CN114377196B - Coating with biological activity and antibacterial function and application thereof - Google Patents

Coating with biological activity and antibacterial function and application thereof Download PDF

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CN114377196B
CN114377196B CN202111628016.3A CN202111628016A CN114377196B CN 114377196 B CN114377196 B CN 114377196B CN 202111628016 A CN202111628016 A CN 202111628016A CN 114377196 B CN114377196 B CN 114377196B
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coating
solution
porous metal
deionized water
reacting
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CN114377196A (en
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陆玲玲
魏崇斌
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Tianyan Medical Equipment Co ltd
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    • 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
    • A61L27/02—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
    • A61L27/303—Carbon
    • 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
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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
    • A61L27/50—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
    • A61L27/54—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
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    • 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
    • A61L2300/104—Silver, e.g. silver sulfadiazine
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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
    • A—HUMAN NECESSITIES
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    • 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
    • A61L2300/406—Antibiotics
    • 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
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    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/04—Coatings containing a composite material such as inorganic/organic, i.e. material comprising different phases
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • 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
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses

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Abstract

The invention discloses a coating with biological activity and antibiosis and application thereof; the method comprises the following steps: s1: cleaning and drying the porous metal for later use; s2: dissolving a calcium precursor and a phosphorus precursor in absolute ethyl alcohol, uniformly mixing, and aging for 8-12h to obtain HA sol; s3: uniformly stirring the antibacterial agent and the HA sol, and aging to obtain HA gel; s4: and (4) taking the porous metal cleaned in the step S1, slowly immersing the porous metal into HA gel, drying, and repeating for 3-5 times to form a coating on the surface of the porous metal. The invention aims at the porous structure forms of tantalum, titanium and alloy materials thereof, is used as an implant, and has higher bonding strength with bones; the HA coating is attached to the surface of the porous metal structure, so that the biological activity of the implant is effectively increased, and the HA coating is doped with components such as antibiotics and silver nitrate, so that the coating HAs certain antibacterial performance.

Description

Coating with biological activity and antibacterial function and application thereof
Technical Field
The invention relates to the technical field of medical instruments, in particular to a coating with bioactivity and antibacterial property and application thereof.
Background
In recent years, biomaterials that come into contact with biological tissues for medical purposes have been intensively studied. The biological materials including medical polymer materials, biological ceramic materials and medical metal materials have been developed rapidly in the aspects of medical treatment, health care and improvement of life quality since the 80 s in the 19 th century. When the material is used as a long-term implant material, the material generally has good biological stability, biocompatibility and bioactivity. At diagnosis or body organ-tissue replacement, the biological material will come into contact with the body. At the moment, the materials need to be ensured to have no obvious toxic or side effect, and when the materials are contacted with body fluid such as saliva, lymph fluid and blood, the materials need to show good corrosion resistance and even have certain antibacterial capacity.
Along with the continuous improvement of living standard of people, high requirements are also put forward on the performance of biomedical materials contacted with human bodies. After being implanted into a human body, the biopolymer material has relatively poor corrosion resistance and unstable factors such as low reduced mechanical strength, so that the biopolymer material is limited in practical application.
Bioactive ceramics are represented by light apatite ceramics (HA) having high crystallinity and have excellent surface activity. The chemical composition and crystal structure of HA are similar to those of human bone. Compared with inert biological materials, HA does not have the problems of immunity and interference on an immune system in vivo, is nontoxic, HAs high corrosion resistance and polarity on the surface, can be combined with polysaccharide, glycoprotein and the like on the surface of a cell membrane through hydrogen bonds, can be directly combined with bones, and HAs higher clinical application value. But the defects are that the mechanical property is poor and the brittleness is high. This limits its application to some extent. In practical applications, HA is often combined with a high strength bioceramic or biomedical metal to improve the overall mechanical strength of the implant.
The defects and shortcomings of the prior art:
(1) the elastic modulus of the metal implant is higher than that of a human skeleton, and stress shielding can be caused after the metal implant is implanted, so that the prosthesis can fall off finally;
(2) because the metal implant material is biologically inert, the metal implant material needs to be made biologically active by coating the surface with a biologically active coating or directly surface-activating the metal implant material;
(3) currently, methods for preparing the HA composite coating are more, such as a plasma spraying method, a magnetron sputtering method and the like. However, most of the methods belong to linear methods, and the HA composite coating can not be prepared on the inner surface and the outer surface of a substrate with a complex shape, such as (porous titanium).
Disclosure of Invention
The present invention aims to provide a coating with both biological activity and antibacterial property and an application thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the coating comprises the following raw materials in percentage by mass: 22-25% of precursor of calcium, 4-6% of precursor of phosphorus, 10-15% of antibacterial agent and the balance of absolute ethyl alcohol.
Further, the precursor of calcium is Ca (NO) 3 ) 2 ·4H 2 O、CaCO 3 、CaCl 2 、Ca 3 (PO 4 ) 2 One or more of Ca (NO) 3 ) 2 The average particle size of 4H2O is 300-800 nm; CaCO 3 The average particle size of (B) is 0.7 to 1.2 mu m; CaCl 2 The average particle size of (A) is 74 to 150 μm; ca 3 (PO 4 ) 2 The average particle size of (A) is 12 to 68 μm; the precursor of the phosphorus is P 2 O 5 、Ca 4 P 2 O 9 、C 3 H 7 Na 2 O 6 P、NH 4 H 2 PO 4 、Ca 3 (PO 4 ) 2 One or more of, P 2 O 5 The average particle size of (A) is 200-700 nm; ca 4 P 2 O 9 The average particle size of (A) is 500-700 nm; c 3 H 7 Na 2 O 6 The average particle size of P is 2.6-12.9 μm; NH (NH) 4 H 2 PO 4 The average particle size of (A) is 16 to 30 μm; ca 3 (PO 4 ) 2 Average of 300 to 600 nm.
Further, the antibacterial agent is one or more of gentamicin, cefamycin and silver nitrate, and when the antibacterial agent is a mixture of gentamicin and silver nitrate, the concentration ratio of gentamicin to silver nitrate is (1-2): 1; the content of gentamicin is 0.01-0.2mg/g, and the content of silver nitrate is 0.05-0.25 mg/g.
Further, the coating can be used as a coating treatment for the surfaces of porous metals with dental and orthopedic implantation properties.
Further, the porous metal is one or more of Ti, Ti-6Al-4V, Ti-6Al-17Nb and Ta; the porous metal structure is one or more of combination of a full porous material and a solid structure and combination of a surface porous material and the solid structure; the shape of the porous metal material is one or more of column, cone, sphere, block and irregular; the porosity of the porous metal structure is 10-75%, and the pore intercept is 30-600 μm.
Further, the method comprises the following steps:
s1: ultrasonically cleaning porous metal in acetone solution for 3-5 times, each time for 10-15min, ultrasonically cleaning with deionized water for 15-20min, reacting in a mixed solution of sulfuric acid, hydrochloric acid and deionized water at 60-80 ℃ for 3-5h, ultrasonically cleaning with deionized water for 15-20min, reacting in sodium hydroxide solution at 60-80 ℃ for 1-2h, ultrasonically cleaning with deionized water for 15-20min, and drying for later use;
s2: dissolving a precursor of calcium in absolute ethyl alcohol to obtain solution A, dissolving a precursor of phosphorus in absolute ethyl alcohol to obtain solution B, slowly adding the solution A into the solution B, uniformly mixing, and aging at 40-60 ℃ for 8-12h to obtain HA sol;
s3: uniformly stirring the ethanol solution of the antibacterial agent and the HA sol, and aging for 24-36h to obtain HA gel;
s4: and (3) taking the porous metal cleaned in the step S1, slowly immersing the porous metal into HA gel, extracting at the same speed, drying at 50-80 ℃, repeating for 3-5 times, and forming a coating on the surface of the porous metal, wherein the coating is 1-100 mu m.
Further, in step S3, the mass ratio of the HA sol to the antibacterial agent ethanol solution is 1: 0.8.
Further, the leaching speed should satisfy the relation: when 1mm 3 ≤V＜3mm 3 When S is more than or equal to 4mm/S and less than 6.5 mm/S; when the diameter is 3mm 3 ≤V＜10mm 3 When the thickness is more than or equal to 2mm/S and less than 4 mm/S; when V is more than or equal to 10mm 3 When S is 1 mm/S;
wherein, V: a porous metal structure volume; s: the first leaching speed.
Further, the leaching times t and the leaching speed S satisfy the relation: st is 0.7S + 0.5.
Further, the preparation method comprises the following steps:
s1: ultrasonically cleaning porous metal in acetone solution for 3-5 times, each time for 10-15min, ultrasonically cleaning with deionized water for 15-20min, reacting in a mixed solution of sulfuric acid, hydrochloric acid and deionized water at 60-80 ℃ for 3-5h, ultrasonically cleaning with deionized water for 15-20min, reacting in sodium hydroxide solution at 60-80 ℃ for 1-2h, ultrasonically cleaning with deionized water for 15-20min, and drying for later use;
s2: the preparation process of the modified graphene oxide comprises the following steps: dissolving graphene oxide in water, adding aluminum selenide, reacting for 3-5 hours in a closed manner, purging with nitrogen, adding disodium adenosine triphosphate, adjusting the pH to 7-9, reacting for 6-10 hours, filtering, washing and drying to obtain modified graphene oxide;
s3: dissolving chitosan in a hydrochloric acid solution, adding deionized water, uniformly mixing with a water solution of 3, 4-dihydroxyphenyl propionic acid, adjusting the pH value of the solution to 4-6, continuously adding a mixed solution of carbodiimide water and ethanol, adjusting the pH value of the solution to 4-6, reacting for 4-6h, dialyzing for 24-48h with deionized water, freezing and drying to obtain modified chitosan;
s4: dissolving a calcium precursor in deionized water, adjusting the pH value of the solution to 9-10, adding modified graphene oxide, heating to 90-100 ℃ to obtain solution A, dissolving a phosphorus precursor in deionized water, adjusting the pH value of the solution to 9-10 to obtain solution B, heating the solution B to 90-100 ℃, slowly adding the solution B into the solution A, reacting for 3-5h, and aging at 40-60 ℃ for 8-12h to obtain HA sol;
s5: dissolving an antibacterial agent in absolute ethyl alcohol, adding modified chitosan and ytterbium nitrate, uniformly mixing, uniformly stirring with HA sol, and aging for 24-36h to obtain HA gel;
s6: and (3) taking the porous metal cleaned in the step S1, slowly immersing the porous metal into HA gel, extracting at the same speed, drying at 50-80 ℃, repeating for 3-5 times, and forming a coating on the surface of the porous metal, wherein the coating is 1-100 mu m.
(1) And performing acid-base treatment on the surface of the porous metal to generate more hydroxyl groups on the surface of the porous metal, so that the deposition of HA on the surface of the porous metal is facilitated, and a compact coating layer is formed. The active sites of surface carboxyl are increased by using the graphene oxide and the aluminum selenide, a large number of carboxyl groups are introduced into the edge of a graphene oxide sheet layer to react with amino on the surface of the disodium adenosine triphosphate, and the disodium adenosine triphosphate is intercalated into the graphene oxide sheet layer, so that the dispersibility of the graphene oxide can be improved.
(2) The hydrophilicity of the coating can be further enhanced by increasing the carboxyl on the surface of the graphene oxide, the biocompatibility of the porous metal is improved by the graphene oxide, the bone regeneration is promoted, the graphene oxide has antibacterial property, and the antibacterial property of the porous metal can be further improved by combining the graphene oxide with an antibacterial agent.
(3) The catechol structure is introduced to the surface of the chitosan, so that the cohesiveness of the coating and the surface of the porous metal is improved, the chitosan has the property similar to dopamine, the antibacterial property and the oxidation resistance are improved, and the coating and the antibacterial agent can be prevented from falling off. In addition, the chitosan has a slow release effect on the antibacterial agent, so that the antibacterial agent has a long-acting antibacterial effect, the whole sol is alkaline, the chitosan is subjected to surface modification, and the compatibility of the chitosan and alkaline substances is improved. The addition of chitosan can improve the biocompatibility of the porous metal, and the amino group on the surface of the chitosan can improve the hydrophilicity of the material. Simultaneously, the nano porous metal material has synergistic effect with graphene oxide and hydroxyapatite, inhibits the aggregation of bacteria, reduces the adhesion of bacteria, and simultaneously avoids the corrosion phenomenon of the porous metal in a human body along with the change of time.
(4) The rare earth element ytterbium is added into the coating and implanted into the human body, so that the bone repair of the human body can be accelerated, the porosity of the surface of the coating can be further increased when the rare earth element ytterbium and the graphene oxide are added into the coating together, the proliferation and adhesion of cells are facilitated, in addition, the addition of the rare earth element does not have toxic action on the human body, and the addition of low-concentration rare earth ions can promote the proliferation of the human body.
(5) The invention aims at the porous structure forms of tantalum, titanium and alloy materials thereof, is used as an implant, and has higher bonding strength with bones; the HA coating is attached to the surface of the porous metal structure, so that the biological activity of the implant is effectively increased, and the HA coating is doped with components such as antibiotics, silver nitrate and the like, so that the coating HAs certain antibacterial performance; the HA antibacterial composite coating is prepared by a sol-gel method, the thickness of the coating can be increased by leaching for multiple times, and the finally obtained coating is loose and HAs a uniform surface.
Compared with the prior art, the invention has the following beneficial effects: the coating prepared by the invention has bioactivity and antibacterial property, can accelerate bone regeneration and bone proliferation when used as a surface coating of an implantable device, and does not contain toxicity.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of the structures of HA sols and HA gels of the present invention;
in the figure: (1) HA sol; (2) HA gel.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: a preparation method of a coating with biological activity and antibiosis comprises the following steps:
s1: ultrasonically cleaning porous metal Ti in an acetone solution for 3 times, after 10min each time, ultrasonically cleaning the porous metal Ti with deionized water for 15min, reacting in a mixed solution of sulfuric acid, hydrochloric acid and deionized water at 60 ℃ for 3h, ultrasonically cleaning the porous metal Ti with deionized water for 15min, reacting in a sodium hydroxide solution at 60 ℃ of 5mol/L for 1h, ultrasonically cleaning the porous metal Ti with deionized water for 15min, and drying the porous metal Ti for later use;
s2: 23.6gCa (NO) 3 ) 2 ·4H 2 Dissolving O in anhydrous ethanol to obtain solution A, and mixing 4.192gP 2 O 5 Dissolving in absolute ethyl alcohol to obtain solution B, slowly adding 500mLA solution into 500mLB solution, mixing, aging at 45 deg.C for 10 hr to obtain HA sol;
s3: dissolving 10g of silver nitrate in absolute ethyl alcohol, uniformly mixing, uniformly stirring 800mL of absolute ethyl alcohol solution containing silver nitrate and HA sol, and aging for 24h to obtain HA gel;
s4: and (3) taking the porous metal Ti cleaned in the step S1, immersing the porous metal Ti into HA gel at the speed of 4.5mm/S, staying for 10S, extracting at the speed of 4.5mm/S, drying at 55 ℃, and repeating for 3 times to form a coating on the surface of the porous metal, wherein the coating is 35 mu m.
In this embodiment, the porous metal Ti is a columnar porous structure with a structural volume of 1mm 3 The average porosity of the porous structure was 45% and the average pore intercept was 60 μm.
The volume ratio of the sulfuric acid to the hydrochloric acid to the deionized water is 1:1: 1.
The mass ratio of the HA sol to the silver nitrate ethanol solution is 1: 0.8.
Example 2: a preparation method of a coating with biological activity and antibiosis comprises the following steps:
s1: ultrasonically cleaning porous metal Ti in an acetone solution for 3 times, after each time of 10min, ultrasonically cleaning the porous metal Ti with deionized water for 15min, reacting the porous metal Ti in a mixed solution of sulfuric acid, hydrochloric acid and deionized water at 60 ℃ for 3h, ultrasonically cleaning the porous metal Ti with deionized water for 15min, reacting the porous metal Ti in a sodium hydroxide solution at 60 ℃ of 5mol/L for 1h, ultrasonically cleaning the porous metal Ti with deionized water for 15min, and drying the porous metal Ti for later use;
s2: dissolving 3mmol of chitosan in 5mL of hydrochloric acid solution, adding 45mL of deionized water, mixing uniformly with 1.6mmol of 3, 4-dihydroxyphenyl propionic acid aqueous solution, adjusting the pH value of the solution to 4, continuously adding a mixed solution of 50mL of water and 50mL of ethanol containing 0.65mmol of carbodiimide, adjusting the pH value of the solution to 4, reacting for 4-6h, dialyzing for 24h with deionized water, freezing and drying to obtain modified chitosan;
s3: dissolving 30mg of graphene oxide in water, adding 10mg of aluminum selenide, carrying out closed reaction for 3 hours, carrying out nitrogen purging, adding 1.2g of disodium adenosine triphosphate, adjusting the pH to 7, carrying out reaction for 6-10 hours, and then filtering, washing and drying to obtain modified graphene oxide;
s4: 23.6gCa (NO) 3 ) 2 ·4H 2 Dissolving O in deionized water, adjusting the pH value of the solution to 9, adding 10g of modified graphene oxide, heating to 90 ℃ to obtain solution A, and mixing 4.192gP 2 O 5 Dissolving in deionized water, adjusting pH to 9 to obtain solution B, and heating to 90 deg.CSlowly adding 500mL of solution B into 500mL of solution A, reacting for 3h, and aging at 40-60 ℃ for 8-12h to obtain HA sol;
s5: dissolving 10g of silver nitrate in 500mL of absolute ethanol, adding 10g of modified chitosan and 0.01mol/L of ytterbium nitrate solution, uniformly mixing, uniformly stirring with HA sol, and aging for 24-36h to obtain HA gel;
s6: and (3) taking the porous metal Ti cleaned in the step S1, immersing the porous metal Ti into HA gel at the speed of 4.5mm/S, staying for 10S, extracting at the speed of 4.5mm/S, drying at 55 ℃, and repeating for 3 times to form a coating on the surface of the porous metal, wherein the coating is 35 mu m.
In this example, the porous metal Ti is a columnar porous structure with a structure volume of 1mm 3 The average porosity of the porous structure was 45% and the average pore intercept was 60 μm.
The volume ratio of the sulfuric acid to the hydrochloric acid to the deionized water is 1:1: 1.
The mass ratio of the HA sol to the silver nitrate ethanol solution is 1: 0.8.
Example 3: a preparation method of a coating with biological activity and antibiosis comprises the following steps:
s1: ultrasonically cleaning porous metal Ti in an acetone solution for 3 times, after 10min each time, ultrasonically cleaning the porous metal Ti with deionized water for 15min, reacting in a mixed solution of sulfuric acid, hydrochloric acid and deionized water at 60 ℃ for 3h, ultrasonically cleaning the porous metal Ti with deionized water for 15min, reacting in a sodium hydroxide solution at 60 ℃ of 5mol/L for 1h, ultrasonically cleaning the porous metal Ti with deionized water for 15min, and drying the porous metal Ti for later use;
s2: dissolving 3mmol of chitosan in 5mL of hydrochloric acid solution, adding 45mL of deionized water, uniformly mixing with 1.6mmol of 3, 4-dihydroxyphenyl propionic acid aqueous solution, adjusting the pH value of the solution to 6, continuously adding 0.65mmol of carbodiimide mixed solution of 50mL of water and 50mL of ethanol, adjusting the pH value of the solution to 6, reacting for 4-6h, dialyzing for 48h with deionized water, freezing and drying to obtain modified chitosan;
s3: dissolving 30mg of graphene oxide in water, adding 10mg of aluminum selenide, carrying out a closed reaction for 5 hours, carrying out nitrogen purging, adding 1.5g of disodium adenosine triphosphate, adjusting the pH to 9, carrying out a reaction for 6-10 hours, and then filtering, washing and drying to obtain modified graphene oxide;
s4: 23.6gCa (NO) 3 ) 2 ·4H 2 Dissolving O in deionized water, adjusting the pH value of the solution to 10, adding 10g of modified graphene oxide, heating to 100 ℃ to obtain solution A, and mixing 4.192g of P 2 O 5 Dissolving in deionized water, adjusting the pH value of the solution to 10 to obtain a solution B, heating the solution B to 90-100 ℃, slowly adding 500mL of the solution B into 500mL of the solution A, reacting for 5h, and aging at 60 ℃ for 12h to obtain HA sol;
s5: dissolving 10g of silver nitrate in 500mL of absolute ethanol, adding 10g of modified chitosan and 0.01mol/L of ytterbium nitrate solution, uniformly mixing, uniformly stirring with HA sol, and aging for 36 hours to obtain HA gel;
s6: and (3) taking the porous metal Ti cleaned in the step S1, immersing the porous metal Ti into HA gel at the speed of 4.5mm/S, staying for 10S, extracting at the speed of 4.5mm/S, drying at 55 ℃, and repeating for 3 times to form a coating on the surface of the porous metal, wherein the coating is 35 mu m.
In this embodiment, the porous metal Ti is a columnar porous structure with a structural volume of 1mm 3 The average porosity of the porous structure was 45% and the average pore intercept was 60 μm.
The volume ratio of the sulfuric acid to the hydrochloric acid to the deionized water is 1:1: 1.
The mass ratio of the HA sol to the silver nitrate ethanol solution is 1: 0.8.
Comparative example
Comparative example 1: a preparation method of a coating with biological activity and antibiosis comprises the following steps:
s1: ultrasonically cleaning porous metal Ti in an acetone solution for 3 times, after 10min each time, ultrasonically cleaning the porous metal Ti with deionized water for 15min, reacting in a mixed solution of sulfuric acid, hydrochloric acid and deionized water at 60 ℃ for 3h, ultrasonically cleaning the porous metal Ti with deionized water for 15min, reacting in a sodium hydroxide solution at 60 ℃ of 5mol/L for 1h, ultrasonically cleaning the porous metal Ti with deionized water for 15min, and drying the porous metal Ti for later use;
s2: dissolving 3mmol of chitosan in 5mL of hydrochloric acid solution, adding 45mL of deionized water, mixing uniformly with 1.6mmol of 3, 4-dihydroxyphenyl propionic acid aqueous solution, adjusting the pH value of the solution to 4, continuously adding a mixed solution of 50mL of water and 50mL of ethanol containing 0.65mmol of carbodiimide, adjusting the pH value of the solution to 4, reacting for 4-6h, dialyzing for 24h with deionized water, freezing and drying to obtain modified chitosan;
s3: 23.6gCa (NO) 3 ) 2 ·4H 2 Dissolving O in deionized water, adjusting pH to 9, heating to 90 deg.C to obtain solution A, and mixing 4.192gP 2 O 5 Dissolving in deionized water, adjusting the pH value of the solution to 9 to obtain a solution B, heating the solution B to 90 ℃, slowly adding 500mL of the solution B into 500mL of the solution A, reacting for 3h, and aging at 40-60 ℃ for 8-12h to obtain HA sol;
s4: dissolving 10g of silver nitrate in 500mL of absolute ethanol, adding 10g of modified chitosan and 0.01mol/L of ytterbium nitrate solution, uniformly mixing, uniformly stirring with HA sol, and aging for 24-36h to obtain HA gel;
s5: and (3) taking the porous metal Ti cleaned in the step S1, immersing the porous metal Ti into HA gel at the speed of 4.5mm/S, staying for 10S, extracting at the speed of 4.5mm/S, drying at 55 ℃, and repeating for 3 times to form a coating on the surface of the porous metal, wherein the coating is 35 mu m.
In this example, the porous metal Ti is a columnar porous structure with a structure volume of 1mm 3 The average porosity of the porous structure was 45% and the average pore intercept was 60 μm.
The volume ratio of the sulfuric acid to the hydrochloric acid to the deionized water is 1:1: 1.
Comparative example 2: a preparation method of a coating with biological activity and antibiosis comprises the following steps:
s1: ultrasonically cleaning porous metal Ti in an acetone solution for 3 times, after each time of 10min, ultrasonically cleaning the porous metal Ti with deionized water for 15min, reacting the porous metal Ti in a mixed solution of sulfuric acid, hydrochloric acid and deionized water at 60 ℃ for 3h, ultrasonically cleaning the porous metal Ti with deionized water for 15min, reacting the porous metal Ti in a sodium hydroxide solution at 60 ℃ of 5mol/L for 1h, ultrasonically cleaning the porous metal Ti with deionized water for 15min, and drying the porous metal Ti for later use;
s2: dissolving 30mg of graphene oxide in water, adding 10mg of aluminum selenide, carrying out a closed reaction for 3 hours, carrying out nitrogen purging, adding 1.2g of disodium adenosine triphosphate, adjusting the pH to 7, carrying out a reaction for 6-10 hours, and then filtering, washing and drying to obtain modified graphene oxide;
s3: 23.6gCa (NO) 3 ) 2 ·4H 2 Dissolving O in deionized water, adjusting the pH value of the solution to 9, adding 10g of modified graphene oxide, heating to 90 ℃ to obtain solution A, and mixing 4.192gP 2 O 5 Dissolving in deionized water, adjusting the pH value of the solution to 9 to obtain a solution B, heating the solution B to 90 ℃, slowly adding 500mL of the solution B into 500mL of the solution A, reacting for 3h, and aging at 40-60 ℃ for 8-12h to obtain HA sol;
s4: dissolving 10g of silver nitrate in 500mL of absolute ethanol, adding 0.01mol/L of ytterbium nitrate solution, uniformly mixing, uniformly stirring with HA sol, and aging for 24-36h to obtain HA gel;
s5: and (3) taking the porous metal Ti cleaned in the step S1, immersing the porous metal Ti into HA gel at the speed of 4.5mm/S, staying for 10S, extracting at the speed of 4.5mm/S, drying at 55 ℃, and repeating for 3 times to form a coating on the surface of the porous metal, wherein the coating is 35 mu m.
In this embodiment, the porous metal Ti is a columnar porous structure with a structural volume of 1mm 3 The average porosity of the porous structure was 45% and the average pore intercept was 60 μm.
The volume ratio of the sulfuric acid to the hydrochloric acid to the deionized water is 1:1: 1.
Experimental data
The bacteriostasis rate is as follows: according to QB/T2591-2003, namely an antibacterial plastic antibacterial performance test method and an antibacterial effect.
Water contact angle: a drop of water was placed on the sample surface and its water contact angle was measured after 10 s.
Cell activity: according to GB/T16886.5-2003 "in vitro cytotoxicity test for medical device biological evaluation".
Figure BDA0003440432630000091
Wherein the cell activity is more than 80%, the cytotoxicity is grade 1, the cell activity is less than 80%, and the cytotoxicity is grade 2
And (4) conclusion:
1. compared with the example 2, the antibacterial property and the water contact angle of the porous metal are reduced because the modified graphene oxide is not added in the comparative example 1, which shows that the antibacterial property and the hydrophilicity of the porous metal can be further improved when the antibacterial agent is used together with the antibacterial agent after the graphene oxide reacts with the adenosine disodium triphosphate.
2. Compared with the example 2, the comparative example 2 does not add the modified chitosan, which causes the reduction of antibacterial property and cell activity, and shows that the chitosan is surface modified, the compatibility of the chitosan and alkaline substances is improved, the biocompatibility of the porous metal can be improved by adding the chitosan,
the coating prepared by the invention has better biological activity and antibacterial property, is used on the surface of implantable porous metal, and can promote bone repair and bone propagation.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A coating with biological activity and antibacterial performance is characterized in that: the preparation method comprises the following steps:
s1: ultrasonically cleaning porous metal in acetone solution for 3-5 times, each time for 10-15min, ultrasonically cleaning with deionized water for 15-20min, reacting in a mixed solution of sulfuric acid, hydrochloric acid and deionized water at 60-80 ℃ for 3-5h, ultrasonically cleaning with deionized water for 15-20min, reacting in sodium hydroxide solution at 60-80 ℃ for 1-2h, ultrasonically cleaning with deionized water for 15-20min, and drying for later use;
s2: the preparation process of the modified graphene oxide comprises the following steps: dissolving graphene oxide in water, adding aluminum selenide, reacting for 3-5h in a sealed manner, purging with nitrogen, adding adenosine disodium triphosphate, adjusting the pH to 7-9, reacting for 6-10h, filtering, washing and drying to obtain modified graphene oxide;
s3: dissolving chitosan in a hydrochloric acid solution, adding deionized water, uniformly mixing with a water solution of 3, 4-dihydroxyphenyl propionic acid, adjusting the pH value of the solution to 4-6, continuously adding a mixed solution of carbodiimide water and ethanol, adjusting the pH value of the solution to 4-6, reacting for 4-6h, dialyzing for 24-48h with deionized water, freezing and drying to obtain modified chitosan;
s4: dissolving a calcium precursor in deionized water, adjusting the pH value of the solution to 9-10, adding modified graphene oxide, heating to 90-100 ℃ to obtain solution A, dissolving a phosphorus precursor in deionized water, adjusting the pH value of the solution to 9-10 to obtain solution B, heating the solution B to 90-100 ℃, slowly adding the solution B into the solution A, reacting for 3-5h, and standing at 40-60 ℃ for 8-12h to obtain HA sol;
s5: dissolving an antibacterial agent in absolute ethyl alcohol, adding modified chitosan and ytterbium nitrate, uniformly mixing, uniformly stirring with HA sol, and aging for 24-36h to obtain HA gel;
s6: and (3) taking the porous metal cleaned in the step S1, slowly immersing the porous metal into HA gel, extracting at the same speed, drying at 50-80 ℃, repeating for 3-5 times, and forming a coating on the surface of the porous metal, wherein the coating is 1-100 mu m.
2. The coating of claim 1, wherein the coating is both bioactive and antimicrobial, and further comprising: the HA sol comprises the following raw materials in percentage by mass: 22-25% of precursor of calcium, 4-6% of precursor of phosphorus, 10-15% of antibacterial agent and the balance of absolute ethyl alcohol.
3. The coating of claim 1, wherein the coating is both bioactive and antimicrobial, and further comprising: the precursor of the calcium is Ca (NO) 3 ) 2 ·4H 2 O、CaCO 3 、CaCl 2 、Ca 3 (PO 4 ) 2 One or more of, Ca (NO) 3 ) 2 ·4H 2 The average particle size of O is 300-800 nm; CaCO 3 The average particle size of (a) is 0.7 to 1.2 μm; CaCl 2 The average particle size of (a) is 74-150 μm; ca 3 (PO 4 ) 2 The average particle size of (A) is 12 to 68 μm; the precursor of the phosphorus is P 2 O 5 、Ca 4 P 2 O 9 、C 3 H 7 Na 2 O 6 P、NH 4 H 2 PO 4 、Ca 3 (PO 4 ) 2 One or more of, P 2 O 5 The average particle size of (A) is 200-700 nm; ca 4 P 2 O 9 The average particle size of (2) is 500-700 nm; c 3 H 7 Na 2 O 6 The average particle size of P is 2.6-12.9 μm; NH 4 H 2 PO 4 The average particle size of (A) is 16 to 30 μm; ca 3 (PO 4 ) 2 Average of 300 to 600 nm.
4. The coating of claim 1, wherein the coating is both bioactive and antimicrobial, and further comprising: the antibacterial agent is one or more of gentamicin, cefamycin and silver nitrate, and when the antibacterial agent is a mixture of gentamicin and silver nitrate, the concentration ratio of gentamicin to silver nitrate is (1-2): 1; the content of gentamicin is 0.01-0.2mg/g, and the content of silver nitrate is 0.05-0.25 mg/g.
5. The coating of claim 1, wherein the coating is both bioactive and antimicrobial, and further comprising: the porous metal is one or more of Ti, Ti-6Al-4V, Ti-6Al-17Nb and Ta; the porous metal structure is one or more of combination of a full porous material and a solid structure and combination of a surface porous material and the solid structure; the shape of the porous metal material is one or more of column, cone, sphere, block and irregular; the porosity of the porous metal structure is 10-75%, and the pore intercept is 30-600 mu m.
6. The use of a coating according to claim 1, wherein the coating is both bioactive and antimicrobial, and wherein: in step S3, the mass ratio of the HA sol to the antibacterial agent ethanol solution is 1: 0.8.
7. The coating of claim 1, wherein the coating is both bioactive and antimicrobial, and further comprising: the leaching speed should satisfy the relation: when V is more than or equal to 1mm3 and less than or equal to 3mm3, S is more than or equal to 4mm/S and less than or equal to 6.5 mm/S; when V is more than or equal to 3mm3 and less than or equal to 10mm3, S is more than or equal to 2mm/S and less than or equal to 4 mm/S; when V is more than or equal to 10mm3, S is 1 mm/S;
wherein, V: a porous metal structure volume; s: the first leaching speed.
8. The coating of claim 1, wherein the coating is both bioactive and antimicrobial, and further comprising: the leaching times t and the leaching speed S satisfy the relation: st is 0.7S + 0.5.
9. Use of a coating according to any of claims 1-8, which is both bioactive and antibacterial, characterized in that: the coating is used for coating the surface of the porous metal for dental and orthopedic implantation.
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