PEEK porous scaffold surface functional modification method and PEEK porous scaffold
By forming micro- and nanoporous structures on the surface of PEEK porous scaffolds, depositing HA nanolayers in situ, and loading chitosan hydrogels, the bioinertness problem of PEEK scaffolds was solved, achieving functional modification for bone integration and anti-infection, and promoting bone repair.
Patent Information
- Application Number
- CN202511332898.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-18
- Publication Date
- 2026-01-06
AI Technical Summary
PEEK porous scaffolds are bioinert, which limits their ability to integrate and ingrowth into bone, easily induces aseptic loosening of the implant, and are not effective in repairing infected bone defects.
A microporous structure is formed by sulfonation treatment, HA nanolayers are deposited in situ in steps, and pH-responsive chitosan hydrogel is loaded. Calcium peroxide nanoparticles are electrostatically adsorbed to construct a biomimetic natural bone surface, thereby enhancing bioactivity and antibacterial ability.
It improves the bioactivity and osseointegration capacity of PEEK porous scaffolds, provides anti-infection function, promotes bone healing and reduces implant loosening.
Smart Images
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of surface bioactivation modification of medical polymer materials, and particularly relates to a method for surface functionalization modification of a PEEK porous scaffold and the PEEK porous scaffold. BACKGROUND
[0002] Polyether ether ketone (PEEK) is widely used in orthopedic implants due to its excellent biocompatibility and mechanical properties close to human bone. The elastic modulus of PEEK (3-4 GPa) is relatively close to the elastic modulus of cortical bone (about 18 GPa), which is much lower than that of metal (such as titanium alloy of 110 GPa), which can reduce the "stress shielding effect", reduce the risk of adjacent bone absorption and implant loosening, and is not easy to break under long-term dynamic load. PEEK is non-toxic and non-sensitizing, which makes it difficult to cause immune response during long-term implantation, and it is also resistant to corrosion, high temperature and hydrolysis, and suitable for complex physiological environments. In addition, the radiolucency of PEEK (no artifacts under X-ray) and image compatibility (no magnetic interference during magnetic resonance imaging (MRI)) facilitate postoperative image evaluation and bone healing monitoring. Personalized 3D printing technology can customize an implant prosthesis that matches the bone defect site, and the porous structure design helps bone ingrowth. However, the inherent biological inertness of PEEK limits its bone integration and bone ingrowth ability, which can easily induce aseptic loosening of the implant, and even implant failure. Surface bioactivation modification technology is often used to improve the bone repair application of 3D printed PEEK porous scaffolds. Based on the surface microtopography of natural bone matrix and the inorganic components mainly composed of hydroxyapatite (HA, accounting for more than 50% of bone mineral phase), the surface of the 3D printed PEEK porous scaffold is activated and modified to be bone-like, and an intelligent bone repair scaffold for specific application scenarios is constructed, such as a self-regulating anti-infection bone repair scaffold. An innovative solution is provided for the repair of infected bone defects. SUMMARY
[0003] In view of the deficiencies in the prior art, the purpose of the present application is to provide a method for surface functionalization modification of a PEEK porous scaffold and a PEEK porous scaffold, which improves the biological activity, bone integration and antibacterial ability of the PEEK porous scaffold.
[0004] The present application is realized by the following technical solutions:
[0005] A method for surface functionalization modification of a PEEK porous scaffold, comprising the following steps:
[0006] First, a sulfonation treatment is used to form a micro-nano pore structure on the surface layer of the 3D printed PEEK porous scaffold, and the micro-nano pores are uniformly distributed with different pore sizes of 100 nm to 5 um;
[0007] Secondly, HA nanolayer is prepared on the surface of the PEKK scaffold after sulfonation treatment by in-situ step-by-step deposition technology;
[0008] Thirdly, calcium peroxide nanoparticles-containing chitosan hydrogel is loaded on the HA-coated PEKK porous scaffold by electrostatic adsorption principle.
[0009] Preferably, the sulfonation treatment is specifically performed as follows: the 3D-printed PEEK porous scaffold is completely immersed in a concentrated HSO solution, and sulfonation treatment is performed under magnetic stirring for 5 min, then the scaffold is washed with distilled water until the pH is neutral, and then dried for standby use.
[0010] Preferably, the in-situ step-by-step deposition of HA coating on the surface of the sulfonated PEEK scaffold is specifically performed as follows:
[0011] 2.1) The sulfonated PEEK scaffold is immersed in a 5M NaOH solution and treated by magnetic stirring for 24 h to obtain a surface hydroxylated scaffold, which is then washed with distilled water until the pH is neutral, and then dried for standby use;
[0012] 2.2) The hydroxylated PEEK scaffold is immersed in a POCl3 solution and treated by magnetic stirring for 30 min to obtain a phosphate group-modified scaffold, which is then washed with distilled water until the pH is neutral, and then dried for standby use;
[0013] 2.3) The phosphate group-modified scaffold is immersed in a 1M NaOH solution and treated by magnetic stirring for 30 min to obtain a second surface hydroxylated scaffold, which is then washed with distilled water until the pH is neutral, and then dried for standby use;
[0014] 2.3) The second hydroxylated scaffold is immersed in a 1M CaCl2 solution and treated by magnetic stirring for 30 min to enable positively charged Ca 2 + to be adsorbed to the negatively charged phosphate groups, and then the HA-coated porous scaffold is obtained after sufficient washing with distilled water.
[0015] Preferably, the calcium peroxide nanoparticles-containing chitosan hydrogel is loaded on the HA-coated porous scaffold, and the specific operation is as follows:
[0016] The HA-coated porous scaffold is completely immersed in a calcium peroxide nanoparticles-containing chitosan hydrogel solution, and magnetic stirring is performed overnight, followed by freeze-drying to obtain an nCaO2 / chitosan hydrogel-modified HA-coated porous scaffold.
[0017] Preferably, the concentration of the calcium peroxide nanoparticles-containing chitosan hydrogel solution is 2wt%, the content of calcium peroxide nanoparticles nCaO2 in the chitosan hydrogel solution is 5%, and the particle size of the calcium peroxide nanoparticles is 50-200nm.
[0018] The PEEK porous scaffold is prepared by a method for surface functional modification of PEEK porous scaffold.
[0019] The method for surface functional modification of the PEEK porous scaffold of the application forms a surface microporous morphology through sulfonation treatment, deposits an in-situ step-by-step hydroxyapatite (HA) bioactive ceramic coating, and uses a preparation technology of loading nano calcium peroxide (nCaO) to construct an anti-infection bone defect repair scaffold, so that the 3D printed PEEK porous scaffold is functionally modified in structure and composition, and is used for clinical treatment of infectious bone defects.
[0020] The application has the following beneficial effects:
[0021] 1. Sulfonation treatment improves the surface bioactivity of PEEK
[0022] The inherent biological inertness of PEEK limits its bone regeneration and bone reconstruction ability in clinical application. Sulfonation treatment helps to introduce microporous morphology and sulfonic acid groups on the surface of PEEK, thereby improving its biological activity and hydrophilicity. In addition, the sulfonic acid groups introduced on the surface of PEEK can facilitate the functional surface modification of other functional groups.
[0023] 2. In-situ step-by-step deposition of HA coating improves the osteogenic ability while retaining the microporous structure of the surface layer
[0024] The application uses an in-situ step-by-step deposition process to make phosphate and calcium ions penetrate into the microporous structure of the PEEK scaffold surface layer, and forms a HA coating that mimics the natural bone, which can promote the adhesion, proliferation and differentiation of cells (such as osteoblasts and mesenchymal stem cells), and accelerate the bone integration process. Step-by-step deposition helps the bioactive ions to freely penetrate the microporous and nanometer pores, which can avoid the blockage of the microporous structure of the PEEK scaffold surface layer by HA particles formed by the combination of phosphate and calcium ions in the one-step in-situ deposition process. The in-situ step-by-step deposition of the HA coating improves the osteogenic ability of the PEEK scaffold while retaining the microporous structure of the surface layer, and realizes the biomimicry of the surface structure and chemical composition of the natural bone.
[0025] 3. Loading nCaO2 on the HA-coated PEEK scaffold using pH-responsive chitosan hydrogel
[0026] O2 is electrostatically adsorbed onto the HA-coated PEEK scaffold to construct an intelligent anti-infection bone repair scaffold. Given the acidic nature of the PH of the infection microenvironment, the application uses pH-responsive chitosan hydrogel to load and control the release of nCaO2 on the HA-coated PEEK scaffold, and continuously releases oxygen (O2) and calcium ions (Ca 2+), improve the hypoxic environment of the bone defect site, promote osteoblast proliferation and differentiation. On the one hand, according to the change of the infected microenvironment, the pH-responsive slow-release nCaO plays an antibacterial and anti-inflammatory effect by scavenging reactive oxygen species. On the other hand, the bionic natural bone microtopography and HA coating help blood vessel neogenesis, accelerate bone matrix deposition, and promote bone integration and bone ingrowth.
[0027] The method for surface functionalization modification of the PEEK porous scaffold of the present application in-situ step-by-step deposits hydroxyapatite. The in-situ step-by-step deposited HA surface presents a nanoparticle morphology, and Ca, P and O elements are uniformly distributed and correspond to the HA surface morphology characteristics. The characteristic chemical bonds on the PEEK scaffolds treated by different surfaces respectively confirm the in-situ step-by-step deposition of HA and the successful loading of chitosan hydrogel. The present application bionically mimics natural bone, and functionally modifies the 3D printed PEEK porous scaffold in terms of structure and composition, develops an intelligent anti-infection bone repair scaffold, and constructs a fine and functional bone repair material, so as to promote bone healing under the condition of eliminating infection and overcome the current problem of treating infected bone defects by staged surgery in clinical practice. BRIEF DESCRIPTION OF DRAWINGS
[0028] Figure 1 is a process flow chart of the surface functionalization modification of the PEEK porous scaffold of the present application;
[0029] Figure 2 SEM photos of the micro-nano pore structure formed on the surface layer of the PEEK scaffold treated by sulfonation according to the present application;
[0030] Figure 3 SEM photos and element Mapping diagrams of the in-situ step-by-step deposition of HA coating on the surface of the sulfonated PEEK scaffold according to the present application;
[0031] Figure 4 FTIR diagram of the chitosan hydrogel layer containing nCaO2 loaded on the surface of the HA coated PEEK scaffold according to the present application;
[0032] Figure 5 Cell proliferation curves of BMSC and HUVEC cells cultured on the scaffold according to the present application for 24, 48 and 72 h;
[0033] Figure 6 Alizarin red staining diagram of mineralized calcium nodules of BMSC cells stimulated by the scaffold according to the present application for 14 days;
[0034] Figure 7 Bacterial dilution spread plate of Staphylococcus aureus stimulated by the scaffold according to the present application for 24 h. DETAILED DESCRIPTION
[0035] The application will be further described in detail below with reference to specific examples, which are intended to explain but not limit the application.
[0036] Example 1:
[0037] As Figure 1 is the modification process diagram of the application, the 3D printed PEEK porous scaffold is completely immersed in concentrated H2SO4(98%) solution, and sulfonated under the action of magnetic stirring for 5 min. After washing with distilled water until the pH is neutral, it is dried for standby use.
[0038] The sulfonated PEEK scaffold is immersed in 5M NaOH solution and treated by magnetic stirring for 24h to obtain a surface hydroxylated scaffold. After washing with distilled water until the pH is neutral, it is dried for standby use. The hydroxylated scaffold is immersed in POCl3 solution and treated by magnetic stirring for 30 min to obtain a phosphate group modified scaffold. After washing with distilled water until sufficient, it is dried for standby use. The phosphate group modified scaffold is immersed in 1M NaOH solution and treated by magnetic stirring for 30 min to obtain a secondary surface hydroxylated scaffold. After washing with distilled water until the pH is neutral, it is dried for standby use. The secondary hydroxylated scaffold is immersed in 1M CaCl2 solution and treated by magnetic stirring for 30 min. After washing with distilled water until sufficient, it is dried for standby use to obtain a HA coated porous scaffold, realizing in-situ step-by-step deposition of HA coating.
[0039] The HA coated porous scaffold is completely immersed in a chitosan hydrogel solution containing 5% nano calcium peroxide particles (nCaO2) with a concentration of 2wt%, and is treated by magnetic stirring overnight. After freeze-drying, a nCaO2 / chitosan gel modified HA coated porous scaffold is obtained.
[0040] Referring to Figure 2 It is shown that the 3D printed PEEK scaffold is immersed in concentrated hydrochloric acid solution for sulfonation treatment, and the surface layer forms a micro-nano pore structure morphology. The micro-nano pores are uniformly distributed, and the pore size is 100nm-5um in size.
[0041] Referring to Figure 3 It is shown that the sulfonated PEEK scaffold surface in-situ step-by-step deposits HA coating, and the surface presents a nano-particle morphology. Element Mapping shows that Ca, P and O elements are uniformly distributed, and correspond to the surface morphology characteristics of SEM.
[0042] Referring to Figure 4As shown, the Fourier transform infrared spectrum (FTIR) diagram respectively shows the characteristic chemical bonds of each molecule of the original PEEK scaffold (P), the HA coated PEEK scaffold (CP) and the nano calcium peroxide particle containing chitosan hydrogel loaded on the HA modified PEEK scaffold (nCP), the C-H and O-H on the P spectrum line (the lowest spectrum line) are the characteristic chemical bonds on the PEEK; the -PO4 on the CP spectrum line (the middle spectrum line) appears, -PO4 is the characteristic chemical bond of HA, indicating that HA is deposited in situ step by step; the -NH2, -CO and -CH on the nCP spectrum line (the uppermost spectrum line) all appear, which are the characteristic chemical bonds of chitosan, and the surface chitosan gel is loaded on the HA modified PEEK scaffold.
[0043] Referring to Figure 5 As shown, the cell proliferation curves of BMSC and HUVEC cells on the above three kinds of scaffolds for 24, 48 and 72 hours show that the scaffold of the application has better biocompatibility.
[0044] Referring to Figure 6 As shown, the alizarin red staining of mineralized calcium nodules of BMSC cells stimulated by the scaffold of the application for 14 days shows that the scaffold of the application has better osteogenic ability.
[0045] Referring to Figure 7 As shown, the bacterial dilution spread plate of Staphylococcus aureus stimulated by the scaffold of the application for 24 hours shows that the scaffold of the application has good antibacterial function.
[0046] Many examples can be listed, but not all are listed here, in summary, within the scope provided by the application, functional composite coatings can be prepared on the surface of 3D printed PEEK porous scaffolds by using sulfonation reaction, in-situ step-by-step deposition and electrostatic adsorption, and an intelligent anti-infection bone repair scaffold is constructed.
[0047] The modified PEEK porous scaffold of the application has biological activity, bone integration and antibacterial ability.
[0048] Finally, it should be pointed out that: the above examples are only used to illustrate the technical solutions of the application, but not to limit them; although the application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: they can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the application.
Claims
1. A method for surface functionalization modification of PEEK porous scaffolds, characterized in that The method comprises the following steps: First, a micro-nano pore structure is formed on the surface of the 3D-printed PEEK porous scaffold by sulfonation treatment, and the micro-nano pores are uniformly distributed and have different sizes of 100 nm to 5 um; Second, a HA nano layer is prepared on the surface of the PEEK scaffold after sulfonation treatment by in-situ step-by-step deposition technology; Third, calcium peroxide nanoparticle-containing chitosan hydrogel is loaded on the HA-coated PEEK porous scaffold by electrostatic adsorption principle.
2. The method of surface functionalization modification of PEEK porous scaffolds according to claim 1, characterized in that The specific operation of the sulfonation treatment is as follows: the 3D-printed PEEK porous scaffold is completely immersed in a concentrated HSO solution, and sulfonation treatment is performed under the action of magnetic stirring for 5 min, then the scaffold is washed with distilled water until the pH is neutral, and then the scaffold is dried for standby use.
3. The method of surface functionalization modification of PEEK porous scaffolds according to claim 1, characterized in that The specific operation of the in-situ step-by-step deposition of the HA coating layer on the surface of the sulfonated PEEK scaffold is as follows: 2.1) The sulfonated PEEK scaffold is immersed in a 5M NaOH solution and treated by magnetic stirring for 24 h to obtain a surface hydroxylated scaffold, which is then washed with distilled water until the pH is neutral, and then the scaffold is dried for standby use; 2.2) The hydroxylated PEEK scaffold is immersed in a POCl3 solution and treated by magnetic stirring for 30 min to obtain a phosphate group-modified scaffold, which is then washed with distilled water until the pH is neutral, and then the scaffold is dried for standby use; 2.3) The phosphate group-modified scaffold is immersed in a 1M NaOH solution and treated by magnetic stirring for 30 min to obtain a second surface hydroxylated scaffold, which is then washed with distilled water until the pH is neutral, and then the scaffold is dried for standby use; 2.3) The di-hydroxylated scaffold is immersed in 1 M CaCl2solution and magnetically stirred for 30 min to allow positively charged Ca 2+ After sufficient rinsing with distilled water, the HA-coated porous scaffold is obtained.
4. The method of surface functionalization modification of PEEK porous scaffolds according to claim 1, characterized in that The specific operation of loading the calcium peroxide nanoparticle-containing chitosan hydrogel on the HA-coated porous scaffold is as follows: The HA-coated porous scaffold is completely immersed in a calcium peroxide nanoparticle-containing chitosan hydrogel solution, and magnetic stirring is performed overnight, and then freeze-drying is performed to obtain an nCaO2 / chitosan hydrogel-modified HA-coated porous scaffold.
5. The method of surface functionalization modification of a PEEK porous scaffold according to claim 4, wherein: The concentration of the calcium peroxide nanoparticle-containing chitosan hydrogel solution is 2 wt%, the content of the calcium peroxide nanoparticles nCaO2 in the chitosan hydrogel solution is 5%, and the particle size of the calcium peroxide nanoparticles is 50-200 nm.
6. A PEEK porous scaffold prepared by the method for surface functionalization modification of the PEEK porous scaffold according to any one of claims 1-5.