CN116397203A - Method for bionic modification of polyether-ether-ketone surface - Google Patents
Method for bionic modification of polyether-ether-ketone surface Download PDFInfo
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- CN116397203A CN116397203A CN202310095468.2A CN202310095468A CN116397203A CN 116397203 A CN116397203 A CN 116397203A CN 202310095468 A CN202310095468 A CN 202310095468A CN 116397203 A CN116397203 A CN 116397203A
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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Abstract
The invention relates to the technical field of medical material preparation, in particular to a method for biomimetically modifying the surface of polyether-ether-ketone. Comprises the following steps: sequentially using acetone, ethanol and deionized water to ultrasonically clean the polyether-ether-ketone material; step 2: immersing the polyether-ether-ketone material subjected to ultrasonic cleaning into 98% concentrated sulfuric acid for acid etching, taking out, cleaning in ultrapure water, and sequentially using acetone, ethanol and deionized water for ultrasonic cleaning after the ultrasonic cleaning is completed; step 3: and sputtering the hydroxyapatite on the surface of the polyether-ether-ketone material by using the acid-etched polyether-ether-ketone material as a matrix and using the hydroxyapatite as a target material through magnetron sputtering, so as to prepare the bioactive coating of the bionic mineralized fiber bundle on the surface of the polyether-ether-ketone material. The coating prepared by the invention can simulate the three-dimensional network morphology of the natural bone tissue mineralized collagen fiber bundles and the hydroxyapatite components among the fiber bundles, effectively promote in-vitro cell adhesion and osteogenesis differentiation, and promote in-vivo osseointegration.
Description
Technical Field
The invention relates to the technical field of medical material preparation, in particular to a method for biomimetically modifying the surface of polyether-ether-ketone.
Background
Polyetheretherketone (PEEK) is a semi-crystalline organic polymer material that has been receiving increasing attention from students due to its good corrosion resistance, biocompatibility, minimal interference with imaging and mechanical properties approaching natural bone tissue. Since 1992, PEEK was applied in the oral field, beginning with its aesthetic repair advantages, and then focusing more on its application in jaw implant implantation. PEEK is increasingly favored by clinicians, mainly based on its following advantages:
(1) the chemical property is stable: the PEEK material has the advantages of corrosion resistance, high chemical stability and the like, and the PEEK material is biologically inert in an in-vivo environment. The biosafety experiment proves that the PEEK material has no toxicity of cells, tissues, inheritance and the like, and in vitro and in vivo experiments prove that the PEEK material has good compatibility with various cells and tissues such as epithelium, muscle, bone, cartilage and the like.
(2) The mechanical properties are suitable: the biomechanical parameters such as the elastic modulus (4 GPa) and the tensile strength (93 MPa) of the PEEK material are closer to the cortical bone (16-23 GPa;80-150 MPa) than the biomechanical parameters of titanium and titanium alloy (110 GPa;897-1034 MPa), so that the stress shielding effect can be avoided and the in vivo cell biomechanical microenvironment can be simulated.
(3) Does not interfere with the imaging examination: PEEK material presents transmission shadow on clinical X-ray film, can avoid the artifact that appears when X-ray and CT examine, and it also can avoid phenomena such as magnetic resonance scattering artifact and implant heat production simultaneously to the application advantage is huge in joint surgery, neurosurgery.
(4) The color is beautiful and easy to adjust: since titanium implants can make the buccal side of the upper jaw grey to varying degrees, even a patient with mild gingival atrophy can result in cosmetic exposure of the prosthesis to color that can affect aesthetics. Whereas the PEEK material is white, which makes it very suitable for medical aesthetic areas such as the front teeth of the mouth. In addition, PEEK does not generate heat in high-speed rotation contact with the cutting drill, which is beneficial to temporary adjustment and intraoperative forming of the implant in clinical operation, and improves the fault tolerance and the application range of the implant in clinical use. Therefore, PEEK is considered as an ideal substitute material for the traditional titanium alloy bone implant, clinical application and popularization of PEEK are gradually increased in recent years, and PEEK becomes one of emerging means for fracture fixation, bone defect reconstruction and repair and the like in foreign areas, particularly European and American developed areas.
However, in practice we have found that PEEK materials are too inert and lack bioactive sites to form effective osseointegration with the surrounding bone tissue. After implantation, the screw is used for retention, the local stress is high, and the mechanical risks of screw falling off, local fracture and the like in long-term application are high, so that the application and popularization of the method in the clinical treatment of jawbone defects and deformity are severely restricted. Therefore, the modification of the peek material and the improvement of the bioactivity of the peek material have important clinical value and research significance.
The modification modes of the Peek material mainly comprise blending modification, surface modification and the like. The blending modification (Blending Modification) is to utilize the combination of the bioactive component and the biologically inert PEEK matrix to enhance the bioactivity of PEEK. However, the mechanical properties of the PEEK composite material can be seriously influenced by blending modification, the mechanical strength and ductility of the composite material are reduced, the surface wear resistance of the blending material is reduced, risks such as free particles of the blending material occur, and the surface coating modification can activate the surface of the PEEK material on the premise of avoiding influencing the basic mechanical properties of the PEEK material, so that the PEEK material becomes a main stream modification mode of the PEEK material.
Bone conduction (osteoinductive) refers to the appropriate scaffold provided by the material for the formation of new bone and vascular ingrowth, which requires the material to have surface features that induce the corresponding angiogenic function and spatial dimensions to suit cell adhesion growth, migration. Osteoinductive (osteoinductive) refers to the property of a material that directly induces mesenchymal stem cells to differentiate into osteogenic and osteoblastic cells, thereby forming bone tissue, and has a certain capacity of promoting new bone formation even in a non-bone environment. The definition and characteristics of the bone conductivity and the bone inducibility indicate that the PEEK material can be subjected to bionic modification from two aspects of interface physical structure and chemical composition, so that the PEEK material is endowed with the bone conductivity and the bone inducibility required by the PEEK material, and the bone integration effect is promoted.
The micron-sized structure of bone tissue is composed of collagen fibers and mineral deposits thereon, and is a basic unit for mechanical bearing. The micron-sized structure can furthest increase the embedding of the surface of the implant and the surrounding mineralized bone tissue, and can obviously improve the adhesion and migration capacity of osteoblasts on the premise of good wettability. Therefore, the structure of the natural bone tissue collagen fiber bundles and the mineral substances on the natural bone tissue collagen fiber bundles are simulated, the biological activity of the peek material can be effectively improved, and the combination of the peek material and the bone tissue is promoted.
Micro/nanostructures mimicking natural bone tissue are effective means to promote osseointegration of implant materials. At present, a great deal of research has been conducted to modify the topography of the surface of materials. Highly regular morphologies, such as nanowires, nanopillars, nanoneedles, nanocones, nanopipettes, and nanogrooves, are effective tools for studying the response mechanisms of cells and materials. However, most highly regular nanotopography is limited by low binding strength and therefore lacks clinical transformation potential and it does not fully mimic the micro/nanostructures of bone tissue in vivo. The extracellular matrix of the bone tissue is an irregular fiber network structure composed of fiber bundles of 500 nm-1 mu m, and the fiber bundles have obvious osteogenic advantages in the aspects of cell attachment, stem cell differentiation, mineralized tissue formation and the like. Therefore, the unordered 3D bracket surface with high bonding strength can solve the disadvantages of low bonding strength and insufficient bionic property of highly regular nanotopography to a certain extent.
Modeling the composition of bone tissue is another strategy for material modification. Hydroxyapatite (HA), which consists of calcium phosphate (Ca-P), is the main chemical component of bone tissue (about 70 wt%), is generally considered to be a bioactive coating material that can increase osseointegration. However, high crystallinity HA is essentially non-biodegradable, which contributes to poor bone bioactivity. In contrast, amorphous HA and ion-substituted HA have better biodegradability properties and thus are more favorable for cell attachment and osteogenic differentiation. In addition, osteoblast-coated surfaces that form bone in vivo are mainly composed of amorphous HA and amorphous calcium phosphate, while osteoclast-coated surfaces that are bone-resorbed are highly crystalline HA. Thus, it may be more advantageous to simulate amorphous HA on the surface of a material to increase its osteogenic activity.
In natural bones, organic components such as collagen fibers and inorganic components such as calcium and phosphate are interwoven together to form a micron-sized mineralized fiber bundle structure. The composite structure of mineralized collagen fiber bundles provides initial sites for in vivo mineralization and osteogenesis, regulates in vivo osteogenesis microenvironment, and finally endows bone tissues with toughness and bearing strength. Interestingly, the structure of the network fiber bundles produced by sulfonation of the PEEK surface was similar to that of collagen fiber bundles in bone tissue, but its biological activity was negligible in the absence of active factors. Therefore, the preparation of the biomimetic mineralized collagen fiber bundle surface by more effectively loading mineral components is probably a new research direction for biomimetically modifying the PEEK surface to improve the osteogenic performance of the PEEK surface.
Magnetron sputtering (Magnetron Sputtering) has been rapidly developed in the 70 s of the 20 th century, and is characterized in that high-energy particles bombard the surface of a target material, so that target atoms are transferred to the surface of a matrix material to prepare a coating, and the coating has the characteristics of easy control, uniform and consistent film formation, high film formation rate and the like, and is widely applied to the preparation of surface coatings of various materials such as metals, polymers, ceramics and the like. Therefore, the construction of the bionic modified coating can be effectively realized through the magnetron sputtering technology.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for carrying out bionic modification on the surface of polyether-ether-ketone, which comprises the steps of carrying out acid etching (sulfonation) by concentrated sulfuric acid and magnetron sputtering of hydroxyapatite, and constructing a bionic coating of amorphous hydroxyapatite which is uniformly deposited along sulfonated fiber bundles on the surface of PEEK by adjusting specific parameters. The coating can simulate the three-dimensional reticular morphology of the mineralized collagen fiber bundles of natural bone tissues and amorphous hydroxyapatite components among the fiber bundles, effectively promote in-vitro cell adhesion and osteogenesis differentiation, improve bone conduction and bone induction performance after in-vivo implantation, and finally promote osseointegration.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for biomimetically modifying the surface of polyether-ether-ketone comprises the following steps:
step 1: sequentially using acetone, ethanol and deionized water to ultrasonically clean the polyether-ether-ketone material;
step 2: immersing the polyether-ether-ketone material subjected to ultrasonic cleaning in the step 1 into 98% concentrated sulfuric acid for acid etching, taking out, cleaning in ultrapure water, and sequentially using acetone, ethanol and deionized water for ultrasonic cleaning after the ultrasonic cleaning is completed;
step 3: and (3) taking the polyether-ether-ketone material subjected to acid etching in the step (2) as a matrix, taking hydroxyapatite as a target material, and sputtering the hydroxyapatite on the surface of the polyether-ether-ketone material by magnetron sputtering, so as to prepare the bioactive coating of the biomimetic mineralized fiber bundle on the surface of the polyether-ether-ketone material.
Preferably, in the step 1, the time for ultrasonic cleaning of the acetone, the ethanol and the deionized water is 15min.
Preferably, the acid etching time in the concentrated sulfuric acid in the step 2 is 3min.
Preferably, the vacuum degree of the main sputtering chamber and the sample injection chamber of the magnetron sputtering in the step 3 is 5 multiplied by 10 -5 -8×10 -5 Pa, power 200W, sputtering time 2h.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the invention uses concentrated sulfuric acid to sulfonate to form a net-shaped interweaved filiform fiber bracket structure on the PEEK surface. Then, it was encapsulated with amorphous hydroxyapatite by magnetron sputtering to form a surface similar to the structure of mineralized collagen fiber bundles. The novel biomimetic surface combines the dual advantages of the composition of amorphous hydroxyapatite (the core component of the in vivo osteogenic region) and the physical microstructure stimulation of mineralized collagen fiber bundles. Moreover, the composite design of mineral salts and fibers also solves the inherent brittleness problem of mineral salt coatings. Finally, the coating improves bone conduction and bone induction performance, ensures bone formation activity and bone integration, and ensures that the bone integration effect of the PEEK implant reaches or even partially exceeds that of a titanium implant commonly used in clinic.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
In the drawings:
FIG. 1 is a flow chart of the method of the present invention;
FIG. 2 is a scanning electron microscope image of the sulfonation parameter screening of the present invention;
FIG. 3 shows the scanning electron microscope observation after the optimal sulfonation parameters are processed, and the magnetron sputtering parameters are further screened;
FIG. 4 is a representation of a coating prepared according to the present invention: atomic Force (AFM), roughness, XPS, XRD, hydrophilicity, and scratch detection;
FIG. 5 is an in vitro cell adhesion assay of the invention: DAPI staining and quantitative statistics, electron microscopy and confocal observation of cell morphology;
FIG. 6 is an in vitro osteogenic differentiation assay of the invention: ALP (alkaline phosphatase) detection, qRT-PCR detection of osteogenic related genes (Col-1, runx2, OCN, OPN);
FIG. 7 is a three-dimensional reconstruction and statistics of the implanted micro-CT of the present invention: cancellous bone segments (bone conduction + bone induction) and bone marrow cavity segments (bone induction);
FIG. 8 shows VG staining of the implanted hard tissue sections, quantitative statistics of bone implant contact ratio (BIC%) and dual fluorescent labeling and quantitative statistics according to the present invention.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
Examples:
a method for biomimetically modifying the surface of polyether-ether-ketone comprises the following steps:
step 1: sequentially using acetone, ethanol and deionized water to respectively ultrasonically clean the polyether-ether-ketone material for 15min;
step 2: step 2 is sulfonation operation, specifically, immersing the polyether-ether-ketone material subjected to ultrasonic cleaning in the step 1 into 98% concentrated sulfuric acid for 3min for acid etching, taking out, cleaning in ultrapure water for 15min, sequentially using acetone, ethanol and deionized water for ultrasonic cleaning after cleaning is finished, and finally drying in a dryer for standby.
Observation by SEM is successfully carried out, under the parameter of 98% concentrated sulfuric acid treatment for 3min, the optimal three-dimensional porous network structure of three-dimensional porosity is prepared on the PEEK surface, and the substrate morphology (A in figure 2) of uniformly connecting fine bundle fibers among holes is very similar to that of mineralized collagen fiber bundles, namely basic structural units of human bone tissue, and the naturally formed three-dimensional network cancellous bone structure. However, if the sulfuric acid concentration is reduced, the three-dimensional network will become flattened and uneven connection between holes will occur (B in fig. 2); when the concentration of sulfuric acid and the treatment time are reduced, larger two-dimensional holes appear on the surface of the material, and a three-dimensional network structure in the bone of the human body cannot be formed (C in fig. 2). Meanwhile, if the concentrated sulfuric acid treatment time is prolonged, although the fine fiber bundles can still be seen on the surface of the PEEK material, the fiber filaments of the outermost layer are in a curled state (D in FIG. 2).
Step 3: taking the polyether-ether-ketone material subjected to acid etching in the step 2 as a matrix, taking hydroxyapatite as a target, putting the target and the matrix into a main sputtering chamber and a sample injection chamber, and vacuumizing the main sputtering chamber and the sample injection chamber to 5 multiplied by 10 -5 -8×10 -5 Pa, pre-sputtering and cleaning the implant matrix in a sample injection chamber for 20-40 minutes, and uniformly depositing a hydroxyapatite layer along the three-dimensional reticular fiber bundles of the polyether-ether-ketone material by a magnetron sputtering technology, thereby preparing a bioactive coating of the bionic mineralized fiber bundles on the surface of the polyether-ether-ketone material, wherein the diameter of the obtained bionic mineralized collagen fiber bundles is about 0.34+/-0.026 mu m, and the diameter of the fiber bundles is about 1.83+/-0.351 mu m.
Subsequently, we further used magnetron sputtering technique to sputter Hydroxyapatite (HA) on its surface to simulate the calcium-phosphorus component in human bone. As can be seen by SEM, HA is uniformly coated on the surface of smooth PEEK by magnetron sputtering treatment to form an amorphous spherical island-shaped calcium-phosphorus film (A in figure 3). Based on this, the fiber scaffold was further wrapped under the above-prepared optimal three-dimensional porous mesh substrate using magnetron sputtering. And successfully prepares the optimal substrate morphology (B in figure 3) of the uniform deposition of HA along the fiber bundles under the parameters of 200W of radio frequency power, 100V of direct current bias and 2 hours of deposition time and clearly visible holes. However, if the radio frequency power is enhanced, the substrate three-dimensional network is almost completely covered by the HA film, the pores and the fiber bundle structure of which are substantially invisible; the porous structure of the substrate was seen by increasing the rf power and deposition time, but the HA deposition was not uniform along the pores and the fiber bundle morphology was not seen (C-D in fig. 3). In addition, from the quantitative results on the width and the interval of the fiber bundles, the morphology of the mineralized fiber bundles is more obvious under the parameter treatment of 200W and 2h, and the diameter of the mineralized fiber bundles is 0.34+/-0.026 mu m, which is consistent with the diameter of the mineralized collagen fiber bundles of the natural bone tissues. While the mineralized fiber bundles were covered to form a film morphology (E-F in FIG. 3) under the parameter treatment of 290W, 3 h.
In summary, we have studied two steps, and by specific sulfonation and magnetron sputtering parameters (G in fig. 3), we succeeded in constructing a biomimetic mineralized fiber bundle scaffold surface that mimics mineralized collagen fiber bundles (basic structural units of human bone tissue) from both structure and composition on the PEEK surface.
Further material characterization, experimental grouping: materials were classified into P-group (pure PEEK), sP-group (sPEEK, PEEK with surface treated with optimal sulphonation parameters), spe-group (speek+ha, PEEK with surface treated with optimal sulphonation and optimal magnetron sputtering parameters) and Ti-group (pure titanium).
Each group of materials was characterized by Atomic Force Microscopy (AFM), X-ray photoelectron spectroscopy (XPS), X-RayDiffraction (XRD), contact Angles (CAs) and Scanning Electron Microscopy (SEM). AFM data showed (A, B in FIG. 4), the average roughness (Ra) of P vs. sP vs. sP-HA vs. Ti was 0.028 vs.0.15 0.15 vs.0.12 0.12 vs.0.049 (. Mu.m). Compared with the P group, the roughness of the sP group is obviously different (P is less than 0.0001), which indicates that the surface of the sP group material can form a good bracket structure; compared with the sP group, the roughness of the sPHA group is reduced to a certain extent (P is smaller than 0.01), but the roughness is still higher than that of the P group and the Ti group (both P is smaller than 0.0001), which indicates that the surface of the sPHA group material can still form a better bracket structure. By XPS, XRD analysis (C, D in fig. 4) of the surface elements and crystal phases of the sfa group, it was confirmed that Ca, P, O elements in HA were successfully deposited on the surface thereof, and the deposited HA was amorphous. Contact Angle (CAs) measurements found (E in fig. 4) that the contact angles of the P, sP-HA and Ti groups were 91.83 ±3.10°, 107.57 ±3.52°, 21.40±3.22° and 72.23 ±4.04°, respectively. The sP contact angle after sulfonation treatment is increased (P < 0.01) compared with P; compared with sP, the contact angle of sPHA after magnetron sputtering HA is obviously reduced (P is less than 0.0001), which indicates that the hydrophilicity is better than that of sP; and the hydrophilicity of sPHA is better than Ti (P < 0.0001). Subsequently, we scored the surface of the sPHA group material (F in FIG. 4), and SEM results showed that a uniform three-dimensional network of substrates was visible at low magnification on the material surface, with no film-like coating and no significant edge embrittlement. The scored edges were observed at high magnification and the web was seen to collapse rather than the coating breaking off.
To study the biocompatibility of the scaffold material, we inoculated equivalent amounts of rat P3 generation BMMSCs cells on the surface of each group of materials, and observed and analyzed the number of cells adhered to the surface of the materials by using a confocal microscope after 30min, 60min and 120min of contact. The results show (A, B in FIG. 5) that the cell numbers on the surfaces of all four groups of materials increased with time. Compared with the P group and the sP group, the number of the cell adhesion of the BMMSCs of the sPHA group is obviously increased at any time point, and the difference has statistical significance; compared with the Ti group, the number of BMMSCs cell adhesion of the sPHA group is slightly reduced (P < 0.05) at 30min, and the sPHA group has no statistical significance at 60min and 120 min. The adhesion state of BMMSCs cells is observed by SEM and immunofluorescence staining (C, D in FIG. 5), compared with the P group and the sP group, the sPHA group BMMSCs cells have more filopodia, and the cell morphology is more extended; compared with the Ti group, both BMMSCs can be well stretched, but the sPHA group is based on a three-dimensional network structure after sulfonation, so that more anchor points of the adhesion cells can be in closer contact with the material.
In order to evaluate the influence of the prepared bionic scaffold material on the osteogenic differentiation capacity of BMMSCs, the surface of each group of materials is inoculated with equivalent rat P3 generation BMMSCs cells, and after the BMMSCs are cultured for 7 days by an osteogenic differentiation induction culture medium, ALP staining and quantitative analysis are adopted to detect the ALP expression change of the BMMSCs cultured on each group of materials. ALP detection results show (A, B in FIG. 6), compared with the P group and the sP group, the ALP dyeing depth of the sPHA group is enhanced, the distribution area is increased, and the activity of the quantitative analysis ALP is obviously improved (P is less than 0.01); compared with the Ti group, the ALP dyeing depth and the distribution area of the sPHA ALP are not obviously different, and the activity change is not statistically significant. Indicating that the sPHA group has a certain influence on the early osteogenic differentiation of BMMSCs. To further verify the change in expression of the scaffold material osteogenic related genes, we detected the expression levels of type I collagen (Col-I), encoding specific transcription factors (Runx 2), osteocalcin (Ocn) and osteopontin (Opn) by real-time quantitative polymerase chain reaction (qRT-PCR) on day 7 of conditioned medium induced osteogenic differentiation found (C-F in fig. 6), with significant upregulation of Col-I, runx2, ocn and Opn expression (all P < 0.05) in the sfa group compared to the P and sP groups; compared with the Ti group, the expression of sPHA groups Col-I, runx2, ocn and Opn has no statistical significance.
In order to further explore the influence of the prepared bionic scaffold material on implant osseointegration, a femur defect animal model is constructed by utilizing an SD rat, and various groups of implant materials are implanted into femur on two sides of the rat. The rats are sacrificed 8 weeks after the operation, and the femur is taken to evaluate the bone-combining effect around the implant through micro-CT; detecting the osteogenesis and the osseointegration around the implant by utilizing VG staining of the hard tissue slice; in addition, the process of new bone formation around the implant was examined by continuous fluorescence labeling 10 days before the sacrifice.
micro-CT examination and observation were divided into cancellous bone segments and bone marrow cavity segments (FIG. 7). Firstly, a cancellous bone segment 2mm below the metaphyseal is selected, and a region of interest within 2mm is selected for micro-CT analysis. It can be seen (fig. 7 a) that the cross-sectional two-dimensional image shows that the new bone of the sfa group is continuous, uniformly distributed annularly along the periphery of the implant, the P group and the sP group are discontinuously distributed annularly, and the annular distribution of the Ti group has obvious intermittent defects. The three-dimensional reconstructed image further verifies that the sfa group has higher amounts of new bone growth. Further quantitative statistical analysis indicated (B-E in fig. 7), that the sfa group had the highest amount of new bone formation, superior to the positive control group Ti, significantly superior to the P and sP groups. Meanwhile, the sPHA group has the highest TbTh, tbN and lower TbSp, which indicates that the bone reconstruction of the sPHA group is more mature, the newly-formed bone around the implant is good, and the bone plate is mainly lamellar bone, so that the sPHA group has good bone conduction and bone induction. While the p and sP groups are still in the transition phase of the woven bone to lamellar bone.
Subsequently, the same parameters were used to analyze the region of interest over a 2mm range of the bone marrow cavity segment, and it was seen (F in fig. 7) that the cross-section and three-dimensional reconstructed images of the sfa group indicated that the fresh bone around the implant was continuous and the bone mass was the greatest, while the fresh bone distribution around the implants of the P and sP groups was more defective and the bone mass was less, and the fresh bone of the Ti group was the least continuous and the bone mass was the least. Quantitative statistical analysis showed (G-J in fig. 7), the sfa group had higher TbTh, tbN and lowest TbSp, indicating that it achieved good bone remodeling with good osteoinductive properties on the premise of ensuring bone mass. While the higher TbTh, tbSp and lowest TbN of group P demonstrated that there was only scattered bone remodeling. The bone mass of the sP group was not significantly different from that of the P group, but its lower TbTh and TbSp and higher TbN suggested that bone remodeling was more active than that of the P group. The lowest bone mass, the lowest TbTh, the highest TbN and the higher TbSp of the Ti group prove that the bone reconstruction is not perfect and the osteoinductive property is poor.
VG staining results and quantitative analysis thereof showed that new bone formation was observed around all four groups of implant materials (A-B in FIG. 8). There was significant fibrous tissue between the bone-implant contact interfaces of the P and sP groups, and no continuous direct bone contact was seen. The sPHA group bone implant interface has continuous direct bone contact, and the fibrous tissue is basically invisible; compared with the other three groups, the bone implant contact ratio of the sPHA group is obviously increased (P is less than 0.05). Fibrous tissues exist between the implant of the Ti group and the bone tissues, but the direct bone contact degree is obviously better than that of the P group and the sP group, and the differences have statistical significance (P is less than 0.01). The green color in the continuous fluorescent label represents calcein and the red color represents tetracycline, and it is seen (C-D in FIG. 8) that the two fluorescence pitches are respectively 0.51+ -0.14 unit for P group, 0.24+ -0.08 unit for sP group, 1.91+ -0.28 unit for sPHA group, and 1.26+ -0.10 unit for Ti group. Compared with the other three groups, the fluorescence interval of the sPHA group is the largest, the new bone formation rate is the fastest, and the differences have statistical significance (P is less than 0.05), which indicates that the promotion effect of the sPHA group on bone deposition and bone remodeling is stronger.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A method for biomimetically modifying the surface of polyether-ether-ketone is characterized in that: the method comprises the following steps:
step 1: sequentially using acetone, ethanol and deionized water to ultrasonically clean the polyether-ether-ketone material;
step 2: immersing the polyether-ether-ketone material subjected to ultrasonic cleaning in the step 1 into 98% concentrated sulfuric acid for acid etching, taking out, cleaning in ultrapure water, and sequentially using acetone, ethanol and deionized water for ultrasonic cleaning after the ultrasonic cleaning is completed;
step 3: and (3) taking the polyether-ether-ketone material subjected to acid etching in the step (2) as a matrix, taking hydroxyapatite as a target material, and sputtering the hydroxyapatite on the surface of the polyether-ether-ketone material by magnetron sputtering, so as to prepare the bioactive coating of the biomimetic mineralized fiber bundle on the surface of the polyether-ether-ketone material.
2. The method for biomimetically modifying the surface of polyether-ether-ketone according to claim 1, wherein the method comprises the following steps: in the step 1, the ultrasonic cleaning time of the acetone, the ethanol and the deionized water is 15min.
3. The method for biomimetically modifying the surface of polyether-ether-ketone according to claim 2, wherein the method comprises the following steps: the acid etching time in the concentrated sulfuric acid in the step 2 is 3min.
4. A method for biomimetically modifying a polyetheretherketone surface according to claim 3, wherein: the vacuum degree of the main sputtering chamber and the sample injection chamber of the magnetron sputtering in the step 3 is 5 multiplied by 10 -5 -8×10 -5 Pa, power 200W, sputtering time 2h.
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