires are obtained; mixing hydroxyapatite ultralong nanowires with an aqueous solution containing zinc ions, adding an alkaline substance to cause the zinc ions to precipitate, and the resulting zinc oxide is loaded on the surface of the hydroxyapatite ultralong nanowires. After centrifugation and washing, antibacterial agent modified hydroxyapatite ultralong nanowires are obtained; (2) dispersing the antibacterial agent modified hydroxyapatite ultralong nanowires and disodium pamidronate acrylate in deionized water, adjusting the pH to neutral, stirring, centrifuging, washing, and drying, to obtain antibacterial agent and disodium pamidronate acrylate modified hydroxyapatite ultralong nanowires. When the antibacterial agent is at least one of gentamicin, vancomycin, ciprofloxacin, chlorhexidine hydrochloride, chitosan, carboxymethyl chitosan, and antimicrobial peptide, the preparation method of the modified hydroxyapatite ultralong nanowires includes: dispersing hydroxyapatite ultralong nanowires with the antibacterial agent and disodium pamidronate acrylate in deionized water, adjusting the pH to neutral, and then stirring, centrifuging, washing, and drying to obtain hydroxyapatite ultralong nanowires modified with the antibacterial agent and disodium pamidronate acrylate.

[0037] Modified hydroxyapatite ultralong nanowires, polymethyl methacrylate, and an antibacterial agent are mixed to obtain a solid powder. Then, a liquid containing a curing accelerator and methyl methacrylate is added to it and stirred to obtain a mixture. The resulting mixture is filled into a mold and cured. After demolding, the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement is obtained.

[0038] In an optional embodiment, the modified hydroxyapatite ultralong nanowires account for 0.1% to 70% of the mass of the solid powder, preferably 10% to 50%.

[0039] In an optional embodiment, the solid-liquid ratio of the solid powder to the liquid is (1.0-4.0) g: 1 mL, preferably (1.5-3.0) g: 1 mL.

[0040] Furthermore, the present invention also provides the application of the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement prepared above, wherein the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement is used in the preparation of biomedical materials for bone defect repair, osteoporosis treatment, osteomyelitis treatment, etc.

[0041] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below. Example 1

[0042] One gram of hydroxyapatite ultralong nanowires and 42.6 milligrams of copper chloride dihydrate were dispersed in 150 mL of deionized water and stirred at room temperature for 2 hours. Then, 1 mL of an aqueous solution containing 100 milligrams of polyvinylpyrrolidone and 1 mL of an aqueous solution containing 20 milligrams of sodium borohydride were added sequentially, and the mixture was stirred at room temperature for 20 minutes. After centrifugation, the nanowires were washed with deionized water to obtain copper-modified hydroxyapatite ultralong nanowires (the mass ratio of copper nanowires to hydroxyapatite ultralong nanowires was 0.0152:1). One gram of copper-modified hydroxyapatite ultralong nanowires and 0.3 grams of disodium pamidronate acrylate were added to 200 mL of water. The pH of the mixed solution was adjusted to 7.0 using dilute hydrochloric acid, and the mixture was stirred at room temperature for 24 hours. After centrifugation, the nanowires were washed with deionized water and freeze-dried to obtain copper nanowires and disodium pamidronate acrylate-modified hydroxyapatite ultralong nanowires. 0.6 g of nano-copper and hydroxyapatite ultralong nanowires modified with disodium pamidronate acrylate, 1.4 g of polymethyl methacrylate, and 14 mg of benzoyl peroxide powder were mixed. 1 mL of a mixture of methyl methacrylate and N,N-dimethyl-p-toluidine was added and stirred until homogeneous. The resulting mixture was filled into a mold and cured. After demolding, the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement was obtained. Example 2

[0043] 1 gram of hydroxyapatite ultralong nanowires and 17.0 mg of silver nitrate were dispersed in 150 mL of deionized water and stirred at room temperature for 2 hours. Then, 1 mL of an aqueous solution containing 10 mg of sodium borohydride was added, and the mixture was stirred at room temperature for 20 minutes. After centrifugation, the nanowires were washed with deionized water to obtain silver-modified hydroxyapatite ultralong nanowires (the mass ratio of silver nanowires to hydroxyapatite ultralong nanowires was 0.0101:1). 1 gram of silver-modified hydroxyapatite ultralong nanowires and 0.3 gram of disodium pamidronate acrylate were added to 200 mL of water. The pH of the mixed solution was adjusted to 7.0 using dilute hydrochloric acid, and the mixture was stirred at room temperature for 24 hours. After centrifugation, the nanowires were washed with deionized water and freeze-dried to obtain silver nanowires and disodium pamidronate acrylate-modified hydroxyapatite ultralong nanowires. 0.6 g of nano-silver and hydroxyapatite ultralong nanowires modified with disodium pamidronate acrylate, 1.4 g of polymethyl methacrylate, and 14 mg of benzoyl peroxide powder were mixed. 1 mL of a mixture of methyl methacrylate and N,N-dimethyl-p-toluidine was added and stirred until homogeneous. The resulting mixture was filled into a mold and cured. After demolding, the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement was obtained. Example 3

[0044] One gram of hydroxyapatite ultralong nanowires and 68.2 milligrams of zinc chloride were dispersed in 150 mL of deionized water and stirred at room temperature for 2 hours. The pH of the mixture was adjusted to 10.0 using sodium hydroxide, followed by stirring at 60 °C for 3 hours. After centrifugation, the nanowires were washed with deionized water to obtain zinc oxide-modified hydroxyapatite ultralong nanowires (the mass ratio of zinc oxide to hydroxyapatite ultralong nanowires was 0.0351:1). One gram of zinc oxide-modified hydroxyapatite ultralong nanowires and 0.3 grams of disodium pamidronate acrylate were added to 200 mL of water. The pH of the mixture was adjusted to 7.0 using dilute hydrochloric acid solution, stirred at room temperature for 24 hours, centrifuged, washed with deionized water, and freeze-dried to obtain zinc oxide and disodium pamidronate acrylate-modified hydroxyapatite ultralong nanowires. 0.6 g of zinc oxide and hydroxyapatite ultralong nanowires modified with disodium pamidronate acrylate, 1.4 g of polymethyl methacrylate, and 14 mg of benzoyl peroxide powder were mixed. 1.0 mL of a mixture of methyl methacrylate and N,N-dimethyl-p-toluidine was added and stirred until homogeneous. The resulting mixture was filled into a mold and cured. After demolding, the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement was obtained. Example 4

[0045] One gram of hydroxyapatite ultralong nanowires, 0.2 grams of gentamicin sulfate, and 0.3 grams of disodium pamidronate acrylate were dispersed in 150 ml of deionized water and stirred at room temperature for 24 hours. The mixture was then centrifuged, washed with deionized water, and freeze-dried to obtain hydroxyapatite ultralong nanowires modified with gentamicin and disodium pamidronate acrylate. Another mixture of 0.6 grams of the hydroxyapatite ultralong nanowires modified with gentamicin and disodium pamidronate acrylate, 1.4 grams of polymethyl methacrylate, and 14 mg of benzoyl peroxide powder was added. One ml of a mixture of methyl methacrylate and N,N-dimethyl-p-toluidine was added and stirred until homogeneous. The resulting mixture was then filled into a mold and cured. After demolding, the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement was obtained. Example 5

[0046] One gram of hydroxyapatite ultralong nanowires, 0.2 grams of vancomycin hydrochloride, and 0.3 grams of disodium pamidronate acrylate were dispersed in 150 ml of deionized water and stirred at room temperature for 24 hours. The mixture was then centrifuged, washed with deionized water, and freeze-dried to obtain vancomycin- and disodium pamidronate acrylate-modified hydroxyapatite ultralong nanowires. Another mixture of 0.6 grams of vancomycin- and disodium pamidronate acrylate-modified hydroxyapatite ultralong nanowires, 1.4 grams of polymethyl methacrylate, and 14 mg of benzoyl peroxide powder was added. One ml of a mixture of methyl methacrylate and N,N-dimethyl-p-toluidine was added and stirred until homogeneous. The resulting mixture was then filled into a mold and cured. After demolding, the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement was obtained. Example 6

[0047] One gram of hydroxyapatite ultralong nanowires and 42.6 milligrams of copper chloride dihydrate were dispersed in 150 mL of deionized water and stirred at room temperature for 2 hours. Then, 1 mL of an aqueous solution containing 100 milligrams of polyvinylpyrrolidone and 1 mL of an aqueous solution containing 20 milligrams of sodium borohydride were added sequentially, and the mixture was stirred at room temperature for 20 minutes. After centrifugation, the nanowires were washed with deionized water to obtain copper-modified hydroxyapatite ultralong nanowires (the mass ratio of copper nanowires to hydroxyapatite ultralong nanowires was 0.0152:1). One gram of copper-modified hydroxyapatite ultralong nanowires and 0.3 grams of disodium pamidronate acrylate were added to 200 mL of water. The pH of the mixed solution was adjusted to 7.0 using dilute hydrochloric acid, and the mixture was stirred at room temperature for 24 hours. After centrifugation, the nanowires were washed with deionized water and freeze-dried to obtain copper nanowires and disodium pamidronate acrylate-modified hydroxyapatite ultralong nanowires. The above process was repeated twice. 1.2 g of nano-copper and hydroxyapatite ultralong nanowires modified with disodium pamidronate acrylate, 0.8 g of polymethyl methacrylate, and 14 mg of benzoyl peroxide powder were mixed. 1 mL of a mixture of methyl methacrylate and N,N-dimethyl-p-toluidine was added and stirred until homogeneous. The resulting mixture was filled into a mold and cured. After demolding, the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement was obtained. Comparative Example 1

[0048] One gram of hydroxyapatite ultralong nanowires and 0.3 grams of disodium pamidronate acrylate were added to 150 ml of deionized water. The pH was adjusted to 7.0 using dilute hydrochloric acid, and the mixture was stirred at room temperature for 24 hours. After centrifugation, the nanowires were washed with deionized water and freeze-dried to obtain hydroxyapatite ultralong nanowires modified with disodium pamidronate acrylate. 0.6 grams of the hydroxyapatite ultralong nanowires modified with disodium pamidronate acrylate, 1.4 grams of polymethyl methacrylate, and 14 mg of benzoyl peroxide powder were mixed. One ml of a mixture of methyl methacrylate and N,N-dimethyl-p-toluidine was added and stirred until homogeneous. The resulting mixture was filled into a mold and cured. After demolding, the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement was obtained. Comparative Example 2

[0049] One gram of hydroxyapatite ultralong nanowires and 42.6 milligrams of copper chloride dihydrate were dispersed in 150 ml of deionized water and stirred at room temperature for 2 hours. Then, 1 ml of an aqueous solution containing 100 milligrams of polyvinylpyrrolidone and 1 ml of an aqueous solution containing 20 milligrams of sodium borohydride were added sequentially, and the mixture was stirred at room temperature for 20 minutes. After centrifugation and washing with deionized water, copper-modified hydroxyapatite ultralong nanowires were obtained (the mass ratio of copper nanowires to hydroxyapatite ultralong nanowires was 0.0152:1). 0.6 grams of copper-modified hydroxyapatite ultralong nanowires, 1.4 grams of polymethyl methacrylate, and 14 milligrams of benzoyl peroxide powder were mixed. One ml of a mixture of methyl methacrylate and N,N-dimethyl-p-toluidine was added and stirred until homogeneous. The resulting mixture was filled into a mold and cured. After demolding, the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement was obtained. Comparative Example 3

[0050] 0.6 g of hydroxyapatite ultralong nanowires and 1.4 g of polymethyl methacrylate were mixed with 14 mg of benzoyl peroxide powder. 1 ml of a mixture of methyl methacrylate and N,N-dimethyl-p-toluidine was added and stirred until homogeneous. The resulting mixture was then filled into a mold and cured. After demolding, the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement was obtained. Comparative Example 4

[0051] Mix 2 grams of polymethyl methacrylate with 14 milligrams of benzoyl peroxide powder and 1 milliliter of methyl methacrylate with N,N-dimethyl-p-toluidine liquid and stir until homogeneous. Fill the resulting mixture into a mold and cure it. After demolding, polymethyl methacrylate bone cement is obtained. Comparative Example 5

[0052] One gram of hydroxyapatite ultralong nanowires and 0.3 grams of disodium pamidronate acrylate were added to 200 mL of water. The pH of the mixture was adjusted to 7.0 using dilute hydrochloric acid. The mixture was stirred at room temperature for 24 hours, centrifuged, washed with deionized water, and freeze-dried to obtain hydroxyapatite ultralong nanowires modified with disodium pamidronate acrylate. Another gram of hydroxyapatite ultralong nanowires modified with disodium pamidronate acrylate and 42.6 mg of copper chloride dihydrate were dispersed in 150 mL of deionized water. The mixture was stirred at room temperature for 2 hours. Then, 1 mL of an aqueous solution containing 100 mg of polyvinylpyrrolidone and 1 mL of an aqueous solution containing 20 mg of sodium borohydride were added sequentially. The mixture was stirred at room temperature for 20 minutes, centrifuged, and washed with deionized water to obtain hydroxyapatite ultralong nanowires modified with disodium pamidronate acrylate and copper nanoparticles. 0.6 g of hydroxyapatite ultralong nanowires modified with disodium pamidronate acrylate and nano-copper, 1.4 g of polymethyl methacrylate, and 14 mg of benzoyl peroxide powder were mixed. 1 mL of a mixture of methyl methacrylate and N,N-dimethyl-p-toluidine was added and stirred until homogeneous. The resulting mixture was filled into a mold and cured. After demolding, the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement was obtained. Comparative Example 6

[0053] One gram of hydroxyapatite ultralong nanowires and 42.6 milligrams of copper chloride dihydrate were dispersed in 150 mL of deionized water and stirred at room temperature for 2 hours. Then, 1 mL of an aqueous solution containing 100 milligrams of polyvinylpyrrolidone and 1 mL of an aqueous solution containing 20 milligrams of sodium borohydride were added sequentially, and the mixture was stirred at room temperature for 20 minutes. After centrifugation, the nanowires were washed with deionized water to obtain copper-modified hydroxyapatite ultralong nanowires (the mass ratio of copper nanowires to hydroxyapatite ultralong nanowires was 0.0152:1). One gram of copper-modified hydroxyapatite ultralong nanowires and 0.3 grams of disodium pamidronate acrylate were added to 200 mL of water. The pH of the mixed solution was adjusted to 7.0 using dilute hydrochloric acid, and the mixture was stirred at room temperature for 24 hours. After centrifugation, the nanowires were washed with deionized water and freeze-dried to obtain copper nanowires and disodium pamidronate acrylate-modified hydroxyapatite ultralong nanowires. The above process was repeated twice. 1.5 g of nano-copper and hydroxyapatite ultralong nanowires modified with disodium pamidronate acrylate, 0.5 g of polymethyl methacrylate, and 14 mg of benzoyl peroxide powder were mixed. 1 mL of a mixture of methyl methacrylate and N,N-dimethyl-p-toluidine was added and stirred until homogeneous. The resulting mixture was filled into a mold and cured. After demolding, the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement was obtained.

[0054] Figure 2These are digital photographs of hydroxyapatite ultralong nanowires / polymethyl methacrylate composite bone cement prepared using different molds in Example 1 of this invention. As shown in the figures, filling the mixture obtained in Example 1 into molds of different shapes yields hydroxyapatite ultralong nanowires / polymethyl methacrylate composite bone cements of various shapes, including letter shapes, number shapes, cylindrical shapes, and strip shapes. Experiment 1: Determination of the highest curing temperature

[0055] The surface temperature change curves of the samples prepared in Examples 1-6 and Comparative Examples 1-6 during the curing process were measured using an infrared thermal imager, and the highest curing temperature was recorded.

[0056] Figure 3 The figure shows the highest curing temperature of the samples prepared in Examples 1-6 and Comparative Examples 1-6 of this invention. As can be seen from the figure, the highest curing temperature of the composite bone cement prepared in Examples 1-6, Comparative Examples 1-3, Comparative Examples 5 and Comparative Examples 6 is 33.6-49.4℃, which is significantly lower than the highest curing temperature (96.4℃) of the polymethyl methacrylate bone cement prepared in Comparative Example 4. Experiment 2: Determination of curing time

[0057] The surface temperature change curves of the samples prepared in Examples 1-6 and Comparative Examples 1-6 during the curing process were measured using an infrared thermal imager. The curing time = (maximum curing temperature + ambient temperature) / 2 corresponding to the time point.

[0058] Figure 4 The curing times are those of the samples prepared in Examples 1-6 and Comparative Examples 1-6 of this invention. As shown in the figure, the curing times of the composite bone cements prepared in Examples 1-6, Comparative Examples 1-3, Comparative Examples 5 and 6 are 9.1 to 16.2 minutes, which are all higher than the curing time of the polymethyl methacrylate bone cement prepared in Comparative Example 4 (7.3 minutes). Experiment 3: Determination of compressive strength and elastic modulus

[0059] Samples of Examples 1-6 and Comparative Examples 1-6 were prepared using molds with a diameter of 6 mm and a height of 12 mm. The compressive strength and elastic modulus of the samples were tested using a universal material mechanics analyzer.

[0060] Figure 5The figures show the compressive strength and elastic modulus of the samples prepared in Examples 1-6 and Comparative Examples 1-6 of this invention. As can be seen from the figures, the compressive strength of the composite bone cement prepared in Examples 1-6 and Comparative Example 1 is 73.8–93.1 MPa, which is close to or slightly higher than the compressive strength of the polymethyl methacrylate bone cement prepared in Comparative Example 4 (88.1 MPa). The elastic modulus of the composite bone cement prepared in Examples 1-6 and Comparative Example 1 is 0.73–1.01 GPa, which is significantly lower than the elastic modulus of the polymethyl methacrylate bone cement prepared in Comparative Example 4 (1.29 GPa). The compressive strength and elastic modulus of the composite bone cement prepared in Comparative Examples 2 and 3 are both lower than those of the polymethyl methacrylate bone cement prepared in Comparative Example 4. These experimental results indicate that the modification of hydroxyapatite ultralong nanowires with disodium pamidronate acrylate forms a stable organic-inorganic interfacial bond, which is beneficial for improving compressive strength and reducing elastic modulus. The compressive strength and elastic modulus of the composite bone cement prepared in Comparative Example 5 were both lower than those of the composite bone cement prepared in Example 1, indicating that the modification order of hydroxyapatite ultralong nanowires should be antibacterial agent and disodium pamidronate acrylate in that order. The compressive strength of the composite bone cement prepared in Comparative Example 6 was lower than the ISO 5833-2002 standard (70 MPa), indicating that an excessively high content of modified hydroxyapatite ultralong nanowires will reduce the mechanical properties of the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement. Experiment 4: Determination of flexural strength and modulus of elasticity

[0061] Samples prepared in Examples 1-6 and Comparative Examples 1-6 were prepared using a mold with a length of 75 mm, a width of 10 mm, and a height of 3.5 mm. The flexural strength and elastic modulus of the samples were tested using a universal material mechanics analyzer.

[0062] Figure 6The figures show the flexural strength and elastic modulus of the samples prepared in Examples 1-6 and Comparative Examples 1-6 of this invention. As can be seen from the figures, the flexural strength of the composite bone cement prepared in Examples 1-5 and Comparative Example 1 is 63.1–71.8 MPa, which is close to or slightly higher than the flexural strength of the polymethyl methacrylate bone cement prepared in Comparative Example 4 (69.3 MPa). The elastic modulus of the composite bone cement prepared in Examples 1-5 and Comparative Example 1 is 1.92–2.18 GPa, which is significantly lower than the elastic modulus of the polymethyl methacrylate bone cement prepared in Comparative Example 4 (2.71 GPa). The flexural strength and elastic modulus of the composite bone cement prepared in Comparative Examples 2 and 3 are both lower than those of the polymethyl methacrylate bone cement prepared in Comparative Example 4. These experimental results indicate that the modification of hydroxyapatite ultralong nanowires with disodium pamidronate acrylate forms a stable organic-inorganic interfacial bond, which is beneficial for improving flexural strength and reducing elastic modulus. The composite bone cement prepared in Comparative Example 5 had lower flexural strength and elastic modulus than the composite bone cement prepared in Example 1, indicating that the modification order of hydroxyapatite ultralong nanowires should be antibacterial agent and disodium pamidronate acrylate in that order. The composite bone cement prepared in Comparative Example 6 had lower flexural strength than the ISO 5833-2002 standard (50 MPa), indicating that excessively high content of modified hydroxyapatite ultralong nanowires will reduce the mechanical properties of the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement. Experiment 5: Determination of antibacterial properties

[0063] The antibacterial effects of the composite bone cement prepared in Examples 1-5 and Comparative Example 1 against Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus were determined using the shaking culture method. The composite bone cement prepared in Examples 1-5 and Comparative Example 1 was respectively mixed with 10 mL of 10... 5 CFU mL –1 Mix Escherichia coli or Staphylococcus aureus and incubate at 37 °C with shaking for 24 h. Take a portion of the suspension and dilute it. Spread 100 μL of the diluted suspension onto an agar plate and incubate at 37 °C for 18 h. Take a picture and count the number of colonies.

[0064] Figure 7The figures show the growth of samples prepared in Examples 1-5 and Comparative Example 1 of this invention after being cultured in liquid culture medium with Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus, respectively, and then coated with a portion of the liquid onto a solid culture medium. As can be seen from the figures, the samples prepared in Examples 1, 2, 4, and 5 all showed 100% antibacterial efficiency against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. The sample prepared in Example 3 showed antibacterial efficiencies of 73.9% and 76.4% against Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus, respectively. The sample prepared in Comparative Example 1 showed 0% antibacterial efficiency against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. Industrial application

[0065] The preparation process of this invention is simple and easy to operate, requiring no complex and expensive equipment, and is easy to mass-produce. The hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement prepared by the method provided by this invention has promising applications as a biomedical material in biomedical fields such as bone defect repair, osteoporosis treatment, and treatment of bone-related diseases.

Claims

1. A hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement, characterized in that, It comprises two parts: a powder and a liquid. The powder consists of modified hydroxyapatite ultralong nanowires, polymethyl methacrylate, and an initiator. The liquid consists of methyl methacrylate and a curing accelerator. The modified hydroxyapatite ultralong nanowires are hydroxyapatite ultralong nanowires modified sequentially with an antibacterial agent and disodium pamidronate acrylate.

2. The hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement according to claim 1, characterized in that, The modified hydroxyapatite ultralong nanowires have a length of 10–1000 micrometers, a diameter of 10–100 nanometers, and an aspect ratio greater than 100. The modified hydroxyapatite ultralong nanowires in the powder, by mass percentage, are 0.1-70%, preferably 10-50%, the polymethyl methacrylate is 29.8-99.7%, and the initiator is 0.2-2%.

3. The hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement according to claim 1 or 2, characterized in that, The initiator is selected from at least one of benzoyl peroxide, lauroyl peroxide, and dimethyl azobisisobutyrate; The curing accelerator is selected from at least one of N,N-dimethyl-p-toluidine, N,N-dimethylaniline, and N-methyl-N-2-hydroxyethyl-p-toluidine; preferably, the content of the curing accelerator in the liquid is 1 to 5% by mass percentage.

4. The hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement according to any one of claims 1-3, characterized in that, The mass-to-volume ratio of the powder to the liquid is (1.0–4.0) g: 1 mL, preferably (1.5–3.0) g: 1 mL.

5. The hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement according to any one of claims 1-4, characterized in that, The antibacterial agent includes at least one of the following: nano copper, nano silver, zinc oxide, gentamicin, vancomycin, ciprofloxacin, chlorhexidine hydrochloride, chitosan, carboxymethyl chitosan, and antimicrobial peptides. When the antibacterial agent is at least one of nano-copper, nano-silver, and zinc oxide, the antibacterial agent formation process is as follows: copper ions, silver ions, and zinc ions are loaded onto the surface of hydroxyapatite ultralong nanowires through ion exchange, reduction / precipitation methods. When the antibacterial agent is at least one of gentamicin, vancomycin, ciprofloxacin, chlorhexidine hydrochloride, chitosan, carboxymethyl chitosan, and antimicrobial peptide, the antibacterial agent is loaded onto the surface of hydroxyapatite ultralong nanowires through an electrostatic adsorption process. The disodium pamidronate acrylate is loaded onto the surface of hydroxyapatite ultralong nanowires via an electrostatic adsorption process.

6. A method for preparing hydroxyapatite ultralong nanowires / polymethyl methacrylate composite bone cement according to any one of claims 1-5, characterized in that, Includes the following steps: Modified hydroxyapatite ultralong nanowires, polymethyl methacrylate and an initiator were mixed to obtain a solid powder; then a curing accelerator and liquid methyl methacrylate were added to it and stirred to obtain a mixture; the resulting mixture was filled into a mold and cured, and after demolding, the hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement was obtained.

7. The preparation method according to claim 6, characterized in that, When the antibacterial agent is at least one of nano-copper, nano-silver, and zinc oxide: The preparation method of the modified hydroxyapatite ultralong nanowires includes: (1) When the antibacterial agent is at least one of nano copper and nano silver, hydroxyapatite ultralong nanowires are mixed with an aqueous solution containing copper ions or silver ions, and a reducing agent is added to reduce the copper ions or silver ions. The resulting nano copper or nano silver is loaded on the surface of the hydroxyapatite ultralong nanowires. After centrifugation and washing, antibacterial agent modified hydroxyapatite ultralong nanowires are obtained. When the antibacterial agent is zinc oxide, hydroxyapatite ultralong nanowires are mixed with an aqueous solution containing zinc ions, and an alkaline substance is added to cause the zinc ions to precipitate. The resulting zinc oxide is loaded onto the surface of the hydroxyapatite ultralong nanowires. After centrifugation and washing, antibacterial agent modified hydroxyapatite ultralong nanowires are obtained. (2) The antibacterial agent-modified hydroxyapatite ultralong nanowires and disodium pamidronate acrylate were dispersed in deionized water, the pH was adjusted to neutral, and after stirring, centrifugation, washing and drying, the antibacterial agent and disodium pamidronate acrylate-modified hydroxyapatite ultralong nanowires were obtained.

8. The preparation method according to claim 6 or 7, characterized in that, When the antibacterial agent is at least one of gentamicin, vancomycin, ciprofloxacin, chlorhexidine hydrochloride, chitosan, carboxymethyl chitosan, and antimicrobial peptides: The method for preparing the modified hydroxyapatite ultralong nanowires includes: dispersing hydroxyapatite ultralong nanowires with an antibacterial agent and disodium pamidronate acrylate in deionized water, adjusting the pH to neutral, and then stirring, centrifuging, washing, and drying to obtain hydroxyapatite ultralong nanowires modified with the antibacterial agent and disodium pamidronate acrylate.

9. The preparation method according to any one of claims 6-8, characterized in that, The mass ratio of the antibacterial agent to the hydroxyapatite ultralong nanowires is (0.001-1):1, preferably (0.005-0.5):1; the mass ratio of the disodium pamidronate acrylate to the hydroxyapatite ultralong nanowires is (0.01-1):1, preferably (0.1-0.6):

1.

10. The application of a hydroxyapatite ultralong nanowire / polymethyl methacrylate composite bone cement according to any one of claims 1-5 in the preparation of bone defect repair materials, osteoporosis treatment materials, and bone-related disease treatment materials.

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