CN109276753B - Medical titanium alloy stent modified by mesoporous bioactive glass loaded with potassium ferrate and preparation method thereof - Google Patents

Medical titanium alloy stent modified by mesoporous bioactive glass loaded with potassium ferrate and preparation method thereof Download PDF

Info

Publication number
CN109276753B
CN109276753B CN201811451940.7A CN201811451940A CN109276753B CN 109276753 B CN109276753 B CN 109276753B CN 201811451940 A CN201811451940 A CN 201811451940A CN 109276753 B CN109276753 B CN 109276753B
Authority
CN
China
Prior art keywords
titanium alloy
potassium ferrate
bioactive glass
mesoporous
mesoporous bioactive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811451940.7A
Other languages
Chinese (zh)
Other versions
CN109276753A (en
Inventor
郝永强
符静珂
姜闻博
富灵杰
王磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ninth Peoples Hospital Shanghai Jiaotong University School of Medicine
Original Assignee
Ninth Peoples Hospital Shanghai Jiaotong University School of Medicine
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ninth Peoples Hospital Shanghai Jiaotong University School of Medicine filed Critical Ninth Peoples Hospital Shanghai Jiaotong University School of Medicine
Priority to CN201811451940.7A priority Critical patent/CN109276753B/en
Publication of CN109276753A publication Critical patent/CN109276753A/en
Application granted granted Critical
Publication of CN109276753B publication Critical patent/CN109276753B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • 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
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • 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
    • 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
    • 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
    • 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
    • A61L2300/602—Type of release, e.g. controlled, sustained, slow
    • A61L2300/604—Biodegradation
    • 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
    • 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
    • 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
    • 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
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • 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

Abstract

The invention discloses a medical titanium alloy bracket modified by mesoporous bioactive glass loaded with potassium ferrate and a preparation method thereof. The titanium alloy bracket is printed by adopting a 3D technology. The mesoporous bioactive glass modified on the surface of the titanium alloy stent is beneficial to improving the osteogenesis performance of the material; the potassium ferrate loaded in the mesoporous pore canal of the mesoporous bioactive glass is beneficial to improving the antibacterial performance of the stent; the modification of the chitosan is beneficial to improving the stability of the potassium ferrate and slowing down the release of the potassium ferrate, and is also beneficial to further improving the antibacterial and osteogenic properties of the material; the titanium alloy bracket is of a diamond lattice structure, is beneficial to the growth of new bones into the material, and is matched with the surface modification of the osteogenesis promoting and antibacterial substances to improve the biological performance of the material.

Description

Medical titanium alloy stent modified by mesoporous bioactive glass loaded with potassium ferrate and preparation method thereof
Technical Field
The invention relates to the technical field of medical materials, in particular to a medical titanium alloy stent which is loaded with potassium ferrate and is surface-modified by mesoporous bioactive glass and a preparation method thereof.
Background
The medical titanium alloy material has the characteristics of high specific strength, fatigue resistance, corrosion resistance, excellent biocompatibility and the like, and has the elastic modulus close to that of human bones, so the medical titanium alloy material is used as a hard tissue implantation material and has wide clinical application. However, the current titanium alloy stent lacks biological activity, and has poor bone forming performance after being implanted into a human body, and the clinical effect of the titanium alloy stent is reduced due to possible postoperative infection and the like. The bioactive glass is a material which can repair, replace and regenerate body tissues and can enable the tissues and the materials to form bonding effect. The degradation product can promote the generation of growth factors, promote the multiplication of cells, enhance the gene expression of osteoblasts and the growth of bone tissues, and is the only artificial biomaterial which can be bonded with bone tissues and connected with soft tissues so far. Therefore, the bioactive glass material is modified on the surface of the medical titanium alloy implant material through a physical and chemical process, and the osteogenesis performance of the medical titanium alloy implant material can be improved.
Potassium ferrate (K)2FeO4) The middle iron element is in the highest valence state, namely Fe (VI), and has extremely strong oxidizing property, so that the load and the release of the potassium ferrate are favorable for improving the antibacterial performance of the stent material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a medical titanium alloy bracket with a surface modified with mesoporous bioactive glass and a mesoporous structure of the mesoporous bioactive glass loaded with potassium ferrate, wherein the bracket has the performances of promoting the growth of bone tissues and resisting bacteria.
In order to achieve the aim, the invention provides a preparation method of a medical titanium alloy stent modified by mesoporous bioactive glass loaded with potassium ferrate, which comprises the following steps:
step 1, spin-coating a precursor solution of mesoporous bioactive glass on the surface of the titanium alloy support, and calcining at high temperature to obtain a titanium alloy support modified by a mesoporous bioactive glass layer, which is marked as MBG-Ti;
step 2, loading potassium ferrate in the mesoporous pore canal of the mesoporous bioactive glass of MBG-Ti, wherein the loading potassium ferrate comprises the following steps:
step 2.1, soaking the MBG-Ti in an organic solvent, adding gamma-glycidyl ether propyl trimethoxysilane, and refluxing for 3-6 hours under the protection of dry nitrogen; after the reaction is finished, washing the bracket with acetone and drying in vacuum to obtain ethylene oxide modified MBG-Ti, which is marked as MBG-Ti-G;
step 2.2, soaking the MBG-Ti-G into a potassium ferrate aqueous solution, shaking for 1-3 h, standing, washing with a buffer solution with the pH value of 10-13, and drying at normal temperature in vacuum to obtain the MBG-Ti-G loaded with potassium ferrate, wherein the MBG-Ti-G is marked as K @ MBG-Ti-G;
and 3, dipping the K @ MBG-Ti-G in a dimethyl sulfoxide solution of benzoyl chitosan, shaking for 6-12 h, washing with dimethyl sulfoxide, and drying at normal temperature in vacuum to obtain the titanium alloy scaffold loaded with potassium ferrate and linked with mesoporous bioactive glass modified by chitosan.
Preferably, in step 1, the preparation method of the precursor solution of mesoporous bioactive glass comprises: 9-15 parts by weight of EO20PO70EO20Dissolving the raw materials in 160-200 parts of ethanol solution, stirring at room temperature for 1 hour, adding 15-25 parts of ethyl orthosilicate, 3-6 parts of calcium nitrate tetrahydrate, 1-3 parts of triethyl phosphate and 2-6 parts of 0.5M hydrochloric acid solution, and continuously stirring at room temperature for 24-30 hours.
Preferably, in step 2.1, the volume ratio of the organic solvent to the gamma-glycidyl ether propyl trimethoxysilane is (1-10): 1.
Preferably, in step 2.2, the potassium ferrate aqueous solution is obtained by dispersing potassium ferrate in a buffer solution with a pH value of 10-13, and the concentration of potassium ferrate in the potassium ferrate aqueous solution is 0.1-5 mg/mL.
Preferably, in the step 3, the concentration of the benzoyl chitosan in the dimethyl sulfoxide solution of benzoyl chitosan is 1-20 mg/mL.
The invention also provides a medical titanium alloy bracket modified by the mesoporous bioactive glass loaded with potassium ferrate, which is prepared by the method, wherein the surface of the titanium alloy bracket is modified with a mesoporous bioactive glass layer, and the mesoporous pore canal of the mesoporous bioactive glass is loaded with the potassium ferrate.
Preferably, the titanium alloy support is a porous titanium alloy support printed in a 3D mode, and the porous printing structure of the titanium alloy support is printed according to a diamond lattice structure.
Preferably, the pore diameter of the titanium alloy bracket is 400-500 μm.
Preferably, the mesoporous bioactive glass of the titanium alloy stent is linked with chitosan.
Preferably, the molecular chains of the chitosan are orderly arranged on the surfaces of mesoporous channels of the mesoporous bioactive glass in a physiological environment.
Has the advantages that:
(1) the mesoporous bioactive glass modified on the surface of the titanium alloy stent is beneficial to improving the osteogenesis performance of the stent;
(2) the potassium ferrate loaded in the mesoporous pore canal of the mesoporous bioactive glass is beneficial to improving the antibacterial performance of the stent;
(3) the modification of the chitosan is beneficial to improving the stability of the potassium ferrate and slowing down the release of the potassium ferrate, and is also beneficial to further improving the antibacterial and osteogenic properties of the stent;
(4) the porous scaffold with the diamond lattice structure is beneficial to the growth of new bones into the scaffold, and is matched with the surface modification of the osteogenesis promoting and antibacterial substances, thereby being beneficial to improving the biological performance of the titanium alloy scaffold.
Drawings
Fig. 1 is a transmission electron micrograph of the mesoporous bioactive glass modified titanium alloy scaffold loaded with potassium ferrate and linked with chitosan of example 1.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and examples.
The invention modifies mesoporous bioactive glass on the surface of titanium alloy, and utilizes the mesoporous structure of the mesoporous bioactive glass to load potassium ferrate with antibacterial effect. The modification of the chitosan is beneficial to improving the stability of the potassium ferrate and slowing down the release of the potassium ferrate, and is also beneficial to further improving the antibacterial and osteogenic properties of the material.
Potassium ferrate is very sensitive to water and can be rapidly decomposed to generate oxygen, so that the oxidation and antibacterial properties of the potassium ferrate are lost. According to the invention, potassium ferrate is loaded in the mesoporous bioactive glass, and the modification effect of chitosan on the surface of a mesoporous pore channel of the mesoporous bioactive glass is utilized, so that the contact time of the potassium ferrate and water can be prolonged, the decomposition of the potassium ferrate is slowed down, and the oxidability and the antibacterial capability of the potassium ferrate are improved.
Before loading potassium ferrate, modifying titanium alloy with gamma-glycidyl ether propyl trimethoxysilane (gamma-GPTMS) to make the generated ethylene oxide group react with amino on chitosan molecular chain in the subsequent reaction to make the chitosan of the subsequent reaction linked on the surface of the pore channel of the mesoporous bioactive glass.
The potassium ferrate enters mesoporous channels of the mesoporous bioactive glass through diffusion, and chitosan molecular chains are connected to the surfaces of the mesoporous channels of the mesoporous bioactive glass. The chitosan molecular chain contains a large number of hydroxyl and amino, and under different pH conditions, electrostatic repulsion generated between the amino on the chitosan molecular chain and hydrogen bond interaction between the amino and the hydroxyl have different strengths. Under the physiological environment (pH value of 7.4), the interaction of hydrogen bonds between amino groups on the chitosan molecular chain is larger than the electrostatic repulsion between amino groups and hydroxyl groups, the chitosan molecule is in a crystalline state, the molecular chain is orderly arranged at the mesoporous pore canal of the mesoporous bioactive glass, and the diffusion of water molecules into the mesoporous pore canal is slowed down, so that the decomposition time of the potassium ferrate is prolonged, and the oxidability and the antibacterial capability of the potassium ferrate are improved.
Example 1
Step 1: 3D prints titanium alloy support
Step 1.1: the Ti-6Al-4V powder comprises the following components: 6.04% Al, 4.05% V, 0.013% C, 0.07% Fe, 0.13% O, 89.69% Ti. The powder size is 45-80 μm. The titanium alloy support is designed based on CAD software and printed through an EMB system, the printing temperature is controlled to be 680 ℃, and the scanning speed of an electron beam is controlled to be 400 mm/s. And (5) helium atmosphere protection. The aperture of the porous titanium alloy is controlled to be 400-500 mu m, the height of the support is 2mm, the diameter of the support is 10mm, the thickness of a single layer to be printed is 55 mu m, and the porous printing structure of the titanium alloy support is printed according to a diamond lattice structure.
Step 2: 3D printing titanium alloy bracket surface modification Mesoporous Bioactive Glass (MBG)
Step 2.1: adding 12g of EO20PO70EO20(average molecular weight of 5800) was dissolved in 180g of ethanol solution and stirred at room temperature for 1h, after which 20.1g of ethyl orthosilicate, 4.2g of calcium nitrate tetrahydrate, 2.19g of triethyl phosphate and 3g of 0.5M hydrochloric acid solution were added to the above solution and stirring was continued at room temperature for 24h to obtain a precursor solution of mesoporous bioactive glass.
Step 2.2: setting parameters to be 500rpm for 10s by using spin coating equipment; thereafter 2000rpm continued for 20 s. Then placing the bracket at room temperature for 8 h; the spin coating was repeated 10 times as described above. And (3) keeping the obtained support in a muffle furnace at 650 ℃, heating at the speed of 1 ℃/min, and calcining for 6h to obtain the mesoporous bioactive glass modified titanium alloy support (named as MBG-Ti').
And step 3: potassium ferrate load and chitosan modification
Step 3.1: the MBG-Ti' obtained in step 2 was immersed in 10mL of toluene and sonicated for 15 min. Thereafter, 5mL of gamma-glycidoxypropyltrimethoxysilane (gamma-GPTMS) was added to the toluene solution and refluxed under a blanket of dry nitrogen for 5 h. After the reaction is finished, washing the titanium alloy support with acetone for 3 times, and drying the product in vacuum to obtain the ethylene oxide modified titanium alloy support named as MBG-Ti-G'.
Step 3.2: a phosphate buffer solution (PBS pH12) having a pH of 12 was prepared, and 10mg of potassium ferrate was dissolved in 10mL of a PBS solution (pH12) to prepare a 1mg/mL aqueous solution of potassium ferrate. And (3) soaking the MBG-Ti-G ' prepared in the step (3.1) in the solution, shaking for 2h, stopping shaking, standing for 30min, washing with PBS (phosphate buffer solution) with the pH of 12, and drying in vacuum at normal temperature to obtain the potassium ferrate-loaded MBG-Ti-G ', which is recorded as K @ MBG-Ti-G '.
Step 3.3: and (3) dipping the K @ MBG-Ti-G 'obtained in the step (3.2) into 20mL of dimethyl sulfoxide solution of benzoyl chitosan (Cs) (the concentration of the benzoyl chitosan is 10mg/mL), shaking for 6h, washing with dimethyl sulfoxide for 2h, and drying at normal temperature in vacuum to obtain the mesoporous bioactive glass modified titanium alloy stent loaded with potassium ferrate and linked with chitosan, which is named as K @ MBG-Ti-G-Cs'.
As shown in figure 1, the surface of the titanium alloy is a smooth and flat structure, and after mesoporous bioactive glass modification and potassium ferrate and chitosan modification, the porous structure of the titanium alloy is not changed, which is beneficial to the expansion of new bones. The surface concave-convex structure is a mesoporous bioactive glass nano coating on the surface of the bracket.
Example 2
Example 2 differs from example 1 in that: in the step 3.1, the addition amount of gamma-glycidyl ether propyl trimethoxysilane (gamma-GPTMS) is 1 mL; in the step 3.2, the concentration of the potassium ferrate in the potassium ferrate water solution is 0.1 mg/mL; in step 3.3, the concentration of benzoyl chitosan is 1 mg/mL. The titanium alloy stent modified by mesoporous bioactive glass loaded with potassium ferrate and linked with chitosan can be prepared in example 2, and the titanium alloy stent prepared in example 2 has osteogenesis promoting and antibacterial properties.
Example 3
Example 3 differs from example 1 in that: in the step 3.1, the addition amount of gamma-glycidyl ether propyl trimethoxysilane (gamma-GPTMS) is 10 mL; in the step 3.2, the concentration of the potassium ferrate in the potassium ferrate water solution is 5 mg/mL; in step 3.3, the concentration of benzoyl chitosan is 20 mg/mL. The titanium alloy stent modified by mesoporous bioactive glass loaded with potassium ferrate and linked with chitosan can be prepared in example 3, and the titanium alloy stent prepared in example 3 has osteogenesis promoting and antibacterial properties.
In conclusion, the medical titanium alloy implant stent is constructed by using a 3D printing technology, and mesoporous bioactive glass is modified on the surface of the medical titanium alloy stent by a spin coating process to form a primary nano coating; the mesoporous bioactive glass modified 3D printing titanium alloy bracket with osteogenesis promoting and antibacterial properties can be obtained by utilizing the mesoporous structure of the mesoporous bioactive glass, loading a potassium ferrate compound in a mesoporous pore channel and modifying the surface with chitosan.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.

Claims (9)

1. A preparation method of a medical titanium alloy stent modified by mesoporous bioactive glass loaded with potassium ferrate is characterized by comprising the following steps:
step 1, the titanium alloy support is a porous titanium alloy support printed in a 3D mode, and a porous printing structure of the titanium alloy support is printed according to a diamond lattice structure; spin-coating a precursor solution of the mesoporous bioactive glass on the surface of the titanium alloy bracket, and calcining at high temperature to obtain a titanium alloy bracket modified by a mesoporous bioactive glass layer, which is marked as MBG-Ti;
step 2, loading potassium ferrate in the mesoporous pore canal of the mesoporous bioactive glass of MBG-Ti, wherein the loading potassium ferrate comprises the following steps:
step 2.1, soaking the MBG-Ti in an organic solvent, adding gamma-glycidyl ether propyl trimethoxysilane, and refluxing for 3-6 hours under the protection of dry nitrogen; after the reaction is finished, washing the bracket with acetone and drying in vacuum to obtain ethylene oxide modified MBG-Ti, which is marked as MBG-Ti-G;
step 2.2, soaking the MBG-Ti-G into a potassium ferrate aqueous solution, shaking for 1-3 h, standing, washing with a buffer solution with the pH value of 11-13, and drying at normal temperature in vacuum to obtain the MBG-Ti-G loaded with potassium ferrate, wherein the MBG-Ti-G is marked as K @ MBG-Ti-G;
and 3, dipping the K @ MBG-Ti-G in a dimethyl sulfoxide solution of benzoyl chitosan, shaking for 6-12 h, washing with dimethyl sulfoxide, and drying at normal temperature in vacuum to obtain the titanium alloy scaffold loaded with potassium ferrate and linked with mesoporous bioactive glass modified by chitosan.
2. The preparation method of the medical titanium alloy stent modified by the mesoporous bioactive glass loaded with potassium ferrate according to claim 1, wherein in the step 1, the preparation method of the precursor solution of the mesoporous bioactive glass comprises the following steps:
9-15 parts by weight of EO20PO70EO20Dissolving the mixture in 160-200 parts of ethanol solution, stirring at room temperature for 1 hour, adding 15-25 parts of ethyl orthosilicate, 3-6 parts of calcium nitrate tetrahydrate, 1-3 parts of triethyl phosphate and 2-6 parts of 0.5M hydrochloric acid solution, and continuously stirring at room temperature for 24-30 hours.
3. The preparation method of the medical titanium alloy stent modified by the mesoporous bioactive glass loaded with potassium ferrate according to claim 1, wherein in the step 2.1, the volume ratio of the organic solvent to the gamma-glycidyl ether propyl trimethoxysilane is (1-10): 1.
4. The method for preparing the medical titanium alloy stent modified by the mesoporous bioactive glass loaded with potassium ferrate according to claim 1, wherein in the step 2.2, the potassium ferrate aqueous solution is obtained by dispersing potassium ferrate in a buffer solution with the pH value of 10-13, and the concentration of potassium ferrate in the potassium ferrate aqueous solution is 0.1-5 mg/mL.
5. The preparation method of the medical titanium alloy stent modified by the mesoporous bioactive glass loaded with potassium ferrate according to claim 1, wherein in the step 3, the concentration of the benzoyl chitosan in the dimethyl sulfoxide solution of the benzoyl chitosan is 1-20 mg/mL.
6. The medical titanium alloy stent modified by the mesoporous bioactive glass loaded with potassium ferrate according to any one of claims 1 to 5, which is prepared by the preparation method, wherein the surface of the titanium alloy stent is modified by a mesoporous bioactive glass layer, and potassium ferrate is loaded in mesoporous channels of the mesoporous bioactive glass.
7. The medical titanium alloy stent modified by the mesoporous bioactive glass loaded with potassium ferrate according to claim 6, which is prepared by the preparation method, is characterized in that the pore diameter of the titanium alloy stent is 400-500 μm.
8. The medical titanium alloy stent modified by the potassium ferrate-loaded mesoporous bioactive glass according to claim 6, wherein chitosan is linked to the mesoporous bioactive glass of the titanium alloy stent.
9. The medical titanium alloy stent modified by the mesoporous bioactive glass loaded with potassium ferrate according to claim 8, wherein the molecular chains of the chitosan are orderly arranged on the surfaces of mesoporous channels of the mesoporous bioactive glass in a physiological environment.
CN201811451940.7A 2018-11-30 2018-11-30 Medical titanium alloy stent modified by mesoporous bioactive glass loaded with potassium ferrate and preparation method thereof Active CN109276753B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811451940.7A CN109276753B (en) 2018-11-30 2018-11-30 Medical titanium alloy stent modified by mesoporous bioactive glass loaded with potassium ferrate and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811451940.7A CN109276753B (en) 2018-11-30 2018-11-30 Medical titanium alloy stent modified by mesoporous bioactive glass loaded with potassium ferrate and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109276753A CN109276753A (en) 2019-01-29
CN109276753B true CN109276753B (en) 2021-11-02

Family

ID=65174005

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811451940.7A Active CN109276753B (en) 2018-11-30 2018-11-30 Medical titanium alloy stent modified by mesoporous bioactive glass loaded with potassium ferrate and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109276753B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105080960A (en) * 2015-08-06 2015-11-25 侯力玮 Soil contamination treatment repairing particle and repairing method
CN108659585A (en) * 2018-05-24 2018-10-16 成都今天化工有限公司 A method of preparing anti-moss nano-titanium porcelain coating

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008127287A2 (en) * 2006-10-11 2008-10-23 Biolife, L.L.C. Materials and methods for wound treatment
CN102188749A (en) * 2010-03-10 2011-09-21 中国科学院上海硅酸盐研究所 3D porous bracket with mesoporous biological glass coating and preparation method thereof
CN104096262B (en) * 2013-04-09 2017-02-08 上海交通大学医学院附属第九人民医院 Collagen/chitosan/mesoporous bioactive glass composite nanofiber membrane material and preparation method thereof
US9308351B2 (en) * 2013-05-28 2016-04-12 Smh Device Corp. Tunneled catheter with hemostasis mechanism
CN103342453B (en) * 2013-07-09 2015-12-02 扬州大学 The method of the monodisperse mesoporous bioactivity glass microballoon of template synthesis
CN103961713A (en) * 2014-05-06 2014-08-06 中国科学院上海硅酸盐研究所 Application of mesoporous silica based controlled release material modified by chitosan
CN103920153A (en) * 2014-05-06 2014-07-16 中国科学院上海硅酸盐研究所 Chitosan-modified pH responsive medicine-loading controlled release material and preparation method thereof
CN104548111A (en) * 2015-01-26 2015-04-29 华东理工大学 Composite carrier, pH response type compound drug-loading system and preparation method of composite carrier
CN105412984A (en) * 2015-12-18 2016-03-23 华东理工大学 Albumen-carrying 3D tissue engineering scaffold and preparation method thereof
CN106618809B (en) * 2017-01-01 2019-01-25 常州华森医疗器械有限公司 POROUS TITANIUM Invasive lumbar fusion device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105080960A (en) * 2015-08-06 2015-11-25 侯力玮 Soil contamination treatment repairing particle and repairing method
CN108659585A (en) * 2018-05-24 2018-10-16 成都今天化工有限公司 A method of preparing anti-moss nano-titanium porcelain coating

Also Published As

Publication number Publication date
CN109276753A (en) 2019-01-29

Similar Documents

Publication Publication Date Title
JP2010537763A (en) Bioactive nanocomposite material
CN107149698B (en) Biocompatible materials and uses thereof
EA012091B1 (en) Medical device comprising a reticulated composite material
US20100178278A1 (en) Formable bioceramics
WO2013074748A1 (en) Gelatinous hydroxyapatite-nanocomposites
KR101393462B1 (en) fabricating method of porous calcium-phosphate bone substitute material and porous calcium-phosphate bone substitute material fabricated thereby
CN102008752B (en) Porous biphasic calcium phosphate biological scaffold with nano hydroxyapatite coating and preparation method thereof
US9925306B2 (en) Hyaluronic acid-calcium phosphate composite for growth factor support and method for producing same
Fan et al. A new composite scaffold of bioactive glass nanoparticles/graphene: Synchronous improvements of cytocompatibility and mechanical property
CN113398327A (en) Preparation method of MXene/bioglass microsphere composite material with high biological activity
JP5578499B2 (en) Calcium phosphate / biodegradable polymer hybrid material, its production method and implant using the hybrid material
Gupta et al. Mesoporous bioactive glass and its applications
CN108404222B (en) Porous titanium-based nano composite material for hard tissue material and preparation method and application thereof
CN109205581B (en) Preparation method of composite hydroxyapatite powder with photo-thermal synergistic antibacterial property
TW201720472A (en) Surface-modified dental material having properties of anti-bacteria and stimulating cell growth and manufacturing method thereof
CN109276753B (en) Medical titanium alloy stent modified by mesoporous bioactive glass loaded with potassium ferrate and preparation method thereof
CN103656756A (en) Nano-hydroxyapatite/silk fibroin composite membrane material and preparation method thereof
CN112569403A (en) Construction method of bioactive slow-release coating based on polydopamine/graphene oxide/collagen nano-film
JP4437173B2 (en) Production method of organic-inorganic hybrid
CN108310456B (en) Preparation method of graphene oxide/nano-hydroxyapatite composite silica gel modified porous scaffold material
CN113024278A (en) Calcium phosphate ceramic with in-situ graphene film and preparation method and application thereof
CN113368302A (en) Protein-loaded bioactive calcium phosphate nanoparticles and preparation method thereof
JP2003342011A (en) Organic substance-modified hydroxyapatite porous body
JPS62266065A (en) Living body compatible laminar substance containing calcium phosphate and its production
CN108578776B (en) Preparation method of bioglass/hydrogel composite coating on surface of magnesium-based substrate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant