CN107029297A - Inorganic/organic biphasic graphene oxide composite bone repair stent material and its preparation - Google Patents

Inorganic/organic biphasic graphene oxide composite bone repair stent material and its preparation Download PDF

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CN107029297A
CN107029297A CN201710218876.7A CN201710218876A CN107029297A CN 107029297 A CN107029297 A CN 107029297A CN 201710218876 A CN201710218876 A CN 201710218876A CN 107029297 A CN107029297 A CN 107029297A
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graphene oxide
collagen
inorganic
bone repair
composite bone
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张其清
王建华
孙晓敏
杨秋
张志华
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Fuzhou University
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Fuzhou University
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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
    • A61L27/50—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
    • A61L27/08—Carbon ; Graphite
    • 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
    • A61L27/14—Macromolecular materials
    • A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
    • A61L27/24—Collagen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2389/00—Characterised by the use of proteins; Derivatives thereof

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Abstract

The invention discloses a kind of inorganic/organic biphasic graphene oxide composite bone repair stent material and preparation method thereof, it is using collagen/graphene oxide as templated extracellular matrix, mineralising in situ is carried out to collagen/graphene oxide using simulated body fluid method, so that in-situ crystallization prepares the inorganic/organic biphasic graphene oxide composite bone repair stent material on templated extracellular matrix.The material has good physicochemical property and biocompatibility, is a kind of medical material for being preferably applied to bone tissue defect repair, and its preparation technology is gentle, and processing and forming is convenient.

Description

Inorganic/organic biphasic graphene oxide composite bone repair stent material and its preparation
Technical field
The invention belongs to technical field of biological materials, and in particular to a kind of inorganic/organic biphasic graphene oxide Composite Bone Renovating bracket material and preparation method thereof.
Background technology
The bone tissue defect clinically caused by the factor such as birth defects and wound, infection, osteoporosis is that orthopaedics is normal Reconstruction after the disease seen, bone tissue defect is always one of problem that orthopaedics faces.Although human body bone has certain Regeneration and self-reparing capability, but the difference with fitness with advancing age, are repairing and can not heal by itself merely In the case of, then need to be treated using bone collection operation.Bone alternate material and bone tissue engineer people for bone defect healing Work material, is the hot issue of organizational project and the concern of biomaterial field.
At the beginning of 20 end of the centurys to 21 century, the discovery of CNT and graphene oxide not only extends carbon family, People have been promoted to the further understanding of carbon series elements.Graphene oxide（Grahene oxide, GO）It is graphene functionalized Derivative, its skeleton structure is similar with graphene, to approach the two-dimensional network structure of plane.Graphene oxide carbon atom arrangement Contain a variety of oxy radicals, such as carbonyl in lamellar structure surface（C=O）, carboxyl（-COOH）, hydroxyl（-OH）And epoxy radicals（C-O-C） Deng they impart graphene oxide some new characteristics, and such as interlamellar spacing is significantly increased, piece interlayer electrical mutual row of the same race Reprimand, makes graphene oxide have more preferable dispersiveness；Excellent antibiotic property；Prominent mechanical performance and good bio-compatible Property.
Collagen, as the main component of nature bone, is the template of biomineralization during bon e formation, and its biomineralization is people With vertebrate generate bone, the tissue such as tooth must be through process.Collagen possesses good molding processibility and biocompatibility etc. Advantage, but the defect such as mechanical strength is not enough, antibacterial intensity difference limits its and widely applies.
By simulating the composition and structure of nature bone, collagen/nano-hydroxy-apatite is prepared using biomimetic mineralization method in situ Stone (Col/n-HA) material, and the bone tissue reparation engineering rack prepared on this basis disclosure satisfy that medical science and clinical needs, It is study hotspot in recent years.
Biomineralization is the process that mineral matter is formed in organism, is referred in certain physiological environment, large biological molecule and Inorganic matter ion is under inducible factor effect, and the inorganic ions in solution is converted into inorganic ore deposit by the interaction in interface The process that thing is mutually separated out, so as to form the biomineralization material with special multilevel hierarchy and assembling mode, such as bone, tooth and shellfish Shell etc..Biomimetic mineralization research is current one important research direction in biomimetic material field, and it is to study the mineral in organism Based on matter, it is therefore an objective on the basis of understanding biomineralization material and environmental condition, the process of mimic biology body mineralising is closed Into with the mineral material to natural biological tissue with similar structure and performance.Detailed process is analogue body pendular ring in vitro Border, using timbering material as template, the inorganic mineralizer of target is formed on its surface, so as to prepare with unique purpose design feature Bionic composite material.
The content of the invention
It is an object of the invention to provide a kind of inorganic/organic biphasic graphene oxide composite bone repair stent material and its Preparation method, the composite bone repair stent material has the features such as loose porous, porosity is high, biocompatibility is good, is applicable In bone tissue defect repair.
To achieve the above object, the present invention uses following technical scheme：
A kind of inorganic/organic biphasic graphene oxide composite bone repair stent material, it uses simulated body fluid method to collagen/oxidation Graphene templated extracellular matrix carries out mineralising in situ, so that in-situ crystallization prepares the inorganic/organic biphasic oxidation on templated extracellular matrix Graphene composite bone repair stent material；
In the collagen/graphene oxide templated extracellular matrix, the mass ratio of collagen and graphene oxide is 1:0.01~0.04.
The collagenous source is in fish-skin, pigskin, ox-hide or beef tendon.
The preparation method of the inorganic/organic biphasic graphene oxide composite bone repair stent material comprises the following steps：
（1）Graphene oxide powder is dissolved in ultrasonic 120 min under deionized water, 200 W power, 1g/mL is obtained and is uniformly dispersed Graphene oxide water solution；
（2）Collagen is dissolved in the malonic acid solution that volumetric concentration is 0.4%, is sufficiently stirred for, up to being completely dissolved, obtaining quality dense The collagen solution of degree 0.6%；
（3）After gained graphene oxide water solution and collagen solution are stirred, it is freeze-dried and is crosslinked；
（4）The collagen that crosslinking is obtained/graphene oxide templated extracellular matrix is carried out after mineralising in situ, is washed, removed with distilled water The SBF solions of surface adhesion are removed, then the inorganic/organic biphasic graphene oxide Composite Bone is made through vacuum freeze drying Renovating bracket material.
Crosslinking crosslinking agent used is after mixing 30.026g D-riboses, 100 mL acetone with 20 mL ammoniacal liquor, plus pure water is determined Hold to 1000 mL and be made.
The mineralising in situ is after the collagen after crosslinking/graphene oxide templated extracellular matrix is sterilized with gamma-ray irradiation, It is soaked under aseptic condition in 1.5 × SBF solution, is placed in mineralising reaction 3 days in 37 DEG C of constant temperature low speed shaking tables, during which every 24 h Change fresh SBF solution.
The synthetic method of the graphene oxide is as follows：
（1）By the dense H of 108 mL2SO4With 12mL H3PO4Ice bath stirs 10 min, and 5.0 g are sequentially added while strong agitation The graphite powder of particle diameter≤30 μm and 2.5 g NaNO3；
（2）It is not higher than in controlling reaction temperature under conditions of 5 DEG C, by 15.0 g KMnO4Divide 3-5 times and be slowly added into step 1） In gained mixture, after the h of ice bath stirring reaction 3, move in 40 DEG C of water-baths and continue to stir 60 min；
（3）By step 2）Gained mixed liquor is brought rapidly up to 98 DEG C, and is incubated 60 min, and deionization is continuously added into the process Water is to overall solution volume up to 400 mL；15 mL H are added after 5 min2O2Remove unnecessary oxidant；
（4）Mixed solution is centrifuged, the HCl solution repeated washing of gained precipitation ultra-pure water and volumetric concentration 5%, until washing out In liquid untill sulfate radical-free ion detection, then it is freeze-dried, obtain the graphene oxide powder of individual layer laminated structure.
The remarkable advantage of the present invention is：
（1）The present invention carries out mineralising reaction to it using simulated body fluid immersion, made using collagen/graphene oxide as templated extracellular matrix Standby to obtain inorganic/organic biphasic graphene oxide composite bone repair stent material, resulting materials are loose porous, and biocompatibility is good It is good.
（2）Traditional formaldehyde used is substituted using D-ribose in D-ribose no cytotoxicity, the present invention and prepares crosslinking as raw material Agent, can instead give birth to Maillard reaction with collagen using it, make formed arrangement of collagen fibers more dense regular, so as to obtain excellent Different cross-linking effect.
Brief description of the drawings
Fig. 1 is the section structure scanning electron microscope (SEM) photograph of collagen/graphene oxide templated extracellular matrix prepared by embodiment 1.
Fig. 2 is that the gained graphene oxide after mineralising reaction of templated extracellular matrix prepared by embodiment 1 is combined bone repairing support material The surface scan electron microscope of material.
Fig. 3 is that the gained graphene oxide after mineralising reaction of templated extracellular matrix prepared by embodiment 1 is combined bone repairing support material The X-ray powder diffraction figure of material.
Embodiment
In order that content of the present invention easily facilitates understanding, with reference to embodiment to of the present invention Technical scheme is described further, but the present invention is not limited only to this.
Embodiment 1
（1）The synthesis of graphene oxide
The dense H of 108 mL are measured first2SO4With 12 mL H3PO4It is added in 500 mL three-necked flasks, ice bath stirs 10 min, 5.0 g graphite powder is sequentially added while strong agitation（Particle diameter≤30 μm）With 2.5 g NaNO3；In controlling reaction temperature Under conditions of not higher than 5 DEG C, by 15.0 g KMnO4Divide 3-5 times and be slowly added into said mixture, the h of ice bath stirring reaction 3 Afterwards, move in 40 DEG C of water-baths and persistently stir 60 min；Then mixed liquor is brought rapidly up to 98 DEG C, and is incubated 60 min, herein During be continuously added into deionized water to mixed liquor cumulative volume up to 400 mL；15 mL H are added after 5 min2O2Remove unnecessary oxygen Agent；Mixed solution is centrifuged, the HCl solution repeated washing of gained precipitation ultra-pure water and volumetric concentration 5%, until eluate Middle sulfate radical-free ion is detected, then the freeze-dried GO powder for obtaining individual layer laminated structure；
（2）The preparation of graphene oxide solution
Graphene oxide powder is dissolved in deionized water, and ultrasonic 120 min under 200 W power, 1g/mL is obtained and is uniformly dispersed Graphene oxide water solution；
（3）The preparation of collagen solution
After the beef tendon collagen bought is freeze-dried, 0.6 g is weighed, is dissolved in the malonic acid solution that volumetric concentration is 0.4%, fills Divide stirring until being completely dissolved, prepare the collagen solution that mass concentration is 0.6%；
（4）The preparation of collagen/graphene oxide templated extracellular matrix
Take the prepared mL of graphene oxide water solution 4 uniformly to be mixed with 96 g collagen solutions, obtain collagen/graphene oxide Mixed solution；Mixed solution is freeze-dried after 48 h, is crosslinked in crosslinked fluid（Crosslinked fluid used is with 30.026 g D-ribose, 100 mL acetone and 20 mL ammoniacal liquor add water and are made into 1000 mL）；Composite after crosslinking is rushed repeatedly with deionized water Wash, then it is freeze-dried after, that is, obtain graphene oxide mass fraction be 4% collagen/graphene oxide templated extracellular matrix.
Embodiment 2
In embodiment one, the mL of graphene oxide water solution 2 is well mixed with 98 g collagen solutions, other steps are with implementing Example one is identical, prepares collagen/graphene oxide templated extracellular matrix that graphene oxide mass fraction is 2%.
Embodiment 3
In embodiment one, the mL of graphene oxide water solution 1 is well mixed with 99 g collagen solutions, other steps are with implementing Example one is identical, prepares collagen/graphene oxide templated extracellular matrix that graphene oxide mass fraction is 1%.
After collagen prepared by embodiment 1/graphene oxide templated extracellular matrix is sterilized with gamma-ray irradiation, soaked under aseptic condition Steep in 1.5 times of simulated body fluids（1.5×SBF）In（Simulated body fluid compound method is shown in Table 1）, it is placed in 37 DEG C of constant temperature low speed shaking tables Carry out mineralising reaction 3 days, during which every 24 h changes fresh SBF solution, after reaction terminates, take out sample distillation water washing, then Moisture is removed through vacuum freeze drying, that is, obtains corresponding bone renovating bracket material.
The compound method of the simulated body fluid of table 1（1000mL）
Fig. 1,2 are respectively gained composite bone repair stent material after 1 collagen of embodiment/graphene oxide templated extracellular matrix and its mineralising Scanning electron microscope (SEM) photograph.As seen from the figure, soaked in simulated body fluid after mineralising, there is novel substance deposition on timbering material surface.
Fig. 3 is 1 collagen of embodiment/graphene oxide templated extracellular matrix gained composite bone repair stent material after mineralising reaction XRD.As seen from the figure, timbering material surface and hole wall have nanometer hydroxyapatite generation, show inorganic/organic biphasic oxidation Graphene composite bone repair stent material is successfully prepared.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, should all belong to the covering scope of the present invention.

Claims (7)

1. a kind of inorganic/organic biphasic graphene oxide composite bone repair stent material, it is characterised in that：Using simulated body fluid method Mineralising in situ is carried out to collagen/graphene oxide templated extracellular matrix, thus on templated extracellular matrix in-situ crystallization prepare it is described it is inorganic/have Machine two-phase graphene oxide composite bone repair stent material；
The mass ratio of collagen and graphene oxide is 1 in the collagen/graphene oxide templated extracellular matrix:0.01~0.04.
2. inorganic according to claim 1/organic biphasic graphene oxide composite bone repair stent material, it is characterised in that： The collagenous source is in fish-skin, pigskin, ox-hide or beef tendon.
3. a kind of preparation method of inorganic/organic biphasic graphene oxide composite bone repair stent material as claimed in claim 1, It is characterized in that：Comprise the following steps：
（1）Graphene oxide powder is dissolved in ultrasonic 120 min under deionized water, 200 W power, 1g/mL is obtained and is uniformly dispersed Graphene oxide water solution；
（2）Collagen is dissolved in the malonic acid solution that volumetric concentration is 0.4%, is sufficiently stirred for, up to being completely dissolved, obtaining quality dense The collagen solution of degree 0.6%；
（3）After gained graphene oxide water solution and collagen solution are stirred, it is freeze-dried and is crosslinked；
（4）The collagen that crosslinking is obtained/graphene oxide templated extracellular matrix is carried out after mineralising in situ, is washed with distilled water, then Inorganic/organic biphasic graphene oxide the composite bone repair stent material is made through vacuum freeze drying.
4. the preparation method of inorganic according to claim 3/organic biphasic graphene oxide composite bone repair stent material, It is characterized in that：Crosslinking crosslinking agent used is after mixing 30.026g D-riboses, 100 mL acetone with 20 mL ammoniacal liquor, plus pure Water is settled to 1000 mL and is made.
5. the preparation method of inorganic according to claim 3/organic biphasic graphene oxide composite bone repair stent material, It is characterized in that：The mineralising in situ is after the collagen graphene oxide templated extracellular matrix after crosslinking is sterilized with gamma-ray irradiation, Aseptically it is soaked in 1.5 × SBF solution, is placed in mineralising reaction 3 days in 37 DEG C of constant temperature low speed shaking tables, during which every 24 H changes fresh SBF solution.
6. the preparation method of inorganic according to claim 3/organic biphasic graphene oxide composite bone repair stent material, its It is characterised by：The synthetic method of the graphene oxide powder is as follows：
（1）By the dense H of 108 mL2SO4With 12mL H3PO4Ice bath stirs 10 min, and 5.0 g are sequentially added while strong agitation Graphite powder and 2.5 g NaNO3；
（2）It is not higher than in controlling reaction temperature under conditions of 5 DEG C, by 15.0 g KMnO4Divide 3-5 times and be slowly added into step 1）Institute Obtain in mixture, after the h of ice bath stirring reaction 3, move in 40 DEG C of water-baths and continue to stir 60 min；
（3）By step 2）Gained mixed liquor is brought rapidly up to 98 DEG C, and is incubated 60 min, and deionization is continuously added into the process Water is to overall solution volume up to 400 mL；15 mL H are added after 5 min2O2；
（4）Mixed solution is centrifuged, the HCl solution repeated washing of gained precipitation ultra-pure water and volumetric concentration 5%, until washing out In liquid untill sulfate radical-free ion detection, then it is freeze-dried, obtain the graphene oxide powder of individual layer laminated structure.
7. the preparation method of inorganic according to claim 6/organic biphasic graphene oxide composite bone repair stent material, It is characterized in that：Particle diameter≤30 μm of graphite powder used.
CN201710218876.7A 2017-04-06 2017-04-06 Inorganic/organic biphasic graphene oxide composite bone repair stent material and its preparation Pending CN107029297A (en)

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CN107998444A (en) * 2018-01-12 2018-05-08 李嘉伦 A kind of preparation method and applications of skin repair aerogel type dressing
CN109453430A (en) * 2017-11-09 2019-03-12 华中科技大学同济医学院附属协和医院 A kind of collagen of hydroxyapatite coating layer-graphene oxide biomimetic material and preparation method thereof
CN110755669A (en) * 2019-10-31 2020-02-07 河南亚都实业有限公司 Medical collagen wound repair membrane
CN111939326A (en) * 2020-09-17 2020-11-17 苏州宣医智慧医疗科技有限公司 Bionic gradient mineralization method of conductive hydrogel based on graphene bioactive macromolecules

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109453430A (en) * 2017-11-09 2019-03-12 华中科技大学同济医学院附属协和医院 A kind of collagen of hydroxyapatite coating layer-graphene oxide biomimetic material and preparation method thereof
CN109453430B (en) * 2017-11-09 2021-12-24 华中科技大学同济医学院附属协和医院 Collagen-graphene oxide bionic material of hydroxyapatite coating and preparation method thereof
CN107998444A (en) * 2018-01-12 2018-05-08 李嘉伦 A kind of preparation method and applications of skin repair aerogel type dressing
CN107998444B (en) * 2018-01-12 2020-07-31 李嘉伦 Preparation method and application of skin repair aerogel type dressing
CN110755669A (en) * 2019-10-31 2020-02-07 河南亚都实业有限公司 Medical collagen wound repair membrane
CN110755669B (en) * 2019-10-31 2022-02-01 河南亚都实业有限公司 Medical collagen wound repair membrane
CN111939326A (en) * 2020-09-17 2020-11-17 苏州宣医智慧医疗科技有限公司 Bionic gradient mineralization method of conductive hydrogel based on graphene bioactive macromolecules

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Application publication date: 20170811