CN106563168A - Preparation method of collagen-hydroxyapatite scaffold containing nanometer titanium dioxide - Google Patents

Preparation method of collagen-hydroxyapatite scaffold containing nanometer titanium dioxide Download PDF

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CN106563168A
CN106563168A CN201610962894.1A CN201610962894A CN106563168A CN 106563168 A CN106563168 A CN 106563168A CN 201610962894 A CN201610962894 A CN 201610962894A CN 106563168 A CN106563168 A CN 106563168A
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collagen
titanium dioxide
hydroxyapatite
titanium oxide
nanometer titanium
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王淑芳
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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
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
    • 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
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/602—Type of release, e.g. controlled, sustained, slow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
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  • Oral & Maxillofacial Surgery (AREA)
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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
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  • Organic Chemistry (AREA)
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  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention relates to a preparation method of a collagen-hydroxyapatite scaffold containing nanometer titanium dioxide. The preparation method comprises the following steps: carrying out liquid-phase reduction reaction, thus preparing nanometer titanium dioxide, uniformly mixing nanometer titanium dioxide and collagen-hydroxyapatite solution, carrying out one-step freeze-drying, and carrying out crosslinking, thus obtaining the collagen-hydroxyapatite scaffold containing nanometer titanium dioxide, wherein the concentration range of nanometer titanium dioxide is 10-50 ug/ml, and the diameter of nanometer titanium dioxide particles is 10-30 nm. For the scaffold, the needed raw materials are simple, the complicated technical requirements and high-end equipment demands are not needed, the cost is low, the popularization is easy, a reasonable nanometer titanium dioxide controlled-release system is provided for the wound surface, the long-term effective drug sustained release is provided for the wound surface, the drug concentration on the wound surface is balanced and effective, and no excessive drug exists on the wound surface.

Description

A kind of preparation method of the collagen-hydroxyapatite support containing nano titanium oxide
Technical field
The invention belongs to technical field of biological materials, and in particular to a kind of ash of the collagen-hydroxyl phosphorus containing nano titanium oxide The preparation method of stone support.
Background technology
Hydroxyapatite and collagen protein are topmost inorganic and organic principles in nature bone, and all have good life Thing characteristic, but there is when being used alone different defects again, it is difficult to meet requirement of the organizational project to biomaterial performance, with Collagen protein preferably make use of the caking property of collagen protein and overcome hydroapatite particles with hydroxyapatite compound Mobility.
Nano titanium oxide has excellent conductivity of heat, electric conductivity, surface activity and catalytic performance, in optics, catalysis, micro- The fields such as electronics, bio-sensing, antibacterial have huge using value.The nano titanium oxide mealiness of different-shape can be different, As particle diameter is less, narrow particle size distribution spherical nano TiO 2 powder has good anti-microbial property and electric conductivity.
Due to the high bioactivity of nano titanium oxide, when applying it in organizational project, wound surface or mesh are discharged into Mark organ, it preferentially can be captured by the associated protein in wound exudate or tissue, chloride ion and group, cause nano titanium oxide Granule is in some position high concentration abnormal aggregations, although can effectively participate in antibacterial, but these superfluous nano titanium oxides will be In epidermis cell, macrophage, fibroblast, aggregation, causes the apoptosis of cell, ultimately results in the disunion of wound surface or prolong Heal late.Generally speaking, immoderate use or uncontrolled release nano titanium oxide will certainly run counter to desire, to wound surface Reparation is no advantage.Therefore, safely and effectively rational slow-releasing system is needed using nano titanium oxide, provide length for wound surface Phase effective medicament slow release, keeps the drug level of wound surface balanced effective and not superfluous.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of collagen-hydroxyapatite support containing nano titanium oxide Preparation method, is to prepare nano titanium oxide by Liquid reduction reaction process, is then mixed homogeneously with collagen-hydroxyapatite solution One-step method lyophilizing it is crosslinked preparation and becomes Metal pylon afterwards, the novel nano titanium dioxide prepared with antibacterial, safety is biological Material.
The present invention is achieved by the following technical solutions：
(1) titanium tetrachloride and ammonium sulfate are adopted and is added soluble starch and is carried out for dispersant Liquid reduction reaction process and prepare and received Rice TiO 2 sol；Reaction temperature is 30 DEG C -45 DEG C；
(2) by nano titanic oxide sol microwave heating reaction in confined conditions, first under 250～350W microwave powers 2～2.5min of reaction, then 2.5～3min is reacted under 100～150W microwave powers, nanometer titanium dioxide titanium solution is obtained；
(3) NTx albumen and the hydroxyapatite that cattle heel string is originated is according to 9：1 mass ratio is dissolved into 0.5mol/L Acetic acid solution in, mix 4h after adding a certain amount of titanium solution to nanometer titanium dioxide as aimed concn with 10ppm, be subsequently adding total The glutaraldehyde of the 0.5% of quality is simultaneously mixed, and obtains the collagen-hydroxyapatite containing nano titanium oxide that mass fraction is 0.5% Nano titanium oxide, collagen-hydroxyapatite solution are injected the mould of 4cm × 4cm, are freezed 2 hours at -20 DEG C by solution, Then lyophilizing obtains collagen-hydroxyapatite support of the porous containing nano titanium oxide that thickness is 2mm for 24 hours.Nano-silica The concentration range for changing titanium is 10ug/ml-50ug/ml, and the particle diameter of nano-titania particle is 10-30nm.
Preferably, in the step (2), the condition of microwave heating reaction is：First react under 300W microwave powers 2.25min, then 2.75min is reacted under 120W microwave powers.
The present invention has the advantages that：
1. the present invention replaces traditional hydro-thermal method to prepare nano titanium oxide using microwave-hydrothermal method, with process is simple, With short production cycle, energy-conserving and environment-protective, the features such as having a safety feature.
2. the titanium dioxide nanoparticle using the method preparation is spherical in shape, uniform in size, good dispersion.
3. the support material requested of the present invention is simple, without the need for complicated technical requirements and high-end device requirement, low cost, It is easy to spread.
4. support of the present invention provides rational nano titanium oxide slow-releasing system for wound surface, provides permanently effective for wound surface Medicament slow release, keep the drug level of wound surface balanced effective and not superfluous.
Specific embodiment
The present invention is further illustrated with reference to embodiment.
Embodiment 1
A kind of preparation method of the collagen-hydroxyapatite support containing nano titanium oxide is realized by procedure below 's：
(1) titanium tetrachloride and ammonium sulfate are adopted and is added soluble starch and is carried out for dispersant Liquid reduction reaction process and prepare and received Rice TiO 2 sol；With the addition of soluble starch be the 3% of tetra chlorauric acid quality；Reaction temperature is 40 DEG C；
(2) nano titanic oxide sol stirring 10min is taken, microwave heating treatment (selects the auspicious swan in Beijing under airtight condition HX-300A computer microwaves ultrasound combinatorial compound instrument is microwave source), 2.25min is reacted under 300W microwave powers first, then in 120W 2.75min is reacted under microwave power, obtain nanometer titanium dioxide titanium solution；
(3) NTx albumen and the hydroxyapatite that cattle heel string is originated is according to 9：1 mass ratio is dissolved into 0.5mol/L Acetic acid solution in, mix 4h after adding a certain amount of titanium solution to nanometer titanium dioxide as aimed concn with 10ppm, be subsequently adding total The glutaraldehyde of the 0.5% of quality is simultaneously mixed, and obtains the collagen-hydroxyapatite containing nano titanium oxide that mass fraction is 0.5% Nano titanium oxide, collagen-hydroxyapatite solution are injected the mould of 4cm × 4cm, are freezed 2 hours at -20 DEG C by solution, Then lyophilizing obtains the collagen-hydroxyapatite support containing nano titanium oxide that thickness is 2mm for 24 hours.Nano titanium oxide Concentration range be 10ug/ml-50ug/ml, the particle diameter of nano-titania particle is 10-30nm.
Embodiment 2
A kind of preparation method of the collagen-hydroxyapatite support containing nano titanium oxide is realized by procedure below 's：
(1) titanium tetrachloride and ammonium sulfate are adopted and is added soluble starch and is carried out for dispersant Liquid reduction reaction process and prepare and received Rice TiO 2 sol；With the addition of soluble starch be the 3% of tetra chlorauric acid quality；Reaction temperature is 30 DEG C；
(2) nano titanic oxide sol stirring 10min is taken, microwave heating treatment (selects the auspicious swan in Beijing under airtight condition HX-300A computer microwaves ultrasound combinatorial compound instrument is microwave source), 2.5min is reacted under 250W microwave powers first, then in 150W 2.5min is reacted under microwave power, obtain nanometer titanium dioxide titanium solution；
(3) NTx albumen and the hydroxyapatite that cattle heel string is originated is according to 9：1 mass ratio is dissolved into 0.5mol/L Acetic acid solution in, mix 4h after adding a certain amount of titanium solution to nanometer titanium dioxide as aimed concn with 10ppm, be subsequently adding total The glutaraldehyde of the 0.5% of quality is simultaneously mixed, and it is 0.5% containing nano titanium oxide, collagen-hydroxyapatite to obtain mass fraction Nano titanium oxide, collagen-hydroxyapatite solution are injected the mould of 4cm × 4cm, are freezed 2 hours at -20 DEG C by solution, Then lyophilizing obtains collagen-hydroxyapatite support of the porous containing nano titanium oxide that thickness is 2mm for 24 hours.Nano-silica The concentration range for changing titanium is 10ug/ml-50ug/ml, and the particle diameter of nano-titania particle is 10-30nm.
Although above-mentioned be described to the specific embodiment of the present invention in conjunction with the embodiments, not to present invention protection The restriction of scope, one of ordinary skill in the art should be understood that on the basis of technical scheme, those skilled in the art The various modifications made by creative work need not be paid or deformation are still within protection scope of the present invention.

Claims (2)

1. a kind of preparation method of the collagen-hydroxyapatite support containing nano titanium oxide, is characterized in that, step is as follows：
(1) adopting titanium tetrachloride and ammonium sulfate and adding soluble starch carries out Liquid reduction reaction process preparation nanometer two for dispersant Titanium oxide sol；Reaction temperature is 30 DEG C -45 DEG C；
(2) by nano titanic oxide sol microwave heating reaction in confined conditions, first react under 250～350W microwave powers 2～2.5min, then 2.5～3min is reacted under 100～150W microwave powers, nanometer titanium dioxide titanium solution is obtained；
(3) by cattle NTx albumen and shitosan according to 9：1 mass ratio is dissolved in the acetic acid solution of 0.5mol/L, with 10ppm mixes 4h after being added to nanometer titanium dioxide titanium solution for aimed concn, be subsequently adding gross mass 0.5% glutaraldehyde simultaneously Mix, obtain mass fraction be 0.5% containing nano titanium oxide, collagen-hydroxyapatite solution, by nano titanium oxide, Collagen-hydroxyapatite solution injects the mould of 4cm × 4cm, freezes 2 hours at -20 DEG C, and then lyophilizing obtains thickness in 24 hours Spend collagen-hydroxyapatite support of the porous containing nano titanium oxide for 2mm.
2. the preparation method of a kind of collagen-hydroxyapatite support containing nano titanium oxide according to claim 1, its It is characterized in that：The concentration range of nano titanium oxide is 10ug/ml-50ug/ml, and the particle diameter of nano-titania particle is 10- 30nm。
CN201610962894.1A 2016-11-04 2016-11-04 Preparation method of collagen-hydroxyapatite scaffold containing nanometer titanium dioxide Pending CN106563168A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114732945A (en) * 2022-04-13 2022-07-12 广西农业职业技术大学 Method for improving bioactivity of titanium alloy bone

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114732945A (en) * 2022-04-13 2022-07-12 广西农业职业技术大学 Method for improving bioactivity of titanium alloy bone
CN114732945B (en) * 2022-04-13 2023-01-03 广西农业职业技术大学 Method for improving bioactivity of titanium alloy bone

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