Preparation method of europium-doped black phosphorus nanosheet deposition customized porous TMJ prosthesis

Abstract

The preparation method of the europium-doped black phosphorus nanosheet deposition customized porous TMJ prosthesis comprises the following steps: S1, shooting medical image data by using CBCT (Cone Beam Computed Tomography), importing the medical image data into Mimics software for model reconstruction, and importing a reconstructed model into Geomagic software for simulating osteotomy to obtain a cranio-maxillofacial model STL (Standard Template Library) file; s2, performing TMJ prosthesis customization design on the STL file of the craniomaxillofacial model; s3, performing 3D printing on the customized TMJ prosthesis model by adopting an SLM printing technology to obtain a prosthesis entity; and S4, constructing a polydopamine europium-doped black phosphorus nanosheet surface coating on the porous area of the prosthesis entity model. The computer-aided design and the three-dimensional printing technology are adopted, and product customization is achieved; the europium-doped black phosphorus nanosheet coating is constructed in the porous area of the prosthesis, bone ingrowth of the mandible stump and the buccal side area is promoted, traditional two-dimensional fixation is changed into three-dimensional fixation, and the limitation of screw loosening, falling and bone resorption is avoided.

Description

Technical Field

[0001] The present invention belongs to the field of medical technology, and relates to the preparation of a TMJ prosthesis, in particular to a preparation method of a customized porous TMJ prosthesis deposited with europium-doped black phosphorus nanosheets. Background Art

[0002] TMJ, that is, the temporomandibular joint, as the only movable joint in the oral and maxillofacial region, has a delicate anatomical structure and complex motor functions, and is one of the most active joints in the human body. The occurrence of diseases such as ankylosis, trauma, and tumors often leads to morphological defects and functional loss of the temporomandibular joint, seriously affecting the quality of life of patients. How to perform ideal functional and morphological reconstruction, restore stable occlusal relationships, and the height of the mandibular ramus, etc. are problems that must be faced and solved during defect repair. Autologous bone grafting can only achieve approximate function, cannot achieve anatomical reconstruction, and is prone to donor site complications. Allogeneic bone grafting mainly has immune rejection reactions and slow osteogenesis; while artificial temporomandibular joints have advantages such as rapid prototyping, precise anatomical design, minimally invasive, no need for secondary surgery, ease of use, stable effects, and immediate functional recovery, making artificial temporomandibular joint reconstruction one of the fastest-growing joint reconstruction methods globally.

[0003] The existing standard TMJ prosthesis products on the market mainly originate from abroad, with fewer finished product models and cannot meet all clinical needs; moreover, in the current TMJ condylar prosthesis replacement system, most solutions adopt the contact method between the condylar prosthesis surface and the osteotomy surface as face-to-face connection, and most of the rest rely only on screws for fixation, and intraoperative operation is facilitated by reserving fixation holes, without personalized design according to the patient's jawbone. Eventually, the bone tissue at the bone section fails to grow into the condylar prosthesis internally through the porous structure and form bone, or early screw loosening occurs due to the non-fitting of the fixation plate and the jawbone, resulting in phenomena such as prosthesis loosening and dislocation or late bone resorption, and few existing designs consider the reattachment of the lateral pterygoid muscle to the prosthesis, which is not conducive to the recovery of mandibular function after surgery.

[0004] Based on the current huge market demand for domestic personalized condylar prostheses in China, developing a domestic, customized artificial TMJ prosthesis that conforms to the jawbone anatomical structure of Chinese people and is inexpensive is an extremely urgent task. However, research shows that only treating the microstructure of the prosthesis still cannot meet the good integration between the implant and the bone. Therefore, it is necessary to explore excellent bioactive materials and graft them. Summary of the Invention

[0005] The object of the present invention is to provide a preparation method of an europium-doped black phosphorus nanosheet-deposited customized porous TMJ prosthesis. This preparation method adopts computer-aided design and three-dimensional printing technology to achieve customized services. In addition, the TMJ prosthesis adopts a porous structure to connect with the patient's autogenous bone tissue, transforming the traditional "two-dimensional fixation" into a new "three-dimensional fixation" mode, thus getting rid of the limitations of prosthesis loosening, shedding and bone resorption. At the same time, the present invention constructs an europium-doped black phosphorus nanosheet coating in the porous area of the customized porous TMJ prosthesis, so as to promote the growth of bone tissue in the prosthesis after implantation, which is beneficial to the recovery of mandibular function after surgery, and effectively solves the problems existing in the prior art.

[0006] The technical solution adopted by the present invention to achieve the above object is: a preparation method of an europium-doped black phosphorus nanosheet-deposited customized porous TMJ prosthesis, comprising the following steps: S1. Use CBCT to take the medical image data of the patient's maxillofacial region, and import it into Mimics Medical software for craniofacial three-dimensional model reconstruction; then import the craniofacial three-dimensional model into Geomagic Wrap software, and simulate surgical osteotomy at the temporomandibular joint on the surgical side of the patient according to the surgical requirements of temporomandibular joint reconstruction to obtain the STL file of the craniofacial model; S2. Based on the STL file of the craniofacial model obtained in step S1, perform customized design of the TMJ prosthesis to obtain the STL file of the customized TMJ prosthesis model; S3. Use SLM printing technology to perform 3D printing manufacturing on the STL file of the customized TMJ prosthesis model obtained in step S2 to obtain the physical model of the customized TMJ prosthesis; S4. Construct a polydopamine europium-doped black phosphorus nanosheet PDA@(BP+Eu) surface coating on the porous area of the TMJ prosthesis physical model obtained in step S3, specifically as follows: (1) Construct a polydopamine (PDA) coating on the porous area of the TMJ prosthesis physical model: Pour the polydopamine (PDA) solution into the porous area of the TMJ prosthesis physical model for soaking, incubate it with a shaker for 24 hours, then take out the TMJ prosthesis and immerse the TMJ prosthesis in deionized water and oscillate for 2 minutes, and then dry it in a vacuum environment at 40 °C for 6 hours to fully discard the unpolymerized DA monomers and unadhered PDA on its surface, and obtain a polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA) containing a polydopamine (PDA) coating; (2) Compound the polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA) with the polydopamine europium-doped black phosphorus nanosheet PDA@(BP+Eu) to obtain an europium-doped black phosphorus nanosheet-deposited customized porous TMJ prosthesis.

[0007] A further technical solution of the present invention is: in step S2, the customized design of the TMJ prosthesis includes: (1) Determination of the structural parameters of the condylar prosthesis: The thickness of the external entity simulates the thickness of the cortical bone and is obtained by multi-point sampling and measurement of the patient's CT data; the internal is a rhombic or gradient porous structure, and the pore diameter gradually decreases from the bone contact end of the prosthesis to the lower end of the condylar head, and the porosity is 70% for all; (2) Design of the condylar prosthesis head: The shape is a combination of a hemisphere and a cylinder, and the ball diameter and the cylinder diameter are the same; (3) Porous design of the condylar neck: A porous structure is provided at the anterior medial surface of the mandible at the pterygoid fossa of the articular muscle and on the medial side of the condyle, with a porosity of 70% for the attachment of the lateral pterygoid muscle; (4) Design of the retention wing plate of the condylar prosthesis: The length and width of the retention handle are based on the 3D model data of the mandibular ramus, the shape is "V", and the thickness of the retention handle is 2 mm. The inner side between the upper and lower nail holes of the retention handle is designed as a porous area, the hole depth is 0.5 mm, and the parameter at the contact with the bone section of the hole diameter is the same; (5) Design of the retention nail holes of the condylar prosthesis: The diameter of the retention nail holes is 2 mm, and the length is determined according to the thickness of the retention handle and the bilateral cortical bone. There are 2 retention nails on the upper and lower sides respectively. The retention nails are fixed on the outer side of the mandible along the posterior edge and the lower edge of the mandible, and the working end of the retention nail is set as a sharp thread; (6) Design of the glenoid fossa: When the mandible is stationary, the glenoid fossa prosthesis is designed on the articular eminence slightly in front of the temporomandibular glenoid fossa. The material of the glenoid fossa is ultra-high molecular weight polyethylene and is fixed to the zygomatic arch by 4 titanium nails in an external contact manner. The fossa matches the condylar head and there is a posterior lip at the rear to prevent posterior dislocation of the condyle. The thickness of the glenoid fossa prosthesis is at least 3 mm.

[0008] A further technical solution of the present invention is: in step S3, when using the SLM printing technology to perform 3D printing and manufacturing on the digital model of the customized TMJ prosthesis, the selected printing material is implant-grade Ti6Al4V metal powder, the laser spot diameter is 70 μm, the thickness of each layer is 50 μm, the scanning speed is 0.6 m / s, and the laser power is 200 W; after 3D printing is completed, post-processing operations are performed on it and high-pressure sterilization is carried out to complete the manufacturing of the Ti6Al4V customized porous titanium alloy TMJ prosthesis.

[0009] A further technical solution of the present invention is: in step S4, the synthesis method of the polydopamine (PDA) solution is as follows: Weigh 0.06 g of tris (hydroxymethyl) aminomethane (Tris) and dissolve it in 50 mL of pure water, and stir magnetically for 10 minutes. Use hydrochloric acid to adjust the pH value of the tris (hydroxymethyl) aminomethane (Tris) buffer solution so that its pH value is 8.5; Next, add 0.1 g of dopamine (DA) powder to tris(hydroxymethyl)aminomethane (Tris) buffer solution and stir for 5 minutes to obtain a polydopamine (PDA) solution with a concentration of 2 mg / mL. When the color turns light yellow, it indicates that the synthesis of the polydopamine (PDA) solution is completed.

[0010] A further technical solution of the present invention is that in step S4, the preparation method of the polydopamine-doped europium black phosphorus nanosheets PDA@(BP+Eu) is as follows: First, take 10-20 mL of a black phosphorus nanosheet (BPNS) suspension with a concentration of 0.2 mg / mL and put it into a centrifuge tube. Centrifuge it at 15000 r / min for 20 minutes under refrigeration, discard the supernatant, and wash it. Then add 10-20 mL of acetonitrile solution, and then add 25-50 mg of europium nitrate hexahydrate. Ultrasonic for 3 minutes, stir it in a closed and light-proof manner for 12 hours, centrifuge it at 12000 r / min for 15 minutes under refrigeration, and wash it to obtain europium-doped black phosphorus nanosheets (BP+Eu). Finally, slowly add 10-20 mL of a polydopamine (PDA) solution with a concentration of 2 mg / mL, oscillate it in a closed and light-proof manner for 2 hours, centrifuge and wash it again to obtain polydopamine-doped europium black phosphorus nanosheets PDA@(BP+Eu).

[0011] A further technical solution of the present invention is that in step S4, the compounding method of the polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA) and the polydopamine-doped europium black phosphorus nanosheets PDA@(BP+Eu) is as follows: First, disperse the polydopamine-doped europium black phosphorus nanosheets PDA@(BP+Eu) in deionized water, and introduce the deionized water into the porous area of the polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA). Gently blow the bubbles in the pores of the polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA) with a pipette to make the polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA) fully contact with the polydopamine-doped europium black phosphorus nanosheets PDA@(BP+Eu) solution. After incubating on a shaker for 24 hours, wash it with deionized water, take out the TMJ prosthesis, dry it in an oven at 40 °C for 1-2 hours, and finally sterilize and seal it to obtain a customized porous TMJ prosthesis with europium-doped black phosphorus nanosheets deposited.

[0012] Due to adopting the above technical solutions, the preparation method of the customized porous TMJ prosthesis with europium-doped black phosphorus nanosheets deposited in the present invention has the following beneficial effects: 1. The present invention uses computer-aided design and 3D printing technology to print a titanium alloy TMJ prosthesis that matches the morphology of the patient's own mandible. The prosthesis jawbone fits better, and there is no need to grind a large amount of bone tissue during the operation to adapt to the shape of the prosthesis, effectively reducing the occurrence of intraoperative and postoperative complications, shortening the operation time, and achieving the best stress distribution after implantation; 2. The present invention constructs an europium-doped black phosphorus nanosheet coating in the porous region of the customized porous TMJ prosthesis. Research shows that doping Eu 3+ or Eu compound nanoparticles in biomaterials can regulate the immune microenvironment and promote the osteogenic differentiation of bone marrow mesenchymal stem cells (BMSCs), angiogenesis of human umbilical vein endothelial cells (HUVECs), etc. However, bioactive Eu 3+ cannot be well integrated with the scaffold in the form of a single substance, and black phosphorus nanosheets, due to their unique layered structure and high specific surface area, can be used as excellent carriers for material delivery; PDA is a substance generated by the self-polymerization of dopamine monomer (DA) in a weakly alkaline environment, and has strong adhesion to almost all materials and the ability to recruit stem cells; Therefore, the present invention constructs an europium-doped black phosphorus nanosheet coating in the porous region of the customized porous TMJ prosthesis to achieve the purpose of promoting the growth of bone tissue in the prosthesis after implantation, which is beneficial to the recovery of mandibular function after surgery; 3. The TMJ prosthesis of the present invention uses a porous structure to connect with the patient's autologous bone tissue, transforming the traditional "two-dimensional fixation" into a new "three-dimensional fixation" mode, so that the main force of the TMJ prosthesis is transformed into the common force of the internal structure and bone tissue, thus getting rid of the limitations of prosthesis loosening, shedding and bone resorption.

[0013] The following further describes the preparation method of the europium-doped black phosphorus nanosheet-deposited customized porous TMJ prosthesis of the present invention with reference to the drawings and embodiments. Description of the Drawings

[0014] Figure 1 is a schematic structural diagram of the TMJ prosthesis designed by the preparation method of the europium-doped black phosphorus nanosheet-deposited customized porous TMJ prosthesis of the present invention after being assembled with the patient's mandible; Figure 2 is the STL model of the mandible model in step S2 of the present invention; Figure 3 is the front view of the customized TMJ prosthesis of the present invention; Figure 4 is the rear view of the customized TMJ prosthesis of the present invention; Explanation of the reference numerals in the drawings: 1-articular fossa, 2-condylar head, 3-condylar neck, 4-retaining wing plate, 5-retaining nail. Detailed Embodiments

[0015] AsFigures 1 to 4 As shown in the figure, the preparation method of the customized porous TMJ prosthesis deposited with europium-doped black phosphorus nanosheets of the present invention includes the following steps: S1. Use CBCT to take the medical image data of the patient's maxillofacial region, import it into Mimics Medical 21.0 software (Materialise, Belgium) for cranio-maxillofacial three-dimensional model reconstruction; then import the cranio-maxillofacial three-dimensional model into Geomagic Wrap 2017 software (3D Systems, USA), and according to the surgical requirements of temporomandibular joint reconstruction, simulate surgical osteotomy at the temporomandibular joint on the surgical side of the patient to obtain the STL file of the cranio-maxillofacial model (as Figure 2 shown); S2. Based on the STL file of the cranio-maxillofacial model obtained in step S1, perform customized design of the TMJ prosthesis to obtain the STL file of the customized TMJ prosthesis model (as Figure 3 , Figure 4 shown); It should be noted that in this step, the customized design of the TMJ prosthesis includes: 1) determination of the structural parameters of the condylar prosthesis; 2) design of the head of the condylar prosthesis; 3) porous design of the condylar neck; 4) design of the retention wing plate of the condylar prosthesis; 5) design of the retention nail holes of the condylar prosthesis; 6) design of the glenoid fossa; S3. Use the SLM printing technology to perform 3D printing and manufacturing on the STL file of the customized TMJ prosthesis model obtained in step S2 to obtain the physical model of the customized TMJ prosthesis; S4. Construct a polydopamine europium-doped black phosphorus nanosheet PDA@(BP+Eu) surface coating on the porous area of the TMJ prosthesis physical model obtained in step S3, specifically as follows: (1) Construct a polydopamine (PDA) coating on the surface of the porous area of the TMJ prosthesis physical model: Import the polydopamine (PDA) solution into the porous area of the TMJ prosthesis physical model for soaking, incubate it with a shaker for 24 hours, then take out the TMJ prosthesis and immerse the TMJ prosthesis in deionized water and oscillate for 2 minutes, and then dry the TMJ prosthesis in a vacuum environment at 40 °C for 6 hours to fully discard the unpolymerized DA monomers and unadhered polydopamine (PDA) on its surface, and obtain a polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA) containing a polydopamine (PDA) coating; (2) Compound the polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA) with the polydopamine europium-doped black phosphorus nanosheet PDA@(BP+Eu) to obtain a customized porous TMJ prosthesis deposited with europium-doped black phosphorus nanosheets.

[0016] Furthermore, in step S2, the customized design of the TMJ prosthesis includes: (1)Determination of the structural parameters of the condylar prosthesis: The thickness of the external entity simulates the cortical bone thickness, which is obtained by multi-point sampling and measurement of the patient's CT data, and the thickness is about 1 mm; the internal is a rhombic or gradient porous structure, and the pore size gradually decreases from the bone contact end of the prosthesis to the lower end of the condylar head. In this embodiment, the pore size gradually decreases from 650 um at the bone contact end of the prosthesis to 500 um at the lower end of the condylar head, and the porosity is 70% for all; (2)Design of the condylar prosthesis head: The shape is a combination of a hemisphere and a cylinder, and the ball diameter and the cylinder diameter are the same; in this embodiment, both the ball diameter and the cylinder diameter are 8 mm, and the overall height is 7 mm; (3)Porous design of the condylar neck: Porous structures are provided at the medial anterior surface of the mandible (above the mandibular foramen), at the pterygoid fossa of the joint (above the medial side of the mandibular notch), and on the medial side of the condyle, with a total area of 2.0 ± 0.4 cm 2 , that is: 1.4 ± 0.3 cm at the pterygoid fossa 2 , 0.6 ± 0.2 cm on the medial side of the condyle 2 ; the pore size is 500 um, and the porosity is 70%, for the attachment of the lateral pterygoid muscle; (4)Design of the retaining wing plate of the condylar prosthesis: The length and width of the retaining handle are based on the 3D model data of the ramus of the mandible. The shape is "V", and the thickness of the retaining handle is 2 mm. The inner side within the range of 1 × 1.5 cm (avoiding the safe area of the nail holes) between the upper and lower nail holes of the retaining handle of the condylar prosthesis is designed as a porous area, the pore depth is 0.5 mm, and the parameters at the contact surface with the bone section are the same; (5)Design of the retaining nail holes of the condylar prosthesis: The diameter of the retaining nail holes is 2 mm, and the length is determined according to the thickness of the retaining handle and the bilateral cortical bone. There are 2 retaining nails on the upper and lower sides respectively. In order to avoid damaging the inferior alveolar nerve and the mandibular canal, the retaining nails are fixed on the lateral surface of the mandible along the posterior margin and the lower margin of the mandible, and its initial pre-tension is 100 N, and the working end of the retaining nail is provided with sharp threads; in this embodiment, the retaining nail is a titanium nail; (6)Design of the glenoid fossa: When the mandible is at rest, the glenoid fossa prosthesis is designed on the articular eminence slightly in front of the temporomandibular glenoid fossa. The material of the glenoid fossa is ultra-high molecular weight polyethylene, and it is fixed to the zygomatic arch by 4 titanium nails in an external contact manner. The fossa matches the condylar head and there is a posterior lip at the rear to prevent posterior dislocation of the condylar. The thickness of the glenoid fossa prosthesis is at least 3 mm, and the average depth is 4.32 mm.

[0017] In step S3, when using the SLM printing technology to 3D print and manufacture the digital model of the customized TMJ prosthesis, the selected printing material is implant-grade Ti6Al4V metal powder, the laser spot diameter is 70 μm, the thickness of each layer is 50 μm, the scanning speed is 0.6 m / s, and the laser power is 200 W. After 3D printing is completed, sandblasting and polishing post-treatment operations are performed on it and high-pressure sterilization is carried out to complete the manufacture of the Ti6Al4V customized porous titanium alloy TMJ prosthesis. In addition, the forming process of the SLM printing technology is a prior art and will not be elaborated here too much.

[0018] In step S4, the synthesis method of the polydopamine (PDA) solution is as follows: Weigh 0.06 g of tris(hydroxymethyl)aminomethane (Tris) and dissolve it in 50 mL of pure water, and magnetically stir for 10 minutes. Use hydrochloric acid to adjust the pH value of the tris(hydroxymethyl)aminomethane (Tris) buffer solution so that its pH value is 8.5. Then add 0.1 g of dopamine (DA) powder into the tris(hydroxymethyl)aminomethane (Tris) buffer solution and stir for 5 minutes to obtain a polydopamine (PDA) solution with a concentration of 2 mg / mL. When the color turns light yellow, it indicates that the synthesis of the polydopamine (PDA) solution is completed.

[0019] In step S4, the preparation method of the polydopamine-doped europium black phosphorus nanosheets PDA@(BP+Eu) is as follows: First, take 10 - 20 mL of a 0.2 mg / mL black phosphorus nanosheet (BPNS) suspension and put it into a centrifuge tube, centrifuge at 15000 r / min for 20 minutes under freezing conditions, discard the supernatant, and wash. Then add 10 - 20 mL of acetonitrile solution, and then add 25 - 50 mg of europium nitrate hexahydrate, ultrasonicate for 3 minutes, stir in a closed and light-proof manner for 12 hours, centrifuge at 12000 r / min for 15 minutes under freezing conditions, and wash to obtain europium-doped black phosphorus nanosheets (BP+Eu). Finally, slowly add 10 - 20 mL of a 2 mg / mL polydopamine (PDA) solution, oscillate in a closed and light-proof manner for 2 hours, centrifuge and wash again to obtain polydopamine-doped europium black phosphorus nanosheets PDA@(BP+Eu).

[0020] It should be noted that the polydopamine-doped europium black phosphorus nanosheets PDA@(BP+Eu) of the present invention should be stored in the dark at 4 °C.

[0021] In step S4, the composite method of the polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA) and the polydopamine-doped europium black phosphorus nanosheets PDA@(BP+Eu) is as follows: First, disperse polydopamine-doped europium black phosphorus nanosheets PDA@(BP+Eu) in deionized water to form a polydopamine-doped europium black phosphorus nanosheet PDA@(BP+Eu) solution. Then, introduce this PDA@(BP+Eu) solution into the porous region of the polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA). Gently blow the bubbles in the pores of the Ti-PDA with a pipette to ensure sufficient contact between the Ti-PDA and the PDA@(BP+Eu) solution. After incubating on a shaker for 24 hours, wash with deionized water, take out the TMJ prosthesis, dry it in an oven at 40 °C for 1-2 hours, and finally irradiate it with Co60 for sterilization and then seal it to obtain a customized porous TMJ prosthesis with europium black phosphorus nanosheets deposited. Store this TMJ prosthesis in a 4 °C refrigerator for later use.

[0022] In the present invention, a europium black phosphorus nanosheet coating is constructed on the surface of the customized porous TMJ prosthesis. Research shows that doping Eu 3+ or Eu compound nanoparticles in biomaterials can regulate the immune microenvironment and promote the osteogenic differentiation of bone marrow mesenchymal stem cells (BMSCs), angiogenesis of human umbilical vein endothelial cells (HUVECs), etc. However, the bioactive Eu3+ cannot be well integrated with the scaffold in the form of a single substance. Due to its unique layered structure and high specific surface area, black phosphorus nanosheets can be used as an excellent carrier for material delivery. PDA is a substance produced by the self-polymerization of dopamine monomers (DA) in a weakly alkaline environment, which has strong adhesion to almost all materials and the ability to recruit stem cells. Therefore, in the present invention, by constructing a europium black phosphorus nanosheet coating in the porous region of the customized porous TMJ prosthesis, the growth of bone tissue in the prosthesis can be promoted after implantation, which is beneficial to the recovery of mandibular function after surgery.

[0023] The above embodiments are only preferred embodiments of the present invention. The structure of the present invention is not limited to the forms listed in the above embodiments. Any modifications, equivalent replacements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. Preparation method of customized porous TMJ prosthesis deposited with europium-doped black phosphorus nanosheets, characterized in that: It includes the following steps: S1. Use CBCT to capture the medical imaging data of the patient's maxillofacial region, import it into Mimics Medical software for craniofacial three-dimensional model reconstruction; then import the craniofacial three-dimensional model into Geomagic Wrap software, and simulate osteotomy at the temporomandibular joint on the surgical side of the patient according to the surgical requirements of temporomandibular joint reconstruction to obtain the STL file of the craniofacial model; S2. Based on the STL file of the craniofacial model obtained in step S1, perform customized design of the TMJ prosthesis to obtain the STL file of the customized TMJ prosthesis model; S3. Use SLM printing technology to 3D print and manufacture the STL file of the customized TMJ prosthesis model obtained in step S2 to obtain the physical model of the customized TMJ prosthesis; S4. Construct a polydopamine-doped europium black phosphorus nanosheet PDA@(BP+Eu) surface coating on the porous area of the TMJ prosthesis physical model obtained in step S3, specifically as follows: (1) Construct a polydopamine (PDA) coating on the porous area of the TMJ prosthesis physical model: Pour the polydopamine (PDA) solution into the porous area of the TMJ prosthesis physical model for soaking, incubate it using a shaker for 24 hours, take out the TMJ prosthesis and immerse the TMJ prosthesis in deionized water and oscillate for 2 minutes, and then dry it in a vacuum environment at 40 °C for 6 hours to fully discard the unpolymerized DA monomers and unadhered PDA on its surface, and obtain a polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA) with a polydopamine (PDA) coating; (2) Combine the polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA) with the polydopamine-doped europium black phosphorus nanosheet PDA@(BP+Eu) to obtain a customized porous TMJ prosthesis with europium black phosphorus nanosheets deposited.

2. The preparation method of the customized porous TMJ prosthesis deposited with europium-doped black phosphorus nanosheets according to claim 1, characterized in that: In step S2, the customized design of the TMJ prosthesis includes: (1) Determination of the structural parameters of the condylar prosthesis: The thickness of the external entity simulates the cortical bone thickness and is obtained by multi-point sampling and measurement of the patient's CT data; the internal is a diamond or gradient porous structure, and the pore diameter gradually decreases from the bone contact end of the prosthesis to the lower end of the condylar head, and the porosity is 70% for both; (2) Design of the head of the condylar prosthesis: The shape is a combination of a hemisphere and a cylinder, and the ball diameter and the cylinder diameter are the same; (3) Porous design of the condylar neck: Porous structures are arranged at the anterior inner side of the mandible, the pterygoid fossa of the joint, and the inner side of the condyle, and the porosity is 70% for the attachment of the lateral pterygoid muscle; (4) Design of the retention wing plate of the condylar prosthesis: The length and width of the retention handle are based on the 3D model data of the ascending ramus of the mandible, the shape is "V", and the thickness of the retention handle is 2 mm. The inner side between the upper and lower nail holes of the retention handle is designed as a porous area, the hole depth is 0.5 mm, and the pore diameter is consistent with the parameters at the bone cross-section contact; (5) Design of the retention nail holes of the condylar prosthesis: The diameter of the retention nail holes is 2 mm, and the length is determined according to the thickness of the retention handle and the bilateral cortical bone. There are 2 retention nails on the upper and lower sides. The retention nails are fixed on the outer side of the mandible along the posterior and lower edges of the mandible, and the working end of the retention nail is set as a sharp thread; (6)Glenoid fossa design: When the mandible is stationary, the glenoid fossa prosthesis is designed on the articular eminence slightly anterior to the temporomandibular glenoid fossa. The material of the glenoid fossa is ultra-high molecular weight polyethylene, which is fixed to the zygomatic arch by 4 titanium screws in an external contact manner. The fossa matches the condylar head and has a posterior lip at the rear to prevent posterior dislocation of the condyle. The thickness of the glenoid fossa prosthesis is at least 3 mm.

3. The preparation method of the customized porous TMJ prosthesis deposited with europium-doped black phosphorus nanosheets according to claim 1, wherein: In step S3, when using the SLM printing technology to perform 3D printing and manufacturing on the digital model of the customized TMJ prosthesis, the selected printing material is implant-grade Ti6Al4V metal powder, the laser spot diameter is 70 μm, the thickness of each layer is 50 μm, the scanning speed is 0.6 m / s, and the laser power is 200 W; after 3D printing is completed, post-processing operations are performed on it and high-pressure sterilization is carried out to complete the manufacturing of the Ti6Al4V customized porous titanium alloy TMJ prosthesis.

4. The preparation method of the customized porous TMJ prosthesis deposited with europium-doped black phosphorus nanosheets according to claim 1, characterized in that: In step S4, the synthesis method of the polydopamine (PDA) solution is as follows: Weigh 0.06 g of tris(hydroxymethyl)aminomethane (Tris) and dissolve it in 50 mL of pure water, stir magnetically for 10 minutes, and adjust the pH value of the tris(hydroxymethyl)aminomethane (Tris) buffer solution with hydrochloric acid to make its pH value 8.5; Then add 0.1 g of dopamine (DA) powder to the tris(hydroxymethyl)aminomethane (Tris) buffer solution and stir for 5 minutes to obtain a polydopamine (PDA) solution with a concentration of 2 mg / mL. When the color turns light yellow, it indicates that the synthesis of the polydopamine (PDA) solution is completed.

5. The preparation method of the customized porous TMJ prosthesis deposited with europium-doped black phosphorus nanosheets according to claim 1, characterized in that: In step S4, the preparation method of the polydopamine-doped europium black phosphorus nanosheet PDA@(BP+Eu) is as follows: First, take 10 - 20 mL of a 0.2 mg / mL black phosphorus nanosheet (BPNS) suspension and put it into a centrifuge tube, centrifuge it at 15000 r / min for 20 minutes under refrigeration, discard the supernatant, and wash it; Then add 10 - 20 mL of acetonitrile solution, and then add 25 - 50 mg of europium nitrate hexahydrate, ultrasonicate for 3 minutes, stir it in a sealed and light-proof manner for 12 hours, centrifuge it at 12000 r / min for 15 minutes under refrigeration, and wash it to obtain the europium-doped black phosphorus nanosheet (BP+Eu); Finally, slowly add 10 - 20 mL of a 2 mg / mL polydopamine (PDA) solution, oscillate it in a sealed and light-proof manner for 2 hours, centrifuge and wash it again to obtain the polydopamine-doped europium black phosphorus nanosheet PDA@(BP+Eu).

6. The preparation method of the customized porous TMJ prosthesis deposited with europium-doped black phosphorus nanosheets according to claim 1, wherein: In step S4, the composite method of the polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA) and the polydopamine-doped europium black phosphorus nanosheet PDA@(BP+Eu) is as follows: First, disperse the polydopamine-doped europium black phosphorus nanosheets PDA@(BP+Eu) in deionized water, and introduce the deionized water into the porous region of the polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA). Gently blow the bubbles in the pores of the polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA) with a pipette to make the polydopamine-coated titanium alloy TMJ prosthesis (Ti-PDA) fully contact with the polydopamine-doped europium black phosphorus nanosheets PDA@(BP+Eu) solution. After incubating on a shaker for 24 hours, wash with deionized water, take out the TMJ prosthesis, dry it in an oven at 40 °C for 1-2 hours, and finally sterilize and seal it to obtain a customized porous TMJ prosthesis with europium black phosphorus nanosheets deposited on it.

Images