CN114989475B - Preparation method and product application of biological functionalized surface modified polyether-ether-ketone material - Google Patents
Preparation method and product application of biological functionalized surface modified polyether-ether-ketone material Download PDFInfo
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- 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
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
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- A—HUMAN NECESSITIES
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- 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
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- 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
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
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- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
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- A—HUMAN NECESSITIES
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- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/606—Coatings
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- A—HUMAN NECESSITIES
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- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
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- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
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- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/06—Coatings containing a mixture of two or more compounds
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- A—HUMAN NECESSITIES
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- 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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/04—Polyamides derived from alpha-amino carboxylic acids
Abstract
The invention relates to a preparation method and product application of a bio-functionalized surface modified polyether-ether-ketone material. The material is a surface activated artificial bone repair implant. The preparation process comprises the following steps: preparing a customized polyether-ether-ketone artificial bone repair implant; secondly, preprocessing the surface of the polyether-ether-ketone artificial bone repair implant; and thirdly, fixing hyperbranched polylysine on the surface of the polyether-ether-ketone artificial bone repair implant, and loading drug molecules and fluorescent imaging molecules through electrostatic action to form a bioactive coating. The preparation method disclosed by the invention can obviously improve the biocompatibility of the polyether-ether-ketone material, simultaneously endow the polyether-ether-ketone material with biological activity, promote the proliferation of cells on the surface of the customized polyether-ether-ketone artificial bone repair implant, and the surface-activated polyether-ether-ketone artificial bone repair implant has more excellent bone growth promoting capability.
Description
Technical Field
The invention relates to a preparation method and product application of a bio-functionalized surface modified polyether-ether-ketone material, belonging to the technical field of biomedical polymer materials.
Background
The polyether ether ketone (PEEK) has good in-vitro and in-vivo biocompatibility, no toxicity, no teratogenesis, no mutation and no carcinogenic effect, and can transmit radioactive rays and can not generate artifacts in magnetic resonance scanning. At present, PEEK and a composite material thereof become hot spots for study of materialists and orthopedics specialists, and an intervertebral fusion device, an artificial joint prosthesis and the like are applied to clinic and have good recent follow-up effect. However, PEEK is biologically inert and hydrophobic, lacks biological activity, is difficult to chemically modify, and does not integrate well with host bone after implantation in vivo, greatly limiting its wide clinical application.
The adoption of a surface modification method to endow the PEEK material with biological activity is an effective way for solving the problems without damaging the intrinsic excellent properties of the PEEK material, namely, the PEEK material is functionalized by preparing a biological activity coating through a physical or chemical method. In the past literature, many coatings (including calcium phosphate, bioactive small molecules, hydroxyapatite, titanium, etc.) have been reported to have utility in enhancing the osseointegration of PEEK implants. However, these methods still have many problems to be solved, including easy degradation of the coating, complicated and time-consuming chemical steps, poor adhesion of the coating to the substrate, etc. In addition, surface modification of PEEK implants is currently focused mainly on the multifunctional properties of improving bioactivity, promoting cell growth, or avoiding infection, which are also important functions necessary to promote physiological osseointegration of PEEK implants. At present, few research reports are reported on the PEEK surface functionalization so as to simultaneously obtain key functions of resisting infection, promoting growth and the like, and the practical clinical application is more scarce.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the biological inertia of PEEK materials, treating the surface of PEEK through chemical grafting at normal temperature, and forming a coating by non-covalent bonding of fluorescent molecules and drug molecules only through a soaking means, thereby endowing the PEEK with various biological functions including anti-infection, growth promotion and the like.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the polyether-ether-ketone material is a material which is prepared by injection molding, 3D printing, presoaking and other processes and has a specific shape, the outer layer or the whole body is the polyether-ether-ketone material, and the surface of the polyether-ether-ketone material is subjected to biological functional modification treatment.
The biological functional modification treatment is specifically that after the polyether-ether-ketone material is subjected to plasma treatment, an activation layer is chemically grafted on the surface of the polyether-ether-ketone material through a soaking process to carry out modification.
The soaking process is that carboxyl is generated on the surface through acidification, and the carboxyl reacts with hyperbranched polylysine through amidation to form a positively charged coating, namely an activation layer; the coating contains positively charged hyperbranched polylysine, so that the coating can be combined with negatively charged fluorescent molecules and/or non-covalent high-efficiency loads of growth promoting drugs.
The fluorescent molecule is at least one of fluorescein isothiocyanate, FAM maleimide, rhodamine, sulfonylrhodamine 101, 5-carboxymethyl rhodamine, 1-aminonaphthalene-8-carboxylic acid Texas red and 5- (iodoacetamido) fluorescein.
The growth promoting medicine is at least one of tacrolimus, potassium pralidoxime, oxiracetam and alendronate sodium.
The preparation method of the polyether-ether-ketone material specifically comprises the following steps:
1) Preparing a polyether-ether-ketone material into a shape required by a repair area through injection molding, 3D printing, presoaking and other processes;
2) Activating the surface: the PEEK material was placed in a plasma processor for surface activation.
3) Covalent bonding: immediately placing the PEEK material subjected to plasma treatment in an acrylic acid solution with the concentration of 0.1-5mol/L by weight, heating, taking out and flushing with water for three times; preparing hyperbranched polylysine solution, adding 10-50 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride for activation, adding 10-50 parts of N-hydroxysuccinimide for activation, adding the PEEK material treated by acrylic acid for reaction overnight at normal temperature, taking out, washing with water for three times, and drying.
4) Non-covalent loading: 1-10 parts of fluorescent molecules or medicines with negative electricity are prepared into a solution, and the PEEK material is put in, stirred, taken out and dried.
The functionalized surface modified polyether-ether-ketone material has high-efficiency load of growth promoting drugs, thereby promoting cell growth and resisting infection.
The promotion of cell growth is to promote the growth of mouse embryo osteoblast precursor cells.
The anti-infective property is particularly staphylococcus aureus and escherichia coli.
The invention has the beneficial effects that:
the invention provides a stable and efficient bioactive modification, namely PEEK which can be chemically grafted and acrylated only by soaking at room temperature after plasma treatment, does not change the mechanical properties of a material body, and has various biological properties of promoting osteoblast osteogenic differentiation and having remarkable sterilization effect. The invention has simple process, high efficiency and better repeatability, and can improve the defect that the current PEEK orthopedic implant is applied to clinic.
Drawings
Fig. 1: a PEEK physical diagram before and after modification by acrylic acid;
fig. 2: water contact angle characterization of PEEK before and after acrylic acid modification;
fig. 3: anti-infective properties to E.coli and Staphylococcus aureus after PEEK modification.
Fig. 4: PEEK is modified by sulfuric acid to form a physical diagram;
Detailed Description
The examples are presented for better illustration of the invention, but the invention is not limited to the examples. Those skilled in the art will appreciate from the foregoing disclosure that various modifications and adaptations of the embodiments described herein are possible and can be made without departing from the scope of the invention.
Example 1
Printing the polyether-ether-ketone melt into a shape required by skull repair through a 3D printer, placing the shape in a plasma processor, adjusting parameters, and performing glow discharge for 20min. Immediately placing the PEEK skull repair implant subjected to plasma treatment in a prepared 0.5mol/L acrylic acid solution, soaking for 30min, taking out and flushing with water for three times; preparing hyperbranched polylysine solution, adding 50mmol/L EDC for activation for 20min, adding 50mmol/L NHS for activation for 1h, adding the PEEK skull repairing implant treated by acrylic acid, reacting overnight at normal temperature, taking out, washing with water for three times, and drying. Preparing a solution of 3mg/mL from negative fluorescent molecular rhodamine and drug alendronate sodium, putting the PEEK skull repairing implant into the solution, stirring the mixture for 30min at normal temperature, taking out the mixture and drying the mixture.
The polyether-ether-ketone without any treatment is marked as PEEK, and the polyether-ether-ketone after chemical grafting treatment is marked as PEEK-AAc, and the appearance diagram is shown in figure 1. The static contact angle was measured on PEEK and PEEK after modification at room temperature, and the results are shown in fig. 2. The contact angle of PEEK after grafting treatment is reduced from 80 degrees to 20 degrees, which shows that the hydrophilicity of PEEK is obviously improved after surface treatment.
The cells used in this example were mouse osteoblast precursor cells, but other mouse adult stem cells (adipose-derived mesenchymal stem cells, bone marrow-derived mesenchymal stem cells, etc.) and other stem cells having osteoblast differentiation potential are also suitable for the present invention. The test specimens used were divided into three groups, bare PEEK (unmodified PEEK), PEEK-AAc (chemically grafted PEEK), PEEK-AAc-AS (PEEK loaded with the drug alendronate sodium after chemical grafting). Sterilizing three groups of samples, placing into 48-well plate, arranging 3 multiple wells in each group, inoculating mouse embryo osteoblast precursor cells (MC 3T 3-E1) onto each group of materials, and controlling cell density (2×10) 4 Per ml), 500 μl per well; 1 day and 3 days after inoculation, each PEEK sample was washed with Phosphate Buffered Saline (PBS); proliferation of cells was studied at predetermined time points using the CCK-8 method. The unmodified PEEK group had no cell proliferation on the surface of the material during both the 1 day and 3 day test periods. PEEK-AAc group has promoting effect on cell proliferation both at 1 day and 3 days. In addition, compared with the PEEK-AAc group, the PEEK-AAc-AS group loaded with the alendronate sodium which is a growth promoting drug has obviously improved effect of promoting cell proliferation.
The antibacterial properties of the materials were evaluated using a dilution coating flat plate method in this example. The specific operation is as follows: the PEEK sheet was placed in a 24-well plate, and the bacterial liquid was diluted to 1X 10 with LB medium 6 CFU/mL. Dropwise adding 25 mu L of bacterial liquid on the surface of each PEEK material, filling gaps among holes of the pore plate with PBS to slow down evaporation of water, and culturing in a 37 ℃ incubator for 4 hours; after removal, 1975 μl of PBS was added to each well and the material and liquid were transferred simultaneously to a new centrifuge tube. Will leavePlacing the tube in an ultrasonic water bath (power 40W) for ultrasonic treatment for 5min, and oscillating for 30s by using a vortex oscillator to fully elute the adhered bacteria; sterilizing the prepared LB solid culture medium solution under high pressure, preserving heat at 50 ℃, pouring about 15mL of liquid into a flat plate before solidification, and uniformly cooling and solidifying to obtain a solid culture medium; after the collected bacterial liquid is subjected to gradient dilution, 100 mu L of the bacterial liquid is dripped in the center of a flat plate, is uniformly smeared by a coater, and is placed in a 37 ℃ incubator for 16 hours of culture; after colonies developed, photographs were taken and the number of colonies on the plates was counted. The pure PEEK group is used as a control, and the antibacterial rate calculating method comprises the following steps: antibacterial ratio= (control CFU-experimental CFU)/control cfu×100%. As shown in the test result in FIG. 3, the unmodified PEEK material has no antibacterial capability, and the antibacterial rate of PEEK-AAc group on escherichia coli and staphylococcus aureus can reach 69% and 43% respectively, which shows that the material with surface grafted with HBPL has very good antibacterial effects on gram-positive bacteria and gram-negative bacteria.
Example 2
Printing the polyether-ether-ketone melt into a shape required by skull repair through a 3D printer, placing the shape in a plasma processor, adjusting parameters, and performing glow discharge for 20min. Immediately placing the PEEK skull repair implant subjected to plasma treatment in a prepared sulfuric acid solution of 0.5mol/L for soaking for 30min, taking out and flushing with water for three times; preparing hyperbranched polylysine solution, adding 50mmol/L EDC for activation for 20min, adding 50mmol/LNHS for activation for 1h, adding the PEEK skull repairing implant treated by acrylic acid, reacting overnight at normal temperature, taking out, washing with water for three times, and drying. Preparing a solution of 3mg/mL from negative fluorescent molecular rhodamine or drug alendronate sodium, placing the PEEK skull repair implant into the solution, stirring the solution for 30min at normal temperature, and drying the solution to obtain the bio-functionalized surface modified polyether-ether-ketone material, wherein the appearance diagram is shown in figure 4.
Comparative example 1
PEEK skull repair implant (such as CN114214592A, a surface treatment method for enhancing the biocompatibility of 3D printing PEEK material) is prepared according to the method in the prior art, the surface of polyether ether ketone (PEEK) is treated, the surface smoothness is improved, the dust particles on the surface of the 3D printing PEEK are eliminated, and the specific treatment procedures are as follows: sand blasting: firstly, carrying out sand blasting treatment on the 3D printing PEEK material; polishing: grinding and polishing the PEEK material subjected to sand blasting under sand paper and diamond grinding paste; ultrasonic cleaning: placing the PEEK material subjected to sand blasting treatment into an acetone solution for ultrasonic vibration cleaning; and (3) adopting a Physical Vapor Deposition (PVD) technology to deposit pure Ta on the surface of the polyether-ether-ketone to obtain the PEEK-based coating material. The total preparation time of comparative example 1 is 2-3 days, a large amount of equipment is needed in the treatment process, the energy consumption is high, and the preparation process is complex and tedious. And heavy metals are in the implant coating and there is a risk of release after long-term implantation.
Comparative example 2
The preparation method for preparing the PEEK skull repair implant (such as CN111116964A, bio-functionalized surface modified polyether-ether-ketone material and the preparation method and application thereof) according to the method in the prior art comprises the following steps: immersing the polyether-ether-ketone material in a strong acid solution for 0.5h, immersing in deionized water for 24h to remove redundant acid, ultrasonically cleaning with deionized water for 3 times each for 20min, and drying to obtain the surface modified polyether-ether-ketone material. The total preparation time is short, the hydrophilia of PEEK is only improved after acidification, the surface is unstable, and the PEEK cannot be acted on a human body for a long time. The PEEK material with the biological functional surface modified disclosed by the invention can be subjected to surface treatment by chemical grafting at normal temperature within 24 hours, and fluorescent molecules and drug molecules are non-covalently combined only by a soaking means to form a coating, so that the PEEK material is endowed with various biological functions including anti-infection, growth promotion and the like.
Claims (7)
1. A preparation method of a bio-functionalized surface modified polyether-ether-ketone material is characterized in that the material is a customized polyether-ether-ketone material, which is prepared by injection molding, 3D printing and presoaking technology, has a specific shape and is provided with an outer layer or is integrally polyether-ether-ketone, and the surface of the polyether-ether-ketone material is subjected to bio-functionalized modification treatment; the biological functionalization modification treatment is that after the polyetheretherketone material is treated by plasma, an activation layer is chemically grafted on the surface of the polyetheretherketone material by a soaking process, wherein the soaking process is as follows: immersing the polyether-ether-ketone material subjected to plasma treatment into an acid solution to generate carboxyl on the surface through acidification, immersing the polyether-ether-ketone material into a hyperbranched polylysine solution activated by 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride EDC and N-hydroxysuccinimide NHS to enable the carboxyl to react with the hyperbranched polylysine in amidation to form a positively charged coating, and finally immersing the coating into a negatively charged fluorescent imaging molecule and/or a growth-promoting drug solution to be combined with a non-covalent load of the negatively charged fluorescent molecule and/or the growth-promoting drug.
2. The method of preparing a biofunctionalized surface modified polyetheretherketone material of claim 1, wherein said polyetheretherketone material is capable of being used as an artificial bone repair implant.
3. The method for preparing a biofunctionalized surface modified polyetheretherketone material as claimed in claim 1, wherein the acid used for acidification is: at least one of sulfuric acid, acrylic acid, phosphoric acid and acetic acid.
4. The method for preparing the bio-functionalized surface modified polyether ether ketone material according to claim 1, wherein the fluorescent molecule is at least one of fluorescein isothiocyanate, FAM maleimide, rhodamine, sulfonylrhodamine 101, 5-carboxymethyl rhodamine, 1-aminonaphthalene-8-carboxylic acid texas red and 5- (iodoacetamido) fluorescein.
5. The method for preparing a bio-functionalized surface modified polyetheretherketone material according to claim 1, wherein the growth-promoting drug is at least one of tacrolimus, potassium pralidoxime, oxiracetam and alendronate sodium.
6. The method for preparing a biofunctionalized surface modified polyetheretherketone material according to any one of claims 1 to 5, wherein the polyetheretherketone material is plasma treated and then combined with acrylic acid, and then covalently reacted with hyperbranched polylysine, and finally forms a stable surface coating by non-covalent interactions with fluorescent molecules and growth promoting drugs.
7. The method of preparing a biofunctionalized surface modified polyetheretherketone material as claimed in any one of claims 1 to 5, wherein said method of preparing comprises the steps of:
1) Preparing polyether-ether-ketone into a shape required by a repair area through injection molding, 3D printing and presoaking processes;
2) Activating the surface: placing a polyether-ether-ketone material in a plasma treatment instrument for surface activation;
3) Covalent bonding: immediately placing the polyether-ether-ketone material subjected to plasma treatment in an acrylic acid solution with the concentration of 0.1-5mol/L by weight, heating, taking out and flushing with water for three times; preparing hyperbranched polylysine solution, adding 10-50 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride for activation, adding 10-50 parts of N-hydroxysuccinimide for activation, adding polyether-ether-ketone treated by acrylic acid for reaction at normal temperature overnight, taking out, washing with water for three times, and drying;
4) Non-covalent loading: preparing 1-10 parts of negatively charged fluorescent molecules or growth promoting drugs into a solution, putting polyether-ether-ketone into the solution, stirring, taking out and drying the solution to obtain the biological functionalized surface modified polyether-ether-ketone material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210600645.3A CN114989475B (en) | 2022-05-30 | 2022-05-30 | Preparation method and product application of biological functionalized surface modified polyether-ether-ketone material |
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| CN202210600645.3A CN114989475B (en) | 2022-05-30 | 2022-05-30 | Preparation method and product application of biological functionalized surface modified polyether-ether-ketone material |
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| CN114989475A CN114989475A (en) | 2022-09-02 |
| CN114989475B true CN114989475B (en) | 2023-07-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106421922A (en) * | 2016-10-09 | 2017-02-22 | 太原理工大学 | Modified hydroxyapatite/carbon nanotube/polyetheretherketon composite material and preparation method thereof |
| DE102017118508A1 (en) * | 2017-08-14 | 2019-02-14 | Verein zur Förderung von Innovationen durch Forschung, Entwicklung und Technologietransfer e.V. (Verein INNOVENT e.V.) | Method for producing a biocompatible layer on an implant surface |
| CN113185740A (en) * | 2021-04-29 | 2021-07-30 | 华东理工大学 | Method for improving antibacterial activity and biocompatibility of substrate surface |
| CN113354786A (en) * | 2021-07-07 | 2021-09-07 | 苏州大学附属第一医院 | Method for preparing difunctional polyether-ether-ketone by using mussel-derived peptide in combination with bioorthogonal reaction and application thereof |
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| KR101770827B1 (en) * | 2011-03-10 | 2017-08-23 | 서울대학교산학협력단 | Stent for selectively capturing epc and process for producing the same |
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| CN111035803B (en) * | 2019-11-07 | 2021-07-06 | 浙江大学 | Titanium implant material with anti-infection and osseointegration promoting functions and preparation method thereof |
| CN113527748B (en) * | 2021-07-12 | 2023-01-03 | 南方科技大学 | Polyether-ether-ketone surface modification method, polyether-ether-ketone obtained through modification and application of polyether-ether-ketone |
| CN113713172B (en) * | 2021-09-08 | 2023-04-11 | 深圳清华大学研究院 | In-situ endothelialization promoting coating and preparation method thereof |
| CN114470324B (en) * | 2022-02-08 | 2023-04-04 | 福建医科大学附属协和医院 | Novel strategy for the modification of universal bone implants for the intervention of bone defects associated with diabetes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106421922A (en) * | 2016-10-09 | 2017-02-22 | 太原理工大学 | Modified hydroxyapatite/carbon nanotube/polyetheretherketon composite material and preparation method thereof |
| DE102017118508A1 (en) * | 2017-08-14 | 2019-02-14 | Verein zur Förderung von Innovationen durch Forschung, Entwicklung und Technologietransfer e.V. (Verein INNOVENT e.V.) | Method for producing a biocompatible layer on an implant surface |
| CN113185740A (en) * | 2021-04-29 | 2021-07-30 | 华东理工大学 | Method for improving antibacterial activity and biocompatibility of substrate surface |
| CN113354786A (en) * | 2021-07-07 | 2021-09-07 | 苏州大学附属第一医院 | Method for preparing difunctional polyether-ether-ketone by using mussel-derived peptide in combination with bioorthogonal reaction and application thereof |
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