CN112920452B - Additive manufactured porous polyether-ether-ketone support, and biological activity improvement method and application thereof - Google Patents

Additive manufactured porous polyether-ether-ketone support, and biological activity improvement method and application thereof Download PDF

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CN112920452B
CN112920452B CN202110291739.2A CN202110291739A CN112920452B CN 112920452 B CN112920452 B CN 112920452B CN 202110291739 A CN202110291739 A CN 202110291739A CN 112920452 B CN112920452 B CN 112920452B
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ether
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scaffold
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CN112920452A (en
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孙大辉
刘哲闻
张梅
董文英
赵姗姗
王子航
周星宇
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First Hospital Jinlin University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/20—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof

Abstract

The invention is applicable to the field of biomedical materials, and provides an additive manufactured porous polyether-ether-ketone scaffold, a biological activity improvement method and application, wherein the biological activity improvement method of the additive manufactured porous polyether-ether-ketone scaffold comprises the following steps: taking a porous polyether-ether-ketone support manufactured by additive manufacturing, and carrying out surface sulfonation treatment on the porous polyether-ether-ketone support manufactured by additive manufacturing to obtain a sulfonated porous polyether-ether-ketone support; and loading the composite material of the methacrylic acid esterified chitosan blended cage type polysilsesquioxane nano particles on the surface of the porous polyether-ether-ketone support subjected to sulfonation treatment by using an ultraviolet grafting method to obtain the improved porous polyether-ether-ketone support. According to the invention, by an additive manufacturing and ultraviolet grafting method, the composite material of the methacrylic acid esterified chitosan blended POSS nano particles is loaded on the surface of the porous polyether-ether-ketone support subjected to sulfonation treatment and additive manufacturing, so that the bioactivity and the osteogenic integration capability of the porous polyether-ether-ketone support can be enhanced.

Description

Additive manufactured porous polyether-ether-ketone support, and biological activity improvement method and application thereof
Technical Field
The invention belongs to the field of biomedical materials, and particularly relates to a porous polyether-ether-ketone support manufactured by additive manufacturing, and a biological activity improvement method and application.
Background
Polyetheretherketone (PEEK) is introduced into orthopedic implants as a candidate material for replacement of metal implants. Unlike typical metal materials with high elastic modulus exceeding 100 GPa, polyetheretherketone (PEEK) has an elastic modulus close to that of cortical bone (-20 GPa), which may mitigate the risk of stress shielding induced osteoporosis and bone resorption due to elastic mismatch between implant and human bone. PEEK also has no toxicity, good chemical resistance, good biocompatibility, natural radiolucency, and even MRI (magnetic resonance imaging) compatibility.
However, although these materials have attracted attention since the 80's 20 th century, the bio-inert surface of the PEEK composite is not conducive to cell growth and adhesion, and its inferior osteointegrative ability makes it impossible to form a firm bond with human bone tissue after implantation into the human body, thereby affecting the long-term stability of the implant material in the human body. These disadvantages severely hamper the clinical use of PEEK composites. In order to improve the bioactivity of PEEK and composite materials thereof, many researchers have performed surface modification on PEEK and composite materials thereof by physical or chemical methods, including PEEK-hydroxyapatite composite materials, PEEK-nano fluorapatite composite materials, etc., but their high brittleness, low strength and poor fatigue resistance limit clinical applications.
Disclosure of Invention
An object of an embodiment of the present invention is to provide a method for improving bioactivity of an additive manufactured porous polyetheretherketone scaffold, which aims to solve the problems set forth in the background art.
The embodiment of the invention is realized by a method for improving the bioactivity of an additive manufactured porous polyetheretherketone scaffold, which comprises the following steps:
taking a porous polyether-ether-ketone support manufactured by additive manufacturing, and carrying out surface sulfonation treatment on the porous polyether-ether-ketone support manufactured by additive manufacturing to obtain a sulfonated porous polyether-ether-ketone support;
and loading the composite material of the methacrylic acid esterified chitosan blended cage type polysilsesquioxane nano particles on the surface of the porous polyether-ether-ketone support after sulfonation treatment by an ultraviolet light grafting method to obtain the improved porous polyether-ether-ketone support.
Specifically, the additive manufactured porous polyetheretherketone scaffold can be obtained by designing and modeling using CATIA software, and printing using FFF system.
As a preferable aspect of the embodiment of the present invention, the step of performing surface sulfonation on the porous peek scaffold manufactured by additive manufacturing to obtain a sulfonated porous peek scaffold specifically includes:
and (3) pretreating the porous polyether-ether-ketone support manufactured by the additive, and then immersing the porous polyether-ether-ketone support in concentrated sulfuric acid for surface sulfonation to obtain the sulfonated porous polyether-ether-ketone support.
As another preferable scheme of the embodiment of the present invention, the step of pretreating the porous peek scaffold manufactured by additive manufacturing, and then immersing the porous peek scaffold in concentrated sulfuric acid to perform surface sulfonation to obtain the sulfonated porous peek scaffold specifically includes:
ultrasonically cleaning a porous polyether-ether-ketone support manufactured by additive manufacturing by acetone, ethanol and distilled water in sequence, and then drying in vacuum to obtain a pretreated porous polyether-ether-ketone support;
immersing the pretreated porous polyether-ether-ketone support in concentrated sulfuric acid, stirring, placing in distilled water to terminate the reaction, sequentially washing in acetone and distilled water respectively to remove concentrated sulfuric acid residues, and then performing vacuum drying to obtain the sulfonated porous polyether-ether-ketone support.
As another preferable scheme of the embodiment of the invention, the mass concentration of the concentrated sulfuric acid is 95-98%.
As another preferred embodiment of the present invention, the step of loading the composite material of the methacrylated chitosan blended cage-type polysilsesquioxane nanoparticles onto the surface of the porous polyether-ether-ketone scaffold after sulfonation treatment by using an ultraviolet light grafting method to obtain the improved porous polyether-ether-ketone scaffold specifically includes:
and adding the porous polyether-ether-ketone support subjected to sulfonation treatment into a suspension of methacrylic acid esterified chitosan blended cage type polysilsesquioxane nano particles for ultraviolet grafting to obtain the improved porous polyether-ether-ketone support.
As another preferable scheme of the embodiment of the invention, in the suspension of the methacrylated chitosan blended cage-type polysilsesquioxane nanoparticles, the mass percentage concentration of the cage-type polysilsesquioxane nanoparticles is 1% -4%.
As another preferable scheme of the embodiment of the invention, in the suspension of the methacrylated chitosan blended cage-type polysilsesquioxane nanoparticles, the mass percentage concentration of the methacrylated chitosan is 1% -3%.
As another preferable scheme of the embodiment of the invention, the preparation method of the methacrylated chitosan comprises the following steps:
adding chitosan into an acetic acid solution for heating and dissolving to obtain a chitosan solution;
slowly adding methacrylic anhydride into a chitosan solution, stirring in a dark place, dispersing in deionized water, dialyzing, purifying, and freeze-drying to obtain the methacrylated chitosan.
Specifically, the preparation method of the methacrylated chitosan comprises the following steps:
adding a predetermined amount of chitosan into 3~5% v/v acetic acid solution, and dissolving for 10 to 14h at 50 to 70 ℃ to prepare 1~2% w/v chitosan solution;
slowly adding 4~8 parts by volume of methacrylic anhydride into 100 parts by volume of chitosan solution, keeping the mixture at 30-50 ℃, stirring for 10-14h in the dark, then re-dispersing in deionized water, purifying in the deionized water through a dialysis membrane for more than 60-84 h, and changing water for more than 6 times; and then, using a vacuum freeze dryer to carry out freeze drying to obtain the methacrylate chitosan.
In addition, the methacrylic acid esterification chitosan is added into water, and the cage type polysilsesquioxane nano particles are added for dispersion, so that the suspension of the methacrylic acid esterification chitosan blended cage type polysilsesquioxane nano particles can be prepared.
It is a further object of embodiments of the present invention to provide an additive manufactured porous polyetheretherketone scaffold improved by the above-described method of improving biological activity.
Another object of an embodiment of the present invention is to provide a use of the above-mentioned additive manufactured porous peek scaffold in preparation of a bone graft material and/or a bone repair material.
In the invention, the methacrylated chitosan is a photosensitive material and is synthesized by reacting methacrylic anhydride and chitosan under the heating condition. Chitosan as a natural polymer has the advantages of no toxicity, no sensitization, adhesion, biocompatibility, biodegradability and the like. In addition, processing chitosan into porous structures is another promising feature for the preparation of various scaffolds, since chitosan is structurally similar to glycosaminoglycans, mimicking the major extracellular matrix components.
Cage Polysilsesquioxanes (POSS) are considered the smallest possible silica particle (1.5 nm), a highly symmetric molecule with a hybrid (inorganic/organic), well-defined cage structure consisting of silicon/oxygen cages and hydrocarbon functional groups attached to the silicon horn. It has an intermediate (RSiO) 1.5 ) Chemical composition between silicon dioxide (SiO) 2 ) And silicone (R) 2 SiO) is added. Thus, POSS nanoparticles can be passed throughThe copolymerization, grafting or blending effectively bonds with the polymer and exhibits a region of properties between the polymer and the ceramic. By varying the R groups, the structural and volumetric properties of POSS/polymer nanocomposites can be tailored. The material properties vary depending primarily on the interaction between the R groups and the polymer matrix which acts as a reinforcing or plasticizing agent. POSS also affects surface chemistry (wettability), changing the surface roughness and morphology of the polymer matrix. These unique properties make POSS a potential nanomaterial for stimulating biological responses on a nanometer scale. The polymer/POSS nanocomposite can be used as biomedical devices and biomaterials with tunable degradation rates required for tissue engineering applications.
According to the method for improving the biological activity of the porous polyether-ether-ketone support manufactured by the additive, the composite material of the methacrylic acid esterified chitosan blended with POSS nano particles is loaded on the surface of the porous polyether-ether-ketone support manufactured by the additive after sulfonation treatment through an ultraviolet grafting method, so that the improved porous polyether-ether-ketone support manufactured by the additive is obtained.
Compared with the prior art, the invention has the following advantages:
(1) The method designs and uses CATIA software for modeling, and uses an FFF system to print the porous polyether-ether-ketone support manufactured by additive manufacturing, and the pore diameter of the printed support is uniform and regular;
(2) The methacrylated chitosan used in the invention is a photosensitive material and has the advantages of no toxicity, no sensitization, adhesiveness, biocompatibility, biodegradability and the like.
(3) The cage type polysilsesquioxane used in the invention is a nano material, is a highly symmetrical molecule, has a hybrid (inorganic/organic) and definite cage-like structure, and consists of a silicon/oxygen cage and hydrocarbon functional groups attached to silicon molecules. It has an intermediate (RSiO) 1.5 ) Chemical composition between silicon dioxide (SiO) 2 ) And silicone (R) 2 SiO) is added. Thus, POSS nanoparticles can be effectively combined with polymers by copolymerization, grafting, or blending and exhibit a region of performance between the polymer and the ceramic. By changingAnd R group can customize the structure and volume performance of the POSS/polymer nano composite material.
(4) The method for improving the PEEK surface is simple in process, low in requirements on instruments, low in cost and easy to realize, and is an excellent PEEK surface modification method.
(5) The porous polyether-ether-ketone scaffold manufactured by the additive disclosed by the invention is excellent in performance and reasonable in structure, and can meet the requirements of most of clinical applications such as bone transplantation and bone repair.
Drawings
FIG. 1 is a graph of 2% total reflection infrared spectra of PEEK, SPEEK, SPEEK-CSMA, SPEEK-CSMA-POSS.
FIG. 2 is an X-ray photoelectron spectrum of 2% PEEK, SPEEK, SPEEK-CSMA, SPEEK-CSMA-POSS.
Fig. 3 is a schematic surface Scanning Electron Microscope (SEM) illustration of an additively manufactured porous peek scaffold before and after improvement of example 1, in which: the additive-fabricated porous peek scaffold (a) was untreated (b) was an additive-fabricated porous peek scaffold sulfonated with concentrated sulfuric acid (i.e., SPEEK before modification), (c) was an additive-fabricated porous peek scaffold (i.e., SPEEK-CSMA) after modification in example 1, (d) was an additive-fabricated porous peek scaffold (i.e., SPEEK-CSMA-POSS 1%) after modification in example 1, (f) was an additive-fabricated porous peek scaffold (i.e., SPEEK-CSMA-POSS 2%) after modification in example 1, and (e) was an additive-fabricated porous peek scaffold (i.e., SPEEK-CSMA-POSS 4%) after modification in example 1.
Fig. 4 is a contact angle plot of the surface of the additively manufactured porous peek scaffold before and after improvement in example 1.
Fig. 5 is a fluorescence microscopy image of cell activity of rat bone marrow mesenchymal stem cells (rBMSCs) of additively-manufactured porous peek scaffolds improved in example 1 and additively-manufactured porous peek scaffolds without surface modification. Wherein the PEEK is an additively manufactured porous PEEK scaffold without any surface modification; SPEEK is a porous polyetheretherketone scaffold manufactured by additive only by sulfonation with concentrated sulfuric acid; SPEEK-CSMA is a porous polyetheretherketone scaffold manufactured by an additive material grafted by methacrylated chitosan; SPEEK-CSMA-POSSX (X =1%,2%, 4%) is a composite grafted additive fabricated porous polyetheretherketone scaffold of methacrylated chitosan blended with POSS.
Fig. 6 is the results of cell adhesion experiments of rat bone marrow mesenchymal stem cells (rBMSCs) of additively-manufactured porous peek scaffolds improved in example 1 and additively-manufactured porous peek scaffolds without surface modification. Wherein the PEEK is an additively manufactured porous PEEK scaffold without any surface modification; SPEEK is a porous polyetheretherketone scaffold manufactured by additive only by sulfonation with concentrated sulfuric acid; SPEEK-CSMA is a porous polyetheretherketone scaffold manufactured by an additive material grafted by methacrylated chitosan; SPEEK-CSMA-POSSX (X =1%,2%, 4%) is a composite grafted additive fabricated porous polyetheretherketone scaffold of methacrylated chitosan blended with POSS.
Fig. 7 is the results of cell proliferation experiments for rat bone marrow mesenchymal stem cells (rBMSCs) for additive manufactured porous peek scaffolds improved in example 1 and for additive manufactured porous peek scaffolds without surface modification. Wherein the PEEK is an additively manufactured porous PEEK scaffold without any surface modification; SPEEK is a porous polyetheretherketone scaffold manufactured by additive only by sulfonation with concentrated sulfuric acid; SPEEK-CSMA is a porous polyetheretherketone scaffold manufactured by an additive material grafted by methacrylated chitosan; SPEEK-CSMA-POSSX (X =1%,2%, 4%) is a composite grafted additively manufactured porous polyetheretherketone scaffold of methacrylated chitosan blended POSS.
Fig. 8 is a laser confocal photograph of rat bone marrow mesenchymal stem cells (rBMSCs) of additively-manufactured porous peek scaffolds improved in example 1 and additively-manufactured porous peek scaffolds without surface modification. PEEK is a porous PEEK scaffold manufactured additively without any surface modification; SPEEK is a porous polyetheretherketone scaffold manufactured by additive only by sulfonation with concentrated sulfuric acid; SPEEK-CSMA is a porous polyetheretherketone scaffold which is made of an additive material grafted by methacrylated chitosan; SPEEK-CSMA-POSSX (X =1%,2%, 4%) is a composite grafted additive fabricated porous polyetheretherketone scaffold of methacrylated chitosan blended with POSS.
Fig. 9 is an alkaline phosphatase staining photograph of rat bone marrow mesenchymal stem cells (rBMSCs) of additively-manufactured porous peek scaffolds improved in example 1 and additively-manufactured porous peek scaffolds without surface modification. PEEK is a porous PEEK scaffold manufactured additively without any surface modification; SPEEK is a porous polyetheretherketone scaffold manufactured by additive only by sulfonation with concentrated sulfuric acid; SPEEK-CSMA is a porous polyetheretherketone scaffold manufactured by an additive material grafted by methacrylated chitosan; SPEEK-CSMA-POSSX (X =1%,2%, 4%) is a composite grafted additive fabricated porous polyetheretherketone scaffold of methacrylated chitosan blended with POSS.
Fig. 10 is an ARS staining photograph of additively manufactured porous peek scaffolds improved in example 1 above and rat bone marrow mesenchymal stem cells (rBMSCs) without surface modification. PEEK is a porous PEEK scaffold manufactured additively without any surface modification; SPEEK is a porous polyetheretherketone scaffold manufactured by additive only by sulfonation with concentrated sulfuric acid; SPEEK-CSMA is a porous polyetheretherketone scaffold manufactured by an additive material grafted by methacrylated chitosan; SPEEK-CSMA-POSSX (X =1%,2%, 4%) is a composite grafted additively manufactured porous polyetheretherketone scaffold of methacrylated chitosan blended POSS.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This embodiment provides a method of improving the bioactivity of an additively manufactured porous polyetheretherketone scaffold comprising the steps of:
s1, designing and modeling by using CATIA software, printing a porous polyether-ether-ketone support manufactured in an additive mode with the size of phi 14X3 by using an FFF system, carrying out ultrasonic cleaning for 3 times (30 min each time) by using acetone, ethanol and distilled water in sequence, then placing the support in a vacuum drying box at 60 ℃ for drying and storing for later use, and obtaining the pretreated porous polyether-ether-ketone support manufactured in the additive mode (named as PEEK).
The specific printing parameters are that the diameter of the printing head is 0.4mm, the temperature of the printing head is 420 ℃, the temperature of the bottom plate is room temperature, the temperature of the material box is 65 ℃, the printing speed is 30mm/min, and the thickness of the printing layer is 0.2mm.
S2, immersing the pretreated additive manufactured porous polyether-ether-ketone support in concentrated sulfuric acid with the mass concentration of 98%, and reacting on a magnetic stirrer for 5min, wherein the rotating speed is set to be 500rpm/min. And (2) carrying out sulfonation treatment reaction for 5min at room temperature, then quickly taking out and placing in distilled water to terminate the reaction, then sequentially cleaning in acetone and distilled water for 30min respectively to remove concentrated sulfuric acid residues, then placing in a vacuum drying oven at 60 ℃ for drying and storing for later use, and thus obtaining the porous polyether-ether-ketone support (named SPEEK) manufactured by the additive after sulfonation treatment.
S3, adding the porous polyether-ether-ketone support subjected to sulfonation treatment and manufactured in an additive manufacturing mode into a suspension of methacrylic acid esterified chitosan blended POSS nano particles for ultraviolet grafting to obtain a porous polyether-ether-ketone support (named SPEEK-CSMA-POSSX, wherein X refers to the mass percentage concentration of POSS nano particles in the suspension of the methacrylic acid esterified chitosan blended POSS nano particles, and X =0,1%,2% and 4%) manufactured in an additive manufacturing mode, wherein the composite material of the methacrylic acid esterified chitosan blended POSS nano particles is loaded; and freeze-drying, sealing and storing at low temperature.
The preparation method of the suspension of the methacrylic acid esterified chitosan blended POSS nano particles comprises the following steps:
(1) A1.5% w/v chitosan solution (100 mL) was prepared by dissolving a predetermined amount of chitosan in a 4% v/v acetic acid solution at 60 deg.C for 12h with heating.
(2) Slowly adding 6 mL of methacrylic anhydride into the 100mL of chitosan solution, keeping the mixture at 40 ℃, stirring for 12 hours in the dark condition, then re-dispersing in deionized water, purifying in 5L of deionized water through a dialysis membrane for more than 72 hours, and changing water for more than 6 times; then, freeze-drying by using a vacuum freeze dryer to obtain the methacrylated chitosan.
(3) And adding a proper amount of the methacrylated chitosan into water, and adding a proper amount of POSS nano particles for dispersion to prepare a suspension of the methacrylated chitosan blended with POSS nano particles, wherein the mass percentage concentration of the methacrylated chitosan is 2%, and the mass percentage concentration of the POSS nano particles is 0,1%,2% and 4%, respectively.
And (3) carrying out performance detection on the porous polyether-ether-ketone support manufactured by the additive material, wherein fig. 1 is a 2% total reflection infrared spectrogram of the PEEK, the SPEEK-CSMA and the SPEEK-CSMA-POSS.
As can be seen from FIG. 1, SPEEK-CSMA-POSS2% is 3443 and 2937 cm −1 Shaking with (-OH) and (-CH 2-) groups at 1100 cm −1 The vibration of Si-O-Si is detected, which shows that the composite material of the base acrylic acid esterified chitosan blended POSS nano particles is successfully loaded on the surface of the bracket.
FIG. 2 is an X-ray photoelectron spectrum of 2% of the above PEEK, SPEEK, SPEEK-CSMA, SPEEK-CSMA-POSS.
As can be seen from FIG. 2, the XPS map of SPEEK-CSMA, SPEEK-CSMA-POSS2% shows that methacrylic acid esterified chitosan is successfully loaded on the surface of the bracket, except for C, O, N peak, and the XPS map of SPEEK-CSMA-POSS2% shows that methacrylic acid esterified chitosan is successfully loaded on the surface of the bracket, and besides C, O, N peak, si peak, and the composite material of methacrylic acid esterified chitosan blended with POSS nano particles is successfully loaded on the surface of the bracket.
Fig. 3 is a schematic surface Scanning Electron Microscope (SEM) illustration of an additive manufactured porous polyetheretherketone scaffold before and after improvement in example 1, wherein: the additive-fabricated porous peek scaffold (a) was untreated (b) was an additive-fabricated porous peek scaffold sulfonated with concentrated sulfuric acid (i.e., SEEK before modification), (c) was an additive-fabricated porous peek scaffold (i.e., SPEEK-CSMA) after modification in example 1, (d) was an additive-fabricated porous peek scaffold (i.e., SPEEK-CSMA-POSS 1%) after modification in example 1, (f) was an additive-fabricated porous peek scaffold (i.e., SPEEK-CSMA-POSS 2%) after modification in example 1, and (e) was an additive-fabricated porous peek scaffold (i.e., SPEEK-CSMA-POSS 4%) after modification in example 1.
As can be seen from fig. 3, the surface of the additive-fabricated porous peek scaffold treated with concentrated sulfuric acid sulfonation in this example has a distinct microporous structure. After ultraviolet light grafting, the SPEEK-CSMA-POSSX (X =0,1%,2%, 4%) surface and macropores are loaded with the composite material of methacrylic acid esterified chitosan blended POSS nano particles, so that the roughness and the adhesion capability of the surface are improved.
Fig. 4 is a hydrophilicity test of the surface of an additive manufactured porous peek scaffold before and after modification in example 1. As can be seen from fig. 4, with the loading of the methacrylated chitosan blended POSS nanoparticle composite, all the modified SPEEK-CSMA-POSSX (X =0,1%,2%, 4%) had significantly increased hydrophilicity compared to untreated PEEK and sulfonated SEEK alone.
Example 2
This embodiment provides a method of improving the bioactivity of an additively manufactured porous polyetheretherketone scaffold comprising the steps of:
s1, designing and modeling by using CATIA software, printing a porous polyether-ether-ketone support manufactured in an additive mode with the size of phi 14X3 by using an FFF system, carrying out ultrasonic cleaning for 3 times (30 min each time) by using acetone, ethanol and distilled water in sequence, then placing the support in a vacuum drying box at 50 ℃ for drying and storing for later use, and obtaining the pretreated porous polyether-ether-ketone support manufactured in the additive mode (named as PEEK).
The specific printing parameters are that the diameter of the printing head is 0.4mm, the temperature of the printing head is 420 ℃, the temperature of the bottom plate is room temperature, the temperature of the material box is 65 ℃, the printing speed is 30mm/min, and the thickness of the printing layer is 0.2mm.
S2, immersing the pretreated additive manufactured porous polyether-ether-ketone support in concentrated sulfuric acid with the mass concentration of 95%, and reacting on a magnetic stirrer for 4min, wherein the rotating speed is set to be 400rpm/min. And (2) carrying out sulfonation treatment reaction for 4min at room temperature, then quickly taking out and placing in distilled water to terminate the reaction, then sequentially cleaning in acetone and distilled water for 20min respectively to remove concentrated sulfuric acid residues, then placing in a vacuum drying oven at 50 ℃ for drying and storing for later use, and thus obtaining the porous polyether-ether-ketone support (named SPEEK) manufactured by the additive after sulfonation treatment.
And S3, adding the porous polyether-ether-ketone support subjected to sulfonation treatment and manufactured by additive manufacturing into a suspension of methacrylic acid esterified chitosan blended POSS nano particles for ultraviolet grafting to obtain the porous polyether-ether-ketone support which is loaded by the composite material of the methacrylic acid esterified chitosan blended POSS nano particles and manufactured by additive manufacturing, and freezing, drying, sealing and storing at low temperature.
The preparation method of the suspension of the methacrylic acid esterified chitosan blended POSS nano particles comprises the following steps:
(1) A1% w/v chitosan solution (100 mL) was prepared by dissolving a predetermined amount of chitosan in a 3% v/v acetic acid solution at 50 ℃ for 10h with heating.
(2) Slowly adding 4 mL of methacrylic anhydride into the 100mL of chitosan solution, keeping the mixture at 30 ℃, stirring for 10 hours in the dark condition, then re-dispersing in deionized water, purifying in 5L of deionized water through a dialysis membrane for more than 60 hours, and changing water for more than 6 times; then, freeze-drying by using a vacuum freeze dryer to obtain the methacrylated chitosan.
(3) And adding a proper amount of the methacrylated chitosan into water, adding a proper amount of POSS nanoparticles, and dispersing to prepare a suspension of the methacrylated chitosan blended with POSS nanoparticles, wherein the mass percentage concentration of the methacrylated chitosan is 1% and the mass percentage concentration of the POSS nanoparticles is 1%.
Example 3
This embodiment provides a method of improving the bioactivity of an additively manufactured porous polyetheretherketone scaffold comprising the steps of:
s1, designing and modeling by using CATIA software, printing a porous polyether-ether-ketone support manufactured in an additive mode with the size of phi 14X3 by using an FFF system, sequentially performing ultrasonic cleaning for 3 times (30 min each time) by using acetone, ethanol and distilled water, then placing the support in a vacuum drying box at 70 ℃ for drying and storing for later use, and obtaining the pretreated porous polyether-ether-ketone support manufactured in an additive mode (named as PEEK).
The specific printing parameters are that the diameter of the printing head is 0.4mm, the temperature of the printing head is 420 ℃, the temperature of the bottom plate is room temperature, the temperature of the material box is 65 ℃, the printing speed is 30mm/min, and the thickness of the printing layer is 0.2mm.
S2, immersing the pretreated additive manufactured porous polyether-ether-ketone support in concentrated sulfuric acid with the mass concentration of 96%, and reacting on a magnetic stirrer for 6min, wherein the rotating speed is set as 600rpm/min. And (2) performing sulfonation treatment reaction for 6min at room temperature, quickly taking out the obtained product, placing the obtained product in distilled water to terminate the reaction, sequentially cleaning the obtained product in acetone and distilled water for 40min to remove concentrated sulfuric acid residues, placing the obtained product in a vacuum drying oven at 70 ℃ for drying and storing the obtained product for later use, and thus obtaining the porous polyether-ether-ketone support (named SPEEK) manufactured by additive manufacturing after sulfonation treatment.
And S3, adding the porous polyether-ether-ketone support subjected to sulfonation treatment and manufactured by additive manufacturing into a suspension of methacrylic acid esterified chitosan blended POSS nano particles for ultraviolet grafting to obtain the porous polyether-ether-ketone support which is loaded by the composite material of the methacrylic acid esterified chitosan blended POSS nano particles and manufactured by additive manufacturing, and freezing, drying, sealing and storing at low temperature.
The preparation method of the suspension of the methacrylic acid esterified chitosan blended POSS nano particles comprises the following steps:
(1) A2% w/v chitosan solution (100 mL) was prepared by dissolving a predetermined amount of chitosan in a 5% v/v acetic acid solution for 14h with heating at 70 ℃.
(2) Slowly adding 8 mL of methacrylic anhydride into the 100mL of chitosan solution, keeping the mixture at 40 ℃, stirring for 12 hours in a dark condition, then re-dispersing in deionized water, purifying in 5L of deionized water for more than 72 hours through a dialysis membrane, and changing water for more than 6 times; then, freeze-drying by using a vacuum freeze dryer to obtain the methacrylated chitosan.
(3) And adding a proper amount of the methacrylated chitosan into water, and adding a proper amount of POSS nano-particles for dispersion to prepare a suspension of the methacrylated chitosan blended POSS nano-particles, wherein the mass percentage concentration of the methacrylated chitosan is 3% and the mass percentage concentration of the POSS nano-particles is 4%.
Example 4
Cytotoxicity of additive-fabricated porous peek scaffolds improved in example 1 and additive-fabricated porous peek scaffolds without surface modification was evaluated using rat bone marrow mesenchymal stem cells (rBMSCs) in vitro culture experiments and detected using Calcein-AM/PI Double Stain Kit (Yeasen, shanghai, china) Kit. The specific operation method comprises the following steps:
(1) Placing porous PEEK scaffold before and after improvement in 24-well culture plate, and dripping into each well at a density of 5 × 10 4 cell/mL cell suspension, incubation with complete medium with reduced sugar, placing the cell culture plate into 5% CO 2 The cells were cultured at 37 ℃ in a cell culture chamber saturated in humidity.
(2) After 24 hours, live cells were fluorescently stained and washed according to the kit instructions.
(3) After the staining was completed, the staining was observed by a fluorescence microscope and photographed, and the result is shown in FIG. 5.
Fig. 5 shows fluorescence microscopy images of rBMSCs cell activity of additive fabricated porous peek scaffolds improved in example 1 and additive fabricated porous peek scaffolds without surface modification. PEEK is a porous PEEK scaffold manufactured additively without any surface modification; SPEEK is a porous polyetheretherketone scaffold manufactured by additive only by sulfonation with concentrated sulfuric acid; SPEEK-CSMA is a porous polyetheretherketone scaffold which is made of an additive material grafted by methacrylated chitosan; SPEEK-CSMA-POSSX (X =1%,2%, 4%) is a composite grafted additive fabricated porous polyetheretherketone scaffold of methacrylated chitosan blended with POSS.
Fig. 5 illustrates that neither the additive-fabricated porous peek scaffold without surface modification nor the additive-fabricated porous peek scaffold after surface modification treatment is cytotoxic to rBMSCs.
Example 5
Cell adhesion of additively manufactured porous peek scaffolds improved by example 1 above to additively manufactured porous peek scaffolds without surface modification was evaluated using rat bone marrow mesenchymal stem cells (rBMSCs) in vitro culture experiments. Scanning electron microscopy was used to observe the adhesion of the rBMSCs to the composite. The specific operation method comprises the following steps:
(1) Culturing rBMSCs on a porous polyether-ether-ketone scaffold manufactured by additive manufacturing for 3 days, taking out a sample, and gently washing the sample for 3 times for 10min each time by PBS;
(2) Fixing the sample with 4% glutaraldehyde at 4 deg.C for more than 2 hr;
(3) Washing the sample with deionized water for 15min;
(4) Ethanol gradient dehydration (10, 30, 50, 70, 90, 95, 100%) dried overnight;
(5) After the surface of the sample is sprayed with gold, the growth of rBMSCs on the composite material is observed by a scanning electron microscope, and the result is shown in FIG. 6.
Fig. 6 shows the results of the rBMSCs cell adhesion experiments for the additively manufactured porous peek scaffold improved in example 1 above and for the additively manufactured porous peek scaffold without surface modification. PEEK is a porous PEEK scaffold manufactured additively without any surface modification; SPEEK is a porous polyetheretherketone scaffold manufactured by additive only by sulfonation with concentrated sulfuric acid; SPEEK-CSMA is a porous polyetheretherketone scaffold manufactured by an additive material grafted by methacrylated chitosan; SPEEK-CSMA-POSSX (X =1%,2%, 4%) is a composite grafted additive fabricated porous polyetheretherketone scaffold of methacrylated chitosan blended with POSS.
As can be seen in FIG. 6, rBMSCs cells on PEEK were round and poorly shaped. The SPEEK has micropores on the surface, so that the adhesion of rBMSCs is facilitated, cells can be seen, but the morphology is general. SPEEK-CSMA-POSSX (X =0,1%,2%, 4%) has rough surface, strong hydrophilicity is more beneficial to cell adhesion and growth, and rBMSCs cells are seen to be pseudopodous and longer, and the material is more beneficial to cell growth compared with the former two materials.
Example 6
In vitro culture experiments of rat bone marrow mesenchymal stem cells (rBMSCs) were used to assess cell proliferation for the additively manufactured porous peek scaffolds improved according to example 1 above versus those manufactured without surface modification. Cell Counting Kit (CKK-8, beyotime, shanghai, china) Kit was used to detect the proliferation of cells on the material surface. The specific operation method comprises the following steps:
(1) Placing porous PEEK scaffold before and after improvement in 24-well culture plate, and dripping into each well at a density of 1 × 10 4 cell/mL cell suspension, addition of low-carbohydrate complete medium, placing the cell culture plate in 5% CO 2 The cells were cultured at 37 ℃ in a cell culture chamber saturated in humidity.
(2) After 1, 4 and 7 days of cell culture, the culture broth was aspirated, 500. Mu.L of fresh culture broth containing 10% CKK-8 solution was added, the plate was placed in an incubator for 2 hours, and then 100. Mu.L of culture broth was taken out from each well and placed in a 96-well plate.
(3) The absorbance value at a wavelength of 450nm of each well was measured using a microplate reader (iMark, bio-Rad, USA), and the result is shown in FIG. 7.
Fig. 7 shows the results of cell proliferation experiments for rBMSCs of additively manufactured porous peek scaffolds improved in example 1 versus additively manufactured porous peek scaffolds without surface modification. Wherein, PEEK is a porous PEEK scaffold manufactured by additive manufacturing without any surface modification; SPEEK is a porous polyetheretherketone scaffold manufactured by additive only by sulfonation with concentrated sulfuric acid; SPEEK-CSMA is a porous polyetheretherketone scaffold manufactured by an additive material grafted by methacrylated chitosan; SPEEK-CSMA-POSSX (X =1%,2%, 4%) is a composite grafted additive fabricated porous polyetheretherketone scaffold of methacrylated chitosan blended with POSS.
Fig. 7 shows that the absorbance of the additively manufactured porous peek scaffold treated by sulfonation with concentrated sulfuric acid is the lowest, and the proliferation of cells on the surface of the additively manufactured porous peek scaffold grafted by the composite material of methacrylated chitosan and POSS is obviously better than that of the additively manufactured porous peek scaffold without surface modification, which indicates that the modified sample has better biological proliferation characteristics.
Example 7
The cell adhesion and growth of the additively manufactured porous peek scaffold improved in example 1 above and the additively manufactured porous peek scaffold without surface modification were evaluated using rat bone marrow mesenchymal stem cells (rBMSCs) in vitro culture experiments. Cytoskeleton and cell nucleus were stained with rhodamine-labeled phalloidin and DAPI, respectively, and observed using a confocal laser microscope. The specific operation method comprises the following steps:
(1) Culturing rBMSCs on the porous polyether-ether-ketone scaffold which is subjected to additive manufacturing before and after improvement for 3 days, taking out a sample, and gently washing the sample for 3 times by PBS (phosphate buffer solution) for 10min each time;
(2) Fixing the sample with 4% paraformaldehyde at 4 deg.C for 30min, and washing with PBS for 10min for 3 times;
(3) Adding Triton-100 (0.5%), reacting for 20min, washing with PBS for 10min for 3 times;
(4) Staining the cytoskeleton and the cell nucleus with rhodamine-labeled phalloidin (100 nM) and DAPI (5. Mu.g/mL), respectively;
(5) After the staining, the staining was observed by confocal laser microscopy, photographed, and processed by imageJ software, and the results are shown in fig. 8.
Fig. 8 shows the rBMSCs cell laser confocal photographs of the additively manufactured porous peek scaffold improved in example 1 above versus the additively manufactured porous peek scaffold without surface modification. PEEK is a porous PEEK scaffold manufactured additively without any surface modification; SPEEK is a porous polyetheretherketone scaffold manufactured by additive only by sulfonation with concentrated sulfuric acid; SPEEK-CSMA is a porous polyetheretherketone scaffold manufactured by an additive material grafted by methacrylated chitosan; SPEEK-CSMA-POSSX (X =1%,2%, 4%) is a composite grafted additive fabricated porous polyetheretherketone scaffold of methacrylated chitosan blended with POSS.
As can be seen from fig. 8, the number of rBMSCs cells on PEEK was small, and cells were visible, but the morphology was general. The SPEEK surface has micropores, so that the adhesion of rBMSCs is facilitated, and the pseudopodous growth of rBMSCs cells can be seen. SPEEK-CSMA-POSSX (X =0,1%,2%, 4%) has rough surface, strong hydrophilicity is more beneficial to cell adhesion and growth, and rBMSCs cells are seen to be pseudopodous and longer, and the material is more beneficial to cell growth compared with the former two materials.
Example 8
In vitro culture experiments of rat bone marrow mesenchymal stem cells (rBMSCs) were used to evaluate the cell differentiation of the additively manufactured porous peek scaffold improved in example 1 above versus an additively manufactured porous peek scaffold without surface modification. The additively manufactured porous polyetheretherketone scaffolds were stained using BCIP/NBT. The specific operation method comprises the following steps:
(1) Placing porous PEEK scaffold before and after improvement in 24-well culture plate, and dripping into each well at a density of 5 × 10 4 cell/mL cell suspension, complete medium with low sugar was added.
(2) Culturing rBMSCs on an additive manufactured porous polyether-ether-ketone scaffold for 1 day, replacing a low-sugar complete culture medium with an osteogenesis induction culture medium, and replacing a culture solution every 2 days;
(2) Culturing rBMSCs cells for 7 days and 14 days, removing the culture medium, and washing with PBS for 3 times;
(3) Fixing rBMSCs cells with 4% paraformaldehyde for 30min at 4 ℃, and washing with PBS for 3 times;
(4) Preparing BCIP/NBT staining working solution, adding 500 mu L staining solution into each hole, and incubating overnight at room temperature in a dark place;
(5) After the staining was completed, the working solution was discarded, washed with PBS 3 times, dried and photographed, and the results are shown in FIG. 9.
Fig. 9 is a photograph of ALP staining of rBMSCs cells for additive fabricated porous peek scaffolds modified from example 1 above versus additive fabricated porous peek scaffolds without surface modification. PEEK is a porous polyetheretherketone scaffold manufactured additively without any surface modification; SPEEK is a porous polyetheretherketone scaffold manufactured by additive only by sulfonation with concentrated sulfuric acid; SPEEK-CSMA is a porous polyetheretherketone scaffold manufactured by an additive material grafted by methacrylated chitosan; SPEEK-CSMA-POSSX (X =1%,2%, 4%) is a composite grafted additive fabricated porous polyetheretherketone scaffold of methacrylated chitosan blended with POSS.
As can be seen from FIG. 9, there was less purple color on the PEEK and SPEEK surfaces, indicating that rBMSCs cells were poorly differentiated. SPEEK-CSMA-POSSX (X =0,1%,2%, 4%) has more purple surface, wherein SPEEK-CSMA-POSS2% group stains most deeply, and compared with the former two materials, the composite material grafted additive manufactured porous polyether ether ketone scaffold of the methacrylated chitosan blended with POSS is more beneficial to cell differentiation.
Example 9
The calcium nodule deposition of additively manufactured porous peek scaffolds improved from example 1 above and additively manufactured porous peek scaffolds without surface modification were evaluated using an in vitro culture experiment with rat bone marrow mesenchymal stem cells (rBMSCs). The additively manufactured porous polyetheretherketone scaffolds were stained using ARS. The specific operation method comprises the following steps:
(1) Placing porous PEEK scaffold before and after improvement in 24-well culture plate, and dripping into each well at a density of 5 × 10 4 cell/mL cell suspension, complete medium with low sugar was added.
(2) Culturing rBMSCs on an additive manufactured porous polyether-ether-ketone scaffold for 1 day, replacing a low-sugar complete culture medium with an osteogenesis induction culture medium, and replacing a culture solution every 2 days;
(2) Culturing rBMSCs cells for 21 days, removing the culture medium, and washing with PBS for 3 times;
(3) Fixing rBMSCs cells with 4% paraformaldehyde for 30min at 4 ℃, and washing with PBS for 3 times;
(4) Adding 1mL of ARS staining solution into each hole, and incubating for 30min at room temperature in a dark place;
(5) After dyeing, the working solution was discarded, rinsed 5 times with double distilled water, dried and photographed, and the results are shown in fig. 10.
Fig. 10 is a photograph of the rBMSCs cell ARS staining of an additively manufactured porous peek scaffold improved in example 1 above versus an additively manufactured porous peek scaffold without surface modification. PEEK is a porous PEEK scaffold manufactured additively without any surface modification; SPEEK is a porous polyetheretherketone scaffold manufactured by additive only by sulfonation with concentrated sulfuric acid; SPEEK-CSMA is a porous polyetheretherketone scaffold manufactured by an additive material grafted by methacrylated chitosan; SPEEK-CSMA-POSSX (X =1%,2%, 4%) is a composite grafted additive fabricated porous polyetheretherketone scaffold of methacrylated chitosan blended with POSS.
As can be seen in FIG. 10, the PEEK and SPEEK surfaces show less redness, indicating less calcium nodule deposition. SPEEK-CSMA-POSSX (X =0,1%,2%, 4%) is more red on the surface, with the SPEEK-CSMA-POSS2% group staining darkest, showing that the composite grafted additive made porous PEEK scaffold of methacrylated chitosan blended with POSS is more favorable for the deposition of calcium nodules than the previous two materials.
Furthermore, it should be understood that although the present specification describes embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and it is to be understood that all embodiments may be combined as appropriate by one of ordinary skill in the art to form other embodiments as will be apparent to those of skill in the art from the description herein.

Claims (8)

1. A method for improving the biological activity of a porous polyether-ether-ketone scaffold manufactured by additive manufacturing is characterized by comprising the following steps:
taking a porous polyether-ether-ketone support manufactured by additive manufacturing, and performing surface sulfonation treatment on the porous polyether-ether-ketone support manufactured by additive manufacturing to obtain a porous polyether-ether-ketone support subjected to sulfonation treatment;
adding the porous polyether-ether-ketone support subjected to sulfonation treatment into a suspension of methacrylic acid esterified chitosan blended cage type polysilsesquioxane nano particles for ultraviolet grafting to obtain an improved porous polyether-ether-ketone support;
in the suspension of the methacrylic acid esterified chitosan blended cage-type polysilsesquioxane nano-particles, the mass percentage concentration of the cage-type polysilsesquioxane nano-particles is 1% -4%.
2. The method for improving the bioactivity of the additive manufactured porous peek scaffold according to claim 1, wherein the step of performing surface sulfonation on the additive manufactured porous peek scaffold to obtain a sulfonated porous peek scaffold specifically comprises:
and (3) pretreating the porous polyether-ether-ketone support manufactured by the additive, and then immersing the porous polyether-ether-ketone support in concentrated sulfuric acid for surface sulfonation to obtain the sulfonated porous polyether-ether-ketone support.
3. The method for improving the bioactivity of the additive manufactured porous peek scaffold according to claim 2, wherein the step of pre-treating the additive manufactured porous peek scaffold, and then immersing the additive manufactured porous peek scaffold in concentrated sulfuric acid for surface sulfonation to obtain the sulfonated porous peek scaffold specifically comprises:
ultrasonically cleaning a porous polyether-ether-ketone support manufactured by additive manufacturing by acetone, ethanol and distilled water in sequence, and then drying in vacuum to obtain a pretreated porous polyether-ether-ketone support;
immersing the pretreated porous polyether-ether-ketone support in concentrated sulfuric acid, stirring, placing in distilled water to terminate the reaction, sequentially and respectively cleaning in acetone and distilled water to remove concentrated sulfuric acid residues, and then carrying out vacuum drying to obtain the porous polyether-ether-ketone support after sulfonation treatment.
4. The method for improving the bioactivity of the additive manufactured porous polyether ether ketone scaffold according to claim 2 or 3, wherein the mass concentration of concentrated sulfuric acid is 95-98%.
5. The method for improving the bioactivity of the additive manufactured porous polyether ether ketone scaffold according to claim 1, wherein the mass percentage concentration of the methacrylated chitosan in the suspension of the methacrylated chitosan blended cage-type polysilsesquioxane nanoparticles is 1% -3%.
6. The method for improving the biological activity of the additive manufactured porous polyetheretherketone scaffold according to claim 1 or 5, wherein the method for preparing methacrylated chitosan comprises the steps of:
adding chitosan into an acetic acid solution for heating and dissolving to obtain a chitosan solution;
slowly adding methacrylic anhydride into the chitosan solution, stirring in the dark place, dispersing in deionized water, dialyzing, purifying and freeze-drying to obtain the methacrylated chitosan.
7. An additively manufactured porous polyetheretherketone scaffold improved by the method of any one of claims 1~6.
8. Use of an additively manufactured porous polyetheretherketone scaffold according to claim 7 in the preparation of a bone graft material and/or a bone repair material.
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