CN-122005924-A - 3D printing triboelectric material and application thereof in bone and cartilage defect repair

Abstract

The invention belongs to the field of tissue regeneration materials, and relates to a 3D printing triboelectric material and application thereof in repairing bone and cartilage defects. The material can be used as 3D printing ink for manufacturing a triboelectric bracket. The scaffold is prepared by taking biodegradable PGS as a matrix, PEDOT: PSS as a conductive component and sodium chloride as a pore-forming agent through a 3D printing combined salt particle pore-forming method, and has a multi-stage porous structure and excellent triboelectric performance. The invention accurately regulates and controls the wire diameter, the interlayer spacing and the micropore distribution of the bracket by a 3D printing technology, so that the bracket realizes in-situ self-energy electric stimulation under the in-vivo dynamic mechanical environment, the bracket can promote BMSCs to differentiate into chondrocytes, construct tissue engineering cartilage, accelerate the process of endochondral ossification, finally realize the efficient repair of bone and cartilage defects, has excellent biocompatibility, can be biodegraded, does not need an external power supply device, and has wide clinical transformation prospect in the field of bone and cartilage defect repair.

Inventors

• LEI DONG
• ZHOU GUANGDONG
• MA YUANQI
• SONG XINGQI
• LUO BIN

Assignees

• 上海交通大学医学院附属第九人民医院

Dates

Publication Date

20260512

Application Date

20260414

Priority Date

20260119

Claims (10)

1. 1. The preparation method of the 3D printing triboelectric material is characterized by comprising the following steps of: taking PEDOT PSS aqueous solution, uniformly mixing, filtering by a 0.3-0.6 mu m filter membrane, freezing the filtrate to obtain PEDOT PSS solid, and grinding the solid into powder; dissolving the powder in the step (1) in a mixed solvent of water and dimethyl sulfoxide to prepare a PEDOT-PSS dispersion liquid with the mass fraction of 1-15%, wherein the volume ratio of water to dimethyl sulfoxide is 1:4-7; And adding PEDOT (polyether glycol) PSS dispersion liquid into a system of the polyglycerol sebacate prepolymer and sodium chloride particles with the particle size of 25-38 mu m, and uniformly mixing to obtain the 3D printing triboelectric material, wherein the mass ratio of the polyglycerol sebacate prepolymer to the sodium chloride to the PEDOT PSS dispersion liquid is 1:1-4:0.01-0.1.
2. 2. The method for preparing a 3D printed triboelectric material according to claim 1, wherein the aqueous solution of PEDOT: PSS in step (1) is a CleviosTM PH model number PEDOT: PSS aqueous solution manufactured by He Lishi electronics company.
3. 3. The method for preparing the 3D printing triboelectric material according to claim 1, wherein the filtrate obtained in the step (1) is frozen for 2-4 hours by liquid nitrogen and then is freeze-dried for 45-60 hours to obtain PEDOT: PSS solid.
4. 4. A 3D printed triboelectric material produced by the method of production as claimed in any one of claims 1 to 3.
5. 5. Use of the 3D printed triboelectric material of claim 4 in a 3D printed triboelectric holder.
6. 6. A method of making a 3D printed triboelectric stand as set forth in claim 5, comprising the steps of: The 3D printing triboelectric material of claim 4 is printing ink, a pressure-assisted direct ink writing system is adopted, the rotation angle is set to be 90 degrees, the filling interval is 1.2mm, a nozzle with the diameter of 0.45mm is selected, the extrusion speed is 0.008mm 3 ・s -1 , the deposition speed is 4mm, s -1 , a bracket blank with a multilayer porous structure is obtained by printing, and a plurality of micro-channels are uniformly arranged on the bracket blank from top to bottom; Placing the bracket blank body in a vacuum oven, treating for 10-15h at 80-100 ℃ and 0.3-0.6bar, thermally curing for 20-30h at 130-140 ℃ and 0.8-1.2 bar, immersing the cured bracket in water for leaching for 20-30h, changing water at intervals during leaching to remove NaCl particles, and freeze-drying to obtain the 3D printing triboelectric bracket.
7. 7. A 3D printed triboelectric holder made by the method of making as claimed in claim 6.
8. 8. Use of the 3D printed triboelectric scaffold of claim 7 in the preparation of a bone or cartilage defect repair material.
9. 9. The use of a 3D printed triboelectric scaffold according to claim 8, in the preparation of a bone or cartilage defect repair material, wherein the bone defect is a skull defect or a long bone defect and the cartilage defect is an ear, nose or meniscus cartilage defect.
10. 10. The use of the 3D printing triboelectric scaffold according to claim 7 or 8 in preparing bone or cartilage defect repair materials, which is characterized by comprising the steps of directly implanting the 3D printing triboelectric scaffold according to claim 7 into a bone or cartilage defect site, or inoculating 90-120 mu L of bone marrow mesenchymal stem cells with the concentration of 60-100 multiplied by 10 6 cells/mL on the 3D printing triboelectric scaffold according to claim 7, placing the bone marrow mesenchymal stem cells in a cartilage-forming induction culture medium, culturing for 4-6 weeks, obtaining a composite scaffold loaded with BMSCs-source tissue engineering cartilage, and then re-implanting the composite scaffold into the bone or cartilage defect site.

Description

3D printing triboelectric material and application thereof in bone and cartilage defect repair Technical Field The invention belongs to the technical field of bone and cartilage tissue regeneration medical materials, relates to a 3D printing triboelectric material and application thereof in repairing bone and cartilage defects, and particularly relates to a 3D printing triboelectric material, a 3D printing triboelectric bracket prepared from the material, and application of the bracket in preparing bone and cartilage defect repairing materials. Background Bone defects are common clinical symptoms of orthopaedics, and are mostly caused by factors such as wounds, tumor excision, infection and the like. Among them, the difficult bone defect of large segment is severely blocked due to severe microenvironment such as local hypoxia, blood vessel lack, etc., and has become a major challenge for clinical repair. Such defects not only cause persistent pain and limb dysfunction, but also may induce secondary complications such as osteomyelitis, osteonecrosis and the like, seriously affecting the quality of life of the patient. Currently, the bone repair means commonly used in clinic mainly comprise autologous bone grafting, allogeneic bone grafting and traditional tissue engineering scaffolds. However, the methods have obvious limitations that autologous bone grafting faces the risks of secondary injury and complications of donor sources and bone extraction areas, allogenic bone grafting has potential hidden hazards of immune rejection and disease transmission, and the traditional tissue engineering scaffold can only provide passive structural support, lacks the functions of actively regulating cell behaviors and improving local microenvironment, and has poor repairing effect on large-section or refractory bone defects. In recent years, a strategy combining tissue engineering with electrical stimulation (electrotherapy) has become a research hotspot in the field of bone defect repair because of its ability to effectively accelerate bone healing and restore physiological functions of regenerated bone. Researches show that the proper electric stimulation can obviously promote proliferation and osteogenic differentiation of bone marrow mesenchymal stem cells (BMSCs) and promote mineralization efficiency of bone matrix by activating a calcium ion channel, regulating and controlling key signal channels such as PI3K/AKT, WNT and the like. Meanwhile, the electric stimulation can also directly act on vascular endothelial cells, promote the release of Vascular Endothelial Growth Factor (VEGF), accelerate the formation of new blood vessels, thereby improving local blood supply and providing necessary nutrition and oxygen for bone regeneration. However, biological materials achieving effective electrical stimulation still face significant technical bottlenecks, limiting their clinical transformation. On one hand, although the piezoelectric material can generate an electric signal through mechanical deformation, the piezoelectric performance of the piezoelectric material is highly dependent on a precise crystal structure, the structure is easily damaged by mechanical force applied in the manufacturing process of 3D printing and the like, so that the electric output is unstable, and in addition, the mechanical performance of the material is often mismatched with natural bone tissue, so that the piezoelectric material is difficult to adapt to a complex dynamic mechanical environment in vivo. On the other hand, although the conductive hydrogel has good biocompatibility and certain conductivity, the conductive hydrogel generally has the problems of low mechanical strength, poor long-term stability, easy swelling or collapse and the like, most systems need to be powered by an external power supply and cannot realize in-situ self-energy supply in the implant, and the biosafety of part of the conductive filler is not fully verified, so that the application of the conductive hydrogel is further limited. The friction nano generator (TENG) is used as an emerging energy collection technology, and can convert biomechanical energy such as muscle contraction, vascular pulsation and the like in a human body into electric energy through the coupling effect of friction electrification and electrostatic induction, so that a new thought is provided for realizing in-situ self-energy supply electric stimulation without an external power supply. However, existing TENG-based bone repair stents often require an additional encapsulation layer to isolate the moist in vivo environment from degradation of their electrical properties. The encapsulation layer may not only deteriorate the biocompatibility and degradability of the material, but may also trigger a foreign body reaction. In addition, the existing bracket often fails to fully consider the suitability of the bracket to the bone regeneration microenvironment in structural design, the mechanical pro