CN108578776B - Preparation method of bioglass/hydrogel composite coating on surface of magnesium-based substrate - Google Patents

Preparation method of bioglass/hydrogel composite coating on surface of magnesium-based substrate Download PDF

Info

Publication number
CN108578776B
CN108578776B CN201810384380.1A CN201810384380A CN108578776B CN 108578776 B CN108578776 B CN 108578776B CN 201810384380 A CN201810384380 A CN 201810384380A CN 108578776 B CN108578776 B CN 108578776B
Authority
CN
China
Prior art keywords
bioglass
magnesium
powder
steps
solution
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.)
Expired - Fee Related
Application number
CN201810384380.1A
Other languages
Chinese (zh)
Other versions
CN108578776A (en
Inventor
温翠莲
裘依梅
吴军茹
李瑞峰
叶健霞
张腾
温娜
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.)
Fuzhou University
Original Assignee
Fuzhou University
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 Fuzhou University filed Critical Fuzhou University
Priority to CN201810384380.1A priority Critical patent/CN108578776B/en
Publication of CN108578776A publication Critical patent/CN108578776A/en
Application granted granted Critical
Publication of CN108578776B publication Critical patent/CN108578776B/en
Expired - Fee Related 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
    • A61L27/50—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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • 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
    • 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
    • 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
    • A61L27/52—Hydrogels or hydrocolloids
    • 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
    • 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
    • A61L2300/412—Tissue-regenerating or healing or proliferative 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
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412—Tissue-regenerating or healing or proliferative agents
    • A61L2300/414—Growth factors

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Veterinary Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Biomedical Technology (AREA)
  • Molecular Biology (AREA)
  • Materials For Medical Uses (AREA)
  • Colloid Chemistry (AREA)

Abstract

The invention belongs to the field of biological functional materials, and discloses a preparation method of a magnesium-based bottom surface biological glass/hydrogel composite coating, which comprises the following steps: micro-arc oxidation pretreatment is carried out on the bottom surface of the magnesium base to obtain porous surface appearance, meanwhile, the bioglass powder is subjected to amination surface modification to improve the surface active sites, polyethylene glycol (DFPEG) with benzaldehyde groups at two ends is synthesized and used as a gel factor to crosslink bioglass/chitosan composite solution, and a bioglass/hydrogel composite coating is obtained on the bottom surface of the magnesium base. The method is simple and efficient, and the used raw materials are cheap and easy to obtain. The bioglass/hydrogel composite coating is prepared on the bottom surface of the magnesium-based substrate, so that the corrosion resistance and biocompatibility of magnesium and magnesium alloy in a physiological environment can be improved, and meanwhile, the quick repair of human tissues can be realized by loading medicines, growth factors and the like in the hydrogel, and the bioglass/hydrogel composite coating has a good application prospect.

Description

Preparation method of bioglass/hydrogel composite coating on surface of magnesium-based substrate
Technical Field
The invention relates to the field of biological functional materials, in particular to a preparation method of a magnesium-based bottom surface biological glass/hydrogel composite coating.
Background
The degradable biological material can be continuously decomposed in vivo after being implanted into organisms, and the decomposition products can be absorbed by the organisms or discharged out of the bodies, so that the degradable biological material becomes the leading edge and the hot spot of international research in the field of the current biological materials. At present, most degradable biological materials applied in bone implant materials mainly comprise high molecular polymers such as polylactic acid (PLA) and polyglycolic acid (PGA), but the strength of the materials is generally low, and the materials are difficult to bear large load. Magnesium not only has good mechanical property, but also is nontoxic to human body and can be gradually degraded and absorbed in vivo through corrosion, so that magnesium and magnesium alloy are increasingly favored by people as a degradable implantation biological material with great development potential.
Compared with the metal implant materials such as titanium alloy and stainless steel which are clinically applied at present, the advantages of magnesium and the alloy thereof are mainly shown as follows: mechanical properties, especially density and elastic modulus (1.74-2.0 g/cm)341-45 GPa) is closer to human bone (1.8-2.1 g/cm)33-20 GPa), the stress shielding effect caused by mismatching of the elastic modulus can be effectively relieved; good biocompatibility: magnesium is an essential element for human body, and can promote the formation of bone cells and accelerate the healing of bones; degradability: the implant does not need to be taken out after being implanted, thereby avoiding the body pain and the economic burden of a patient caused by a secondary operation.
However, magnesium is an active metal element, and the equilibrium potential is about-1.70V when magnesium corrodes, so the most important defect of magnesium and magnesium alloy as a metal implant is poor corrosion resistance, and the corrosion rate of the magnesium metal implant is much faster than that of the magnesium metal implant without chloride ions under the physiological environment of a human body, especially in the presence of chloride ions, so that the mechanical integrity of the implant before fracture healing is difficult to maintain, the mechanical property of the implant is lost, and the operation fails. Therefore, the improvement of the corrosion resistance of magnesium and magnesium alloy and the effective control of the degradation rate of magnesium and magnesium alloy in organisms are the key points for the clinical application and development of magnesium and magnesium alloy as degradable implant materials. And the surface modification is one of effective means for effectively improving the corrosion resistance and the biocompatibility of the magnesium alloy biomaterial.
Bioglass is a biomaterial for regenerative medicine, can promote the deposition of bone-like apatite in a body fluid environment, and can stimulate various favorable cell behaviors. Bioglass has excellent mechanical properties, bioactivity, histocompatibility, osteoconductivity and osteoinductivity, and has been widely used in clinical applications. However, the biological glass product has poor general chemical stability, low mechanical strength, poor dispersibility in an organic organism and easy agglomeration, and the combination of the biological glass and the organic phase is loose, so that the mechanical property of the material is not obviously improved, and the problems limit the clinical application of the biological glass, particularly the application in the fields other than hard tissue repair.
The hydrogel is a three-dimensional space structure formed by cross-linking molecular chains, and solvent molecules are fixed in a network through surface tension and capillary force to form a soft substance. Hydrogel materials have a high-water-content structure similar to human tissues, have good biocompatibility, and can provide an environment similar to that in vivo for biological tissues in vitro, so that the hydrogel materials are widely concerned and applied in the biomedical field. Besides delivering drugs, the method of delivering substances into the body by using hydrogel as a carrier is further expanded and applied to delivering bioactive substances such as cells and genes, and is used in the rapidly-developed medical frontier treatment methods such as cell therapy and gene therapy. However, with the development of modern medicine, biomedical hydrogels face more requirements and challenges, such as the requirement of degradation capability and implantation mode, so that the hydrogel materials need to be further improved.
The combination of the bioglass and the hydrogel material can obtain a novel biomaterial with good biological activity, and the problem that magnesium alloy is easy to corrode in organisms and has poor biocompatibility can be solved by using the biomaterial as a coating of a magnesium alloy bone implant material. According to the invention, the surface appearance of the magnesium-based bottom surface is obtained by micro-arc oxidation pretreatment, meanwhile, the bioglass powder is subjected to amination surface modification, the surface active sites are improved, polyethylene glycol (DFPEG) with benzaldehyde groups at two ends is synthesized, and the DFPEG is used as a gel factor to crosslink bioglass/chitosan composite solution, so that the bioglass/hydrogel composite coating is obtained on the magnesium-based bottom surface. The bioglass/hydrogel composite coating is prepared on the bottom surface of the magnesium-based substrate, so that the corrosion resistance and biocompatibility of magnesium and magnesium alloy in a physiological environment can be improved, and meanwhile, the quick repair of human tissues can be realized by loading medicines, growth factors and the like in the hydrogel, and the bioglass/hydrogel composite coating has a good application prospect.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing a magnesium-based bottom surface bioglass/hydrogel composite coating which has corrosion resistance and biocompatibility and can realize the rapid repair of human tissues by loading medicines, growth factors and the like into hydrogel, can be widely applied to the field of biomedicine, and aims to solve the problems that magnesium and magnesium alloy are easy to corrode in organisms and have poor biocompatibility by obtaining the bioglass/hydrogel composite coating on the magnesium-based bottom surface so as to prepare a composite material with good corrosion resistance and biocompatibility.
The technical scheme of the invention is as follows:
(1) grinding a magnesium substrate by 100-grade sand paper 1000, ultrasonically cleaning and drying by using mixed liquid of alcohol and acetone in a volume ratio of 1:1, and taking a stainless steel plate as a cathode; placing the anode and the cathode in a sodium phosphate and sodium hydroxide electrolyte for micro-arc oxidation for 1-60 min;
(2) ball-milling bioglass powder, sieving to obtain powder with the particle size of below 45 micrometers, putting the powder into constant-temperature water at 37 ℃, continuously introducing nitrogen to remove oxygen dissolved in the water, adding a cerium ammonium nitrate solution with the concentration of 0.1 mol/L, magnetically stirring, fully reacting for 30 min, then continuously dropping polyglycidyl methacrylate (GMA) for 30 min, repeatedly washing the solution to be neutral by deionized water and absolute ethyl alcohol after reacting for 1 h, and centrifugally drying to obtain powder, and putting the powder into ethylenediamine according to the mass ratio: water = 3: 2, stirring for 1-6 h at 80 ℃, repeatedly washing the mixture to be neutral by using deionized water and ethanol, and centrifugally drying the mixture to obtain the surface amination modified bioglass powder;
(3) dissolving chitosan in dilute acetic acid solution (volume ratio of acetic acid to water is 2: 100), and magnetically stirring for 1 hour to obtain chitosan acetic acid solution;
(4) after the surface amination modified bioglass powder obtained in the step (2) is subjected to disinfection treatment by ultraviolet irradiation, slowly adding the disinfected bioglass powder into the chitosan acetic acid solution obtained in the step (3) according to the proportion of 1-20 g/L, performing ultrasonic treatment for 1 hour, and magnetically stirring for 1 hour to obtain a bioglass/chitosan composite solution;
(5) modifying polyethylene glycol (PEG) with p-aldehyde benzoic acid through esterification reaction to obtain polyethylene glycol (DFPEG) with double end benzaldehyde end capping, which comprises the steps of continuously stirring and dissolving PEG into 100 mL Tetrahydrofuran (THF) according to the concentration of 30g/L, adding p-aldehyde benzoic acid and a catalyst 4-dimethylamino pyridine (DMAP) (the mass ratio of PEG: p-aldehyde benzoic acid: DMAP is 3: 1: 0.05) after the PEG is completely dissolved, fully stirring until the PEG is completely dissolved, adding N, N' -dicyclohexyl carbodiimide (DCC) (the mass ratio of PEG: DCC is 2: 1), stirring for 3-12 h at room temperature, filtering to remove precipitates, concentrating the filtrate and drying to obtain DFPEG powder. Dissolving DFPEG powder in deionized water (weight ratio of DFPEG to deionized water is 1: 10) to obtain DFPEG gel factor solution;
(6) and (3) placing the magnesium-based substrate material subjected to micro-arc oxidation treatment in the step (1) in the bioglass/chitosan composite solution obtained in the step (4) for ultrasonic treatment for 10 min, slowly dropwise adding the DFPEG gel factor solution obtained in the step (5), fully stirring until the bioglass/chitosan composite solution is sticky, taking out the magnesium-based substrate material, and washing and drying with deionized water to obtain the bioglass/hydrogel composite coating on the surface of the magnesium-based substrate.
The magnesium-based substrate material in the step (1) is pure magnesium or a magnesium alloy material; the concentration of sodium phosphate in the electrolyte is 20-90 g/L, and the concentration of sodium hydroxide is 5-15 g/L.
The bioglass powder in the step (2) is commercially available common bioglass such as 45S5, 58S and the like, and biomedical system glass such as other silicate, borate, phosphate and the like is also included.
The ceric ammonium nitrate solution in the step (2) is prepared by dissolving ceric ammonium nitrate in 1 mol/L HNO3Configuring; wherein the weight ratio of the bioglass, the ammonium ceric nitrate and the GMA is 10: 20: 2.
in the step (3), the weight ratio of the chitosan to the dilute acetic acid solution is 2-6: 100.
compared with the prior art, the invention has the following advantages:
1. the method has the advantages of simple process, easy operation, cheap and easily obtained raw materials, low time consumption and good industrialization prospect.
2. The method comprises the steps of carrying out micro-arc oxidation pretreatment on the bottom surface of the magnesium-based substrate to obtain a porous surface appearance, carrying out amination surface modification on bioglass powder to improve the surface active sites of the bioglass powder, synthesizing polyethylene glycol (DFPEG) with benzaldehyde groups at two ends, using the DFPEG as a gel factor to crosslink bioglass/chitosan composite solution, and obtaining a bioglass/hydrogel composite coating on the bottom surface of the magnesium-based substrate. The bioglass/hydrogel composite coating is prepared on the bottom surface of the magnesium-based substrate, so that the corrosion resistance and biocompatibility of magnesium and magnesium alloy in a physiological environment can be improved, and meanwhile, the quick repair of human tissues can be realized by loading medicines, growth factors and the like in the hydrogel, and the bioglass/hydrogel composite coating has a good application prospect.
Drawings
FIG. 1 is a flow chart of the preparation of a magnesium-based undersurface bioglass/hydrogel composite coating prepared in accordance with the present invention;
FIG. 2 is an SEM topography of the micro-arc oxidation treatment of the magnesium substrate prepared in example 3;
FIG. 3 is an SEM topography of a magnesium-based bottom surface bioglass/hydrogel composite coating prepared in example 3;
FIG. 4 is an SEM image of a bioglass/hydrogel composite coated magnesium substrate prepared in example 3 immersed in simulated body fluid for 3 days.
Detailed description of the invention
The technical solution of the present invention will be described in detail by examples, but the present invention is not limited thereto.
Example 1
A preparation method of a bioglass/hydrogel composite coating on the surface of a pure magnesium substrate comprises the following steps:
(1) polishing a pure magnesium substrate by 100-grade sand paper 1000, ultrasonically cleaning and drying by using mixed solution of alcohol and acetone in a volume ratio of 1:1, and taking a stainless steel plate as a cathode; placing the anode and the cathode in sodium phosphate and sodium hydroxide electrolyte (the concentration of sodium phosphate is 20 g/L, and the concentration of sodium hydroxide is 15 g/L) to perform micro-arc oxidation for 1 min;
(2) mixing 58S bioglass powder (58 SiO)2-33CaO-9P2O5) Performing ball milling, sieving to obtain powder with the particle size of below 45 micrometers, putting the powder into constant-temperature water at 37 ℃, continuously introducing nitrogen to remove oxygen dissolved in the water, adding a cerium ammonium nitrate solution with the concentration of 0.1 mol/L, magnetically stirring, fully reacting for 30 min, then continuously dripping polyglycidyl methacrylate (GMA) for 30 min, repeatedly cleaning the powder to be neutral by deionized water and absolute ethyl alcohol after reacting for 1 h, and centrifugally drying to obtain powder, wherein the powder is put into ethylenediamine according to the mass ratio: water = 3: 2, stirring for 1 h at 80 ℃, repeatedly washing the mixture to be neutral by using deionized water and ethanol, and centrifugally drying the mixture to obtain surface amination modified bioglass powder;
(3) dissolving 3 g of chitosan in 50 g of dilute acetic acid solution (the volume ratio of acetic acid to water is 2: 100), and magnetically stirring for 1 hour to obtain a chitosan acetic acid solution;
(4) after the bioglass powder with the surface subjected to amination modification obtained in the step (2) is subjected to disinfection treatment by ultraviolet irradiation, slowly adding the bioglass powder into the chitosan acetic acid solution obtained in the step (3) according to the proportion of 1 g/L, performing ultrasonic treatment for 1 h, and magnetically stirring for 1 h to obtain a bioglass/chitosan composite solution;
(5) modifying polyethylene glycol (PEG) with p-aldehyde benzoic acid through esterification reaction to obtain polyethylene glycol (DFPEG) with double end benzaldehyde end capping, which comprises the steps of continuously stirring and dissolving PEG into 100 mL Tetrahydrofuran (THF) according to the concentration of 30g/L, adding p-aldehyde benzoic acid and a catalyst 4-dimethylamino pyridine (DMAP) (the mass ratio of PEG: p-aldehyde benzoic acid: DMAP is 3: 1: 0.05) after the PEG is completely dissolved, fully stirring to completely dissolve, adding N, N' -dicyclohexyl carbodiimide (DCC) (the mass ratio of PEG: DCC is 2: 1), stirring for 3 h at room temperature, filtering to remove precipitates, concentrating the filtrate and drying to obtain DFPEG powder. Dissolving DFPEG powder in deionized water (weight ratio of DFPEG to deionized water is 1: 10) to obtain DFPEG gel factor solution;
(6) and (3) placing the pure magnesium substrate subjected to micro-arc oxidation treatment in the step (1) in the bioglass/chitosan composite solution obtained in the step (4) for ultrasonic treatment for 10 min, slowly dropwise adding the DFPEG gel factor solution obtained in the step (5), fully stirring until the bioglass/chitosan composite solution is sticky, taking out the pure magnesium substrate, and washing and drying with deionized water to obtain the bioglass/hydrogel composite coating on the surface of magnesium.
The ceric ammonium nitrate solution in the step (2) is prepared by dissolving ceric ammonium nitrate in 1 mol/L HNO3Configuring; the weight ratio of the bioglass, the ammonium ceric nitrate and the poly glycidyl methacrylate is 10: 20: 2.
example 2
A preparation method of a ZK60 magnesium alloy surface bioglass/hydrogel composite coating comprises the following steps:
(1) grinding a ZK60 magnesium alloy substrate by using 100-1000 # abrasive paper, ultrasonically cleaning and drying by using mixed liquid of alcohol and acetone in a volume ratio of 1:1, and taking a stainless steel plate as a cathode; placing the anode and the cathode in sodium phosphate and sodium hydroxide electrolyte (the concentration of sodium phosphate is 90 g/L, and the concentration of sodium hydroxide is 5 g/L) to perform micro-arc oxidation for 60 min;
(2) mixing 45S5 bioglass powder (45 SiO)2-24.5CaO-6P2O5-24.5Na2O) ball milling, sieving to obtain powder with particle diameter below 45 μm, adding into constant temperature water of 37 deg.C, and holdingContinuously introducing nitrogen to remove oxygen dissolved in water, adding a 0.1 mol/L ammonium ceric nitrate solution, magnetically stirring and fully reacting for 30 min, then continuously dripping polyglycidyl methacrylate (GMA) for 30 min, repeatedly cleaning with deionized water and absolute ethyl alcohol to be neutral after reacting for 1 h, centrifugally drying to obtain powder, and adding ethylene diamine according to the mass ratio: water = 3: 2, stirring for 6 hours at 80 ℃, repeatedly washing the mixture to be neutral by using deionized water and ethanol, and centrifugally drying the mixture to obtain surface amination modified bioglass powder;
(3) dissolving 1 g of chitosan in 50 g of dilute acetic acid solution (the volume ratio of acetic acid to water is 2: 100), and magnetically stirring for 1 hour to obtain a chitosan acetic acid solution;
(4) after the bioglass powder with the surface subjected to amination modification obtained in the step (2) is subjected to disinfection treatment by ultraviolet irradiation, the bioglass powder is slowly added into the chitosan acetic acid solution obtained in the step (3) according to the proportion of 20 g/L, ultrasonic treatment is carried out for 1 h, and magnetic stirring is carried out for 1 h, so as to obtain a bioglass/chitosan composite solution;
(5) modifying polyethylene glycol (PEG) with p-aldehyde benzoic acid through esterification reaction to obtain polyethylene glycol (DFPEG) with double end benzaldehyde end capping, which comprises the steps of continuously stirring and dissolving PEG into 100 mL Tetrahydrofuran (THF) according to the concentration of 30g/L, adding p-aldehyde benzoic acid and a catalyst 4-dimethylamino pyridine (DMAP) (the mass ratio of PEG: p-aldehyde benzoic acid: DMAP is 3: 1: 0.05) after the PEG is completely dissolved, fully stirring to completely dissolve, adding N, N' -dicyclohexyl carbodiimide (DCC) (the mass ratio of PEG: DCC is 2: 1), stirring for 12 h at room temperature, filtering to remove precipitates, concentrating the filtrate and drying to obtain DFPEG powder. Dissolving DFPEG powder in deionized water (weight ratio of DFPEG to deionized water is 1: 10) to obtain DFPEG gel factor solution;
(6) and (3) placing the ZK60 magnesium alloy subjected to micro-arc oxidation treatment in the step (1) into the bioglass/chitosan composite solution obtained in the step (4) for ultrasonic treatment for 10 min, slowly dropwise adding the DFPEG gel factor solution obtained in the step (5), fully stirring until the bioglass/chitosan composite solution is sticky, taking out the ZK60 magnesium alloy, and washing and drying with deionized water to obtain the bioglass/hydrogel composite coating on the surface of the magnesium alloy.
The ceric ammonium nitrate solution in the step (2) is prepared by dissolving ceric ammonium nitrate in 1 mol/L HNO3Configuring; the weight ratio of the bioglass, the ammonium ceric nitrate and the poly glycidyl methacrylate is 10: 20: 2.
example 3
A preparation method of an AZ31 magnesium alloy surface bioglass/hydrogel composite coating comprises the following steps:
(1) polishing an AZ31 magnesium alloy substrate by 100-1000 # abrasive paper, ultrasonically cleaning and drying by using mixed solution of alcohol and acetone in a volume ratio of 1:1, and taking a stainless steel plate as a cathode; placing the anode and the cathode in sodium phosphate and sodium hydroxide electrolyte (the concentration of sodium phosphate is 60 g/L, and the concentration of sodium hydroxide is 10 g/L) to perform micro-arc oxidation for 30 min;
(2) mixing 35SiO2-40CaO-25P2O5The bioglass powder is subjected to ball milling and then sieved to obtain powder with the particle size of below 45 micrometers, the powder is placed into constant-temperature water with the temperature of 37 ℃, nitrogen is continuously introduced to remove oxygen dissolved in the water, 0.1 mol/L cerium ammonium nitrate solution is added to be magnetically stirred and fully reacted for 30 min, then polyglycidyl methacrylate (GMA) is dripped continuously for 30 min, the powder is repeatedly washed to be neutral by deionized water and absolute ethyl alcohol after reacting for 1 h, and the powder is obtained by centrifugal drying and is placed into ethylenediamine according to the mass ratio: water = 3: 2, stirring for 3.5 hours at 80 ℃, and finally repeatedly cleaning the mixture by deionized water and ethanol until the mixture is neutral, and centrifugally drying the mixture to obtain the surface amination modified bioglass powder;
(3) dissolving 2 g of chitosan in 50 g of dilute acetic acid solution (the volume ratio of acetic acid to water is 2: 100), and magnetically stirring for 1 hour to obtain a chitosan acetic acid solution;
(4) after the bioglass powder with the surface subjected to amination modification obtained in the step (2) is subjected to disinfection treatment by ultraviolet irradiation, slowly adding the bioglass powder into the chitosan acetic acid solution obtained in the step (3) according to the proportion of 10 g/L, performing ultrasonic treatment for 1 hour, and magnetically stirring for 1 hour to obtain a bioglass/chitosan composite solution;
(5) modifying polyethylene glycol (PEG) with p-aldehyde benzoic acid through esterification reaction to obtain polyethylene glycol (DFPEG) with double end benzaldehyde end capping, which comprises the steps of continuously stirring and dissolving PEG into 100 mL Tetrahydrofuran (THF) according to the concentration of 30g/L, adding p-aldehyde benzoic acid and a catalyst 4-dimethylamino pyridine (DMAP) (the mass ratio of PEG: p-aldehyde benzoic acid: DMAP is 3: 1: 0.05) after the PEG is completely dissolved, fully stirring to completely dissolve, adding N, N' -dicyclohexyl carbodiimide (DCC) (the mass ratio of PEG: DCC is 2: 1), stirring for 7 h at room temperature, filtering to remove precipitates, concentrating the filtrate and drying to obtain DFPEG powder. Dissolving DFPEG powder in deionized water (weight ratio of DFPEG to deionized water is 1: 10) to obtain DFPEG gel factor solution;
(6) and (3) placing the AZ31 magnesium alloy subjected to micro-arc oxidation treatment in the step (1) into the bioglass/chitosan composite solution obtained in the step (4) for ultrasonic treatment for 10 min, slowly dropwise adding the DFPEG gel factor solution obtained in the step (5), fully stirring until the bioglass/chitosan composite solution is sticky, taking out the AZ31 magnesium alloy, and washing and drying with deionized water to obtain the bioglass/hydrogel composite coating on the surface of the magnesium alloy.
The ceric ammonium nitrate solution in the step (2) is prepared by dissolving ceric ammonium nitrate in 1 mol/L HNO3Configuring; the weight ratio of the bioglass, the ammonium ceric nitrate and the poly glycidyl methacrylate is 10: 20: 2.
as can be seen from FIG. 2, the SEM appearance of the magnesium substrate after micro-arc oxidation treatment presents a porous structure, and the structure is beneficial to the deposition of the bioglass/hydrogel composite coating. It can be seen from fig. 3 that the pores on the surface of the magnesium alloy are mostly filled after the bioglass/hydrogel composite coating treatment. The SEM appearance after 3 days of soaking in simulated body fluid is shown in figure 4, the surface of the magnesium alloy has no obvious corroded crack and shedding, and a few small needle-shaped substances are deposited on the surface, which shows that the magnesium-based bottom surface bioglass/hydrogel composite coating can protect a magnesium alloy matrix in the simulated body fluid, can induce the deposition of calcium and phosphorus salts in the simulated body fluid, and has good bioactivity.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (8)

1. A method for preparing a bioglass/hydrogel composite coating on the bottom surface of a magnesium-based substrate is characterized by comprising the following steps: the method comprises the following steps:
(1) grinding a magnesium substrate by 100-grade sand paper 1000, ultrasonically cleaning and drying by using mixed liquid of alcohol and acetone in a volume ratio of 1:1, and taking a stainless steel plate as a cathode; placing the anode and the cathode in a sodium phosphate and sodium hydroxide electrolyte for micro-arc oxidation for 1-60 min;
(2) ball-milling bioglass powder, sieving to obtain powder with the particle size of below 45 micrometers, putting the powder into constant-temperature water at 37 ℃, continuously introducing nitrogen to remove oxygen dissolved in the water, adding a 0.1 mol/L ammonium ceric nitrate solution, magnetically stirring, fully reacting for 30 min, then continuously dripping polyglycidyl methacrylate for 30 min, repeatedly cleaning the solution to be neutral by deionized water and absolute ethyl alcohol after reacting for 1 h, and centrifugally drying to obtain powder, wherein the powder is put into ethylenediamine according to the mass ratio: water = 3: 2, stirring for 1-6 h at 80 ℃, repeatedly washing the mixture to be neutral by using deionized water and ethanol, and centrifugally drying the mixture to obtain the surface amination modified bioglass powder;
(3) dissolving chitosan in a dilute acetic acid solution, and magnetically stirring for 1 hour to obtain a chitosan acetic acid solution, wherein the dilute acetic acid solution is prepared by mixing acetic acid and water according to a volume ratio of 2: 100 is configured;
(4) after the surface amination modified bioglass powder obtained in the step (2) is subjected to disinfection treatment by ultraviolet irradiation, slowly adding the disinfected bioglass powder into the chitosan acetic acid solution obtained in the step (3) according to the proportion of 1-20 g/L, performing ultrasonic treatment for 1 hour, and magnetically stirring for 1 hour to obtain a bioglass/chitosan composite solution;
(5) modifying PEG with p-aldehyde benzoic acid through esterification reaction to obtain DFPEG, wherein the steps comprise continuously stirring and dissolving PEG into 100 mL of tetrahydrofuran according to the concentration of 30g/L, adding p-aldehyde benzoic acid and a catalyst 4-dimethylaminopyridine after the PEG is completely dissolved, fully stirring until the PEG is completely dissolved, adding N, N' -dicyclohexyl carbodiimide, stirring for 3-12 h at room temperature, filtering to remove precipitates, concentrating and drying filtrate to obtain DFPEG powder, and dissolving the DFPEG powder into deionized water according to the weight ratio of 1:10 to obtain a DFPEG gel factor solution;
(6) and (3) placing the magnesium-based substrate material subjected to micro-arc oxidation treatment in the step (1) in the bioglass/chitosan composite solution obtained in the step (4) for ultrasonic treatment for 10 min, slowly dropwise adding the DFPEG gel factor solution obtained in the step (5), fully stirring until the bioglass/chitosan composite solution is sticky, taking out the magnesium-based substrate material, and washing and drying with deionized water to obtain the bioglass/hydrogel composite coating on the surface of the magnesium-based substrate.
2. The method of claim 1, wherein the method comprises the steps of: the magnesium-based substrate material in the step (1) is pure magnesium or a magnesium alloy material; the concentration of sodium phosphate in the electrolyte is 20-90 g/L, and the concentration of sodium hydroxide is 5-15 g/L.
3. The method of claim 1, wherein the method comprises the steps of: the bioglass powder in the step (2) comprises one of silicate, borate and phosphate.
4. The method of claim 1, wherein the method comprises the steps of: the ceric ammonium nitrate solution in the step (2) is prepared by dissolving ceric ammonium nitrate in 1 mol/L HNO3And (4) configuring.
5. The method of claim 1, wherein the method comprises the steps of: the weight ratio of the bioglass, the ammonium ceric nitrate and the poly glycidyl methacrylate in the step (2) is 10: 20: 2.
6. the method of claim 1, wherein the method comprises the steps of: in the step (3), the weight ratio of the chitosan to the dilute acetic acid solution is 2-6: 100.
7. the method of claim 1, wherein the method comprises the steps of: in the step (5), PEG: p-aldehyde benzoic acid: the mass ratio of the 4-dimethylamino pyridine is 3: 1: 0.05.
8. the method of claim 1, wherein the method comprises the steps of: in the step (5), PEG: the mass ratio of the N, N' -dicyclohexylcarbodiimide is 2: 1.
CN201810384380.1A 2018-04-26 2018-04-26 Preparation method of bioglass/hydrogel composite coating on surface of magnesium-based substrate Expired - Fee Related CN108578776B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810384380.1A CN108578776B (en) 2018-04-26 2018-04-26 Preparation method of bioglass/hydrogel composite coating on surface of magnesium-based substrate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810384380.1A CN108578776B (en) 2018-04-26 2018-04-26 Preparation method of bioglass/hydrogel composite coating on surface of magnesium-based substrate

Publications (2)

Publication Number Publication Date
CN108578776A CN108578776A (en) 2018-09-28
CN108578776B true CN108578776B (en) 2020-11-10

Family

ID=63609622

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810384380.1A Expired - Fee Related CN108578776B (en) 2018-04-26 2018-04-26 Preparation method of bioglass/hydrogel composite coating on surface of magnesium-based substrate

Country Status (1)

Country Link
CN (1) CN108578776B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109796608A (en) * 2019-01-21 2019-05-24 福建农林大学 A kind of tool adhesiveness of pH response, antibacterial, pressure resistance quick selfreparing collagen based aquagel preparation method

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1269753C (en) * 2004-03-26 2006-08-16 中国科学院上海硅酸盐研究所 Degradable porous glass rack having bioactivity and preparation method
CN101302638A (en) * 2008-01-07 2008-11-12 郑州大学 Preparation of nano-HAP coating/magnesium alloy composite biological material
CN102580685B (en) * 2011-12-15 2013-05-29 清华大学 Porous polysaccharide cell adsorption material as well as preparation method and application thereof
KR101461159B1 (en) * 2013-01-29 2014-11-24 단국대학교 산학협력단 Preparation method of implant comprising drug delivery layer and implant compostion for living donor transplantation comprising the same
GB2528504A (en) * 2014-07-24 2016-01-27 Werner Ernst Ludwig Georg Muller Printable morphogenetic phase-specific chitosan-calcium-polyphosphate scaffold for bone repair
US10926000B2 (en) * 2016-05-13 2021-02-23 Colorado School Of Mines Deposition-conversion method for tunable calcium phosphate coatings on substrates and apparatus prepared thereof
CN107744593B (en) * 2017-09-20 2020-06-19 华南理工大学 Folic acid targeted anti-tumor drug sustained-release carrier and preparation method thereof

Also Published As

Publication number Publication date
CN108578776A (en) 2018-09-28

Similar Documents

Publication Publication Date Title
Kargozar et al. Chemistry of biomaterials: Future prospects
Zhang et al. A novel mineralized high strength hydrogel for enhancing cell adhesion and promoting skull bone regeneration in situ
Gao et al. Polydopamine-templated hydroxyapatite reinforced polycaprolactone composite nanofibers with enhanced cytocompatibility and osteogenesis for bone tissue engineering
Tao et al. Osteoimmunomodulation mediating improved osteointegration by OGP-loaded cobalt-metal organic framework on titanium implants with antibacterial property
Zhao et al. Osteogenic media and rhBMP-2-induced differentiation of umbilical cord mesenchymal stem cells encapsulated in alginate microbeads and integrated in an injectable calcium phosphate-chitosan fibrous scaffold
CN104911427B (en) A kind of Mg Ca Sr Zn systems magnesium alloy and preparation method and application
CN108578764B (en) Rapid preparation method of bioglass/hydrogel composite material
Kim et al. Injectable hydrogels for regenerative medicine
CN102008752B (en) Porous biphasic calcium phosphate biological scaffold with nano hydroxyapatite coating and preparation method thereof
WO2007011172A1 (en) Preparation method of porous beta tricalcium phosphate granules
CN111097068A (en) Bionic hydroxyapatite powder/gelatin/sodium alginate composite 3D printing support and preparation method thereof
CN113633821A (en) Temperature-sensitive injectable collagen/chitosan/zinc-doped biological glass nanoparticle hydrogel material and preparation method thereof
JP2012515607A (en) Β-glucan-based support for tissue engineering using radiation fusion technology and method for producing the same
CN111961227B (en) Graphene quantum dot/hydrogel composite material, and preparation method and application thereof
CN104192817A (en) Method for preparing mesoporous hydroxyapatite nanometer particle with high specific surface area by virtue of template method
Ghafarzadeh et al. Bilayer micro-arc oxidation-poly (glycerol sebacate) coating on AZ91 for improved corrosion resistance and biological activity
CN106492271B (en) The preparation of the antibacterial rush difunctional Guided Bone Regeneration Absorbable membrane of synosteosis
Ataie et al. Carboxymethyl carrageenan immobilized on 3D-printed polycaprolactone scaffold for the adsorption of calcium phosphate/strontium phosphate adapted to bone regeneration
CN108578776B (en) Preparation method of bioglass/hydrogel composite coating on surface of magnesium-based substrate
EP3995531A1 (en) Method of preparing polymeric microparticles, polymeric microparticles, and medical composition, cosmetic composition, medical article, and cosmetic article each comprising same
CN103819702B (en) The preparation method of a kind of Poly-L-lactic acid-modification MgO nanometer rod composite material
EP3300671B1 (en) Titanium clip with drug-loading feature, drug-loaded titanium clip, and manufacturing method thereof
CN102327643B (en) A kind of biological support for osteanagenesis
CN117323471A (en) Cross-linked hyaluronic acid-smooth hydroxyapatite gel and preparation method thereof
CN108578785B (en) Preparation method of magnetic self-healing bioglass/hydrogel composite material

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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20201110

CF01 Termination of patent right due to non-payment of annual fee