CN106730020A - A kind of strontium carbonate modified fibroin composite and preparation method thereof - Google Patents
A kind of strontium carbonate modified fibroin composite and preparation method thereof Download PDFInfo
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- CN106730020A CN106730020A CN201611145102.8A CN201611145102A CN106730020A CN 106730020 A CN106730020 A CN 106730020A CN 201611145102 A CN201611145102 A CN 201611145102A CN 106730020 A CN106730020 A CN 106730020A
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- strontium
- fibroin
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- silk
- formic acid
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- 108010022355 Fibroins Proteins 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 title claims abstract description 38
- 229910000018 strontium carbonate Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 64
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 45
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 30
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 30
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000019253 formic acid Nutrition 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 20
- 239000000835 fiber Substances 0.000 claims abstract description 19
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 18
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- XTBNHDRTEOBELJ-UHFFFAOYSA-L C(=O)O.[Cl-].[Sr+2].[Cl-] Chemical compound C(=O)O.[Cl-].[Sr+2].[Cl-] XTBNHDRTEOBELJ-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000012460 protein solution Substances 0.000 claims abstract description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 13
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- -1 acrylate trimethylolethane cyclic carbonate ester Chemical class 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 9
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 9
- 235000008708 Morus alba Nutrition 0.000 claims description 8
- 240000000249 Morus alba Species 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 235000003846 Ricinus Nutrition 0.000 claims description 2
- 241000322381 Ricinus <louse> Species 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 238000007306 functionalization reaction Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 239000012620 biological material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- XMHCSVHEBCVIFR-UHFFFAOYSA-N 2-(hydroxymethyl)-2-methylpropane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(C)(CO)CO XMHCSVHEBCVIFR-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical group [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000011173 biocomposite Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000005847 immunogenicity Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052806 inorganic carbonate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 210000002997 osteoclast Anatomy 0.000 description 1
- 230000000278 osteoconductive effect Effects 0.000 description 1
- 230000002188 osteogenic effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
Classifications
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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
- A61L27/50—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
- A61L27/58—Materials at least partially resorbable by the body
-
- 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
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/252—Polypeptides, proteins, e.g. glycoproteins, lipoproteins, cytokines
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
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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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
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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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Biomedical Technology (AREA)
- Molecular Biology (AREA)
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- Composite Materials (AREA)
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- Chemical Or Physical Treatment Of Fibers (AREA)
- Materials For Medical Uses (AREA)
Abstract
The present invention relates to a kind of strontium carbonate modified fibroin composite and preparation method thereof.Macromolecular material is dissolved into macromolecular material formic acid solution is obtained in formic acid；Fibroin fiber is obtained after natural silk degumming treatment；The fibroin fiber is dissolved in strontium chloride formic acid solution, silk fibroin protein solution is obtained；Add macromolecular material formic acid solution；Regenerated silk fibroin film containing strontium is dried to obtain after mixing；In the presence of ammonium carbonate or ammonium hydrogen carbonate, will contain strontium regenerated silk fibroin film and insert carries out mineralising treatment in closed container, obtain mineralising film；Mineralising film is placed in deionized water；Then dried process obtains strontium carbonate modified fibroin composite.The 100MPa of fracture of composite materials intensity 70 prepared by the present invention, elongation at break 6 10%；The 5GPa of Young's modulus 3, can apply in bone renovating material is prepared.
Description
Technical field
The invention belongs to Biocomposite material technical field, and in particular to a kind of strontium carbonate modified fibroin composite and its
Preparation method, prepared material has wide application prospects in regenerative medicine field.
Background technology
China is the major producing country of silk, and silk yield accounts for more than the 70% of world wide production.Fibroin albumen not only has good
Good biocompatibility and degradation property, also easy processing are modified, catabolite is nontoxic and low immunogenicity, and excellent thing
Reason mechanical performance, thus as preferable bio-medical material, by both domestic and external widely studied.Wherein, silk fibroin bracket
Research of the material in bone tissue engineer field confirms one of focus.At present, fibroin albumen has successfully been processed into various forms of
Bone tissue engineering scaffold, including film, nanofiber, porous support, hydrogel etc., these materials are in bone lacks, injury repair
Achieve expected therapeutic effect.However, fibroin albumen as the research of bone renovating material still based on inactive, lack
Few characteristic that should possess to the rationality such as bone growth inducing, osteoconductive bone tissue engineering stent material.
Strontium and its compound have important osteogenic action, therefore, strontium biomaterial is mixed as bioactivity Bone Defect Repari material
One of study hotspot of material, but strontium and the pass that the compatibility and interfacial effect of biomaterial are that composite property is played
Key, regrettably, prior art does not have effective method to improve the compatibility of strontium and biomaterial, causes to mix strontium biomaterial reality
Border application is obstructed.
The content of the invention
It is an object of the invention to provide a kind of strontium carbonate modified fibroin composite for possessing self-bone grafting power of regeneration and its
Preparation method, in the composite for obtaining, strontium can suppress the activity of osteoclast while osteoblast activity is promoted, right
The inducibility of ostosis is strong, and newborn bone amount can be caused to increase.
To reach above-mentioned purpose, the invention discloses a kind of preparation method of strontium carbonate modified fibroin composite, including
Following steps：
（1）Macromolecular material is dissolved into macromolecular material formic acid solution is obtained in formic acid；
（2）Fibroin fiber is obtained after natural silk degumming treatment；The fibroin fiber is dissolved in strontium chloride formic acid solution,
Obtain silk fibroin protein solution；Add macromolecular material formic acid solution；Regenerated silk fibroin film containing strontium is dried to obtain after mixing；
（3）In the presence of ammonium carbonate or ammonium hydrogen carbonate, will contain strontium regenerated silk fibroin film and insert carries out mineralising in closed container
Treatment, obtains mineralising film；
（4）Mineralising film is placed in deionized water；Then dried process obtains strontium carbonate modified fibroin composite.
In above-mentioned technical proposal, the silk is one or more in mulberry silk, tussah silk, ricinus silk.
In above-mentioned technical proposal, in the strontium chloride formic acid solution, strontium chloride concentration is 1-5wt%；The fibroin albumen is molten
In liquid, fibroin albumen concentration is 10-20wt%.Can cause that strontium chloride has good dispersiveness in fibroin fiber, for
To the composite lay a good foundation that interfacial effect is excellent；The inducing action to strontium carbonate mineralising can be ensured, bar-shaped carbonic acid is completed
The generation of strontium.
In above-mentioned technical proposal, the temperature of the mineralising treatment is 40-60 DEG C, and the time is 40-60 hours；At the mineralising
The relative humidity of reason is 40-60%.The present invention can not only realize in situ mineralising of the strontium carbonate in fibroin membrane, and regulation and control carbonic acid
The form of strontium, being formed has bar-shaped mode of appearance structure, and the club shaped structure is in nanometer level, helps to lift fibroin membrane
Mechanical property.
In above-mentioned technical proposal, strontium chloride, fibroin albumen, the mass ratio of macromolecular material are（5~8）∶80∶30；By ore deposit
Change film to be placed in 0.5-1 hours in deionized water；The dried process is that room temperature is placed 0.5 hour, and then 60 DEG C are heated 2 hours,
Last 90 DEG C are heated 30-50 seconds.By this treatment, the carbonate of unreacted strontium chloride and residual can be completely removed, it is ensured that mesh
The good biocompatibility of mark material.
In above-mentioned technical proposal, the preparation method of the macromolecular material is, by trimethylene carbonate, acrylate three
Hydroxymethyl ethane cyclic carbonate ester is dissolved in dichloromethane, is stirred 8~15 minutes；It is subsequently adding trimethyl phosphite and double（It is double
Trimethyl silicon substrate）The dichloromethane solution of amine zinc, stirs 20~35 minutes；Propilolic alcohol is subsequently adding, is stirred 30~45 minutes；Connect
And reacted 40~55 hours in 40 DEG C of sealings, then use glacial acetic acid terminating reaction, reaction solution is precipitated in ice ether, will precipitated
Thing vacuum drying obtains macromolecular material；Trimethylene carbonate, acrylate trimethylolethane cyclic carbonate ester, trimethyl are sub-
It is phosphate, double（Double trimethyl silicon substrates）Amine zinc, the mass ratio of propilolic alcohol are 100: 80: 20: 0.1:（5~8）；The macromolecule material
The concentration for expecting formic acid solution is 5~8wt%.
The present invention further discloses the strontium carbonate modified fibroin composite prepared according to the above method, the composite wood
Functive strontium carbonate exists with nano bar-shape in material, a diameter of 10-200 nm of strontium carbonate rod, a length of 10-100 μm.
Fracture of composite materials intensity 70-100MPa, elongation at break 6-10% prepared by the present invention；Young's modulus 3-5GPa.
Therefore the application the present invention further discloses above-mentioned strontium carbonate modified fibroin composite in bone renovating material is prepared.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
（1）Present invention firstly discloses fibroin albumen/strontium carbonate composite, the composite can be sustained strontium element, therefore tool
There is the ability of induction ostosis, be a kind of preferable functionalization bone renovating material.
（2）Preparation method of the invention can not only realize in situ mineralising of the strontium carbonate in fibroin membrane, and strontium carbonate
Form is regulated and controled by fibroin albumen, and being formed has bar-shaped mode of appearance structure, and the club shaped structure is in nanometer level；Especially
It is strontium carbonate rod-like morphology structure disperses inside fibroin protein film, the club shaped structure contribute to lifted fibroin membrane mechanical property
Energy.
（3）Dried process process of the invention is also the process that macromolecular material and silk form good interface performance,
Room temperature is placed contributes to dispersion and infiltration of the macromolecular material combination strontium carbonate nanorods in silk, then progressively add
On the one hand heat, final high temperature short time treatment avoids the problem of local excessive polymerization caused by macromolecular material quick response, two
Aspect avoids silk heat damage, and three aspects can obtain the good inorganic-macromolecule-silk interface of interfacial effect.
（4）The present invention, by adding rational modifying agent and limiting propilolic alcohol, is tied on the basis of carbonate monomer
The consumption of each component is closed, modified carbonate polymer is prepared as macromolecular material, not only with good biological nature, and
And for silk fabric, moreover it is possible to fire-retardant, toughness reinforcing effect is provided, it is particularly compatible with inorganic carbonate strontium.
（5）There is good biocompatibility and stronger present invention firstly discloses fibroin albumen/strontium carbonate composite
Induction ostosis ability；Particularly fibroin albumen is existing with the compound solution of strontium by it as active bone repair material
The problem of strontium biomaterial poor compatibility, correlative study achievement will have wide market application value.
Specific embodiment
With reference to embodiment, the invention will be further described：
Synthesis example
Trimethylene carbonate, acrylate trimethylolethane cyclic carbonate ester are dissolved in dichloromethane, are stirred 15 minutes；So
Trimethyl phosphite and double is added afterwards（Double trimethyl silicon substrates）The dichloromethane solution of amine zinc, stirs 35 minutes；It is subsequently adding
Propilolic alcohol, stirs 30 minutes；Then reacted 40 hours in 40 DEG C of sealings, then use glacial acetic acid terminating reaction, reaction solution is in ice second
Precipitated in ether, sediment vacuum drying is obtained into high-molecular material A；Trimethylene carbonate, acrylate trimethylolethane
It is cyclic carbonate ester, trimethyl phosphite, double（Double trimethyl silicon substrates）Amine zinc, the mass ratio of propilolic alcohol are 100: 80: 20: 0.1: 5；
High-molecular material A is dissolved in formic acid（It is pure）It is the macromolecular material formic acid solution A of 5wt% to prepare concentration；
Trimethylene carbonate, acrylate trimethylolethane cyclic carbonate ester are dissolved in dichloromethane, are stirred 8 minutes；So
Trimethyl phosphite and double is added afterwards（Double trimethyl silicon substrates）The dichloromethane solution of amine zinc, stirs 20 minutes；It is subsequently adding
Propilolic alcohol, stirs 30 minutes；Then reacted 40 hours in 40 DEG C of sealings, then use glacial acetic acid terminating reaction, reaction solution is in ice second
Precipitated in ether, sediment vacuum drying is obtained into macromolecular material B；Trimethylene carbonate, acrylate trimethylolethane
It is cyclic carbonate ester, trimethyl phosphite, double（Double trimethyl silicon substrates）Amine zinc, the mass ratio of propilolic alcohol are 100: 80: 20: 0.1: 8；
Macromolecular material B is dissolved in formic acid（It is pure）It is the macromolecular material formic acid solution B of 8wt% to prepare concentration；
Trimethylene carbonate, acrylate trimethylolethane cyclic carbonate ester are dissolved in dichloromethane, are stirred 15 minutes；So
Trimethyl phosphite and double is added afterwards（Double trimethyl silicon substrates）The dichloromethane solution of amine zinc, stirs 35 minutes；It is subsequently adding
Propilolic alcohol, stirs 45 minutes；Then reacted 50 hours in 40 DEG C of sealings, then use glacial acetic acid terminating reaction, reaction solution is in ice second
Precipitated in ether, sediment vacuum drying is obtained into macromolecular material C；Trimethylene carbonate, acrylate trimethylolethane
It is cyclic carbonate ester, trimethyl phosphite, double（Double trimethyl silicon substrates）Amine zinc, the mass ratio of propilolic alcohol are 100: 80: 20: 0.1: 6；
Macromolecular material C is dissolved in formic acid（It is pure）It is the macromolecular material formic acid solution C of 7wt% to prepare concentration.
Embodiment one
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；By silk
Fibroin fiber is dissolved in strontium chloride formic acid solution（1wt%）In, obtain silk fibroin protein solution（10wt%）；Add macromolecular material
Formic acid solution A；Regenerated silk fibroin film containing strontium is dried to obtain after mixing；
（2）In the presence of ammonium carbonate or ammonium hydrogen carbonate, will contain strontium regenerated silk fibroin film and insert carries out mineralising in closed container
Treatment, obtains mineralising film；Strontium chloride, fibroin albumen, the mass ratio of macromolecular material are（5~8）∶80∶30；The temperature of mineralising treatment
It is 40-60 DEG C to spend, and the time is 40-60 hours, and relative humidity is 40-60%；
（3）Mineralising film is placed in 0.5-1 hours in deionized water；Then dried process obtains strontium carbonate modified fibroin composite wood
Material；The dried process is that room temperature is placed 0.5 hour, and then 60 DEG C are heated 2 hours, and last 90 DEG C are heated 30-50 seconds.
The fracture of composite materials intensity 100MPa of above-mentioned preparation, elongation at break 10%；Young's modulus 3.8GPa, oxygen index (OI)
28, can be applied in functionalization bone renovating material is prepared.
Embodiment two
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；By silk
Fibroin fiber is dissolved in strontium chloride formic acid solution（2wt%）In, obtain silk fibroin protein solution（12wt%）；Add macromolecular material
Formic acid solution A；Regenerated silk fibroin film containing strontium is dried to obtain after mixing；
（2）In the presence of ammonium carbonate or ammonium hydrogen carbonate, will contain strontium regenerated silk fibroin film and insert carries out mineralising in closed container
Treatment, obtains mineralising film；Strontium chloride, fibroin albumen, the mass ratio of macromolecular material are 7: 80: 30；Mineralising treatment temperature be
40 DEG C, the time is 60 hours, and relative humidity is 40%；
（3）Mineralising film is placed in 1 hour in deionized water；Then dried process obtains strontium carbonate modified fibroin composite；Institute
Dried process is stated for room temperature is placed 0.5 hour, then 60 DEG C are heated 2 hours, and last 90 DEG C are heated 50 seconds.
The fracture of composite materials intensity 90MPa of above-mentioned preparation, elongation at break 9%；Young's modulus 5GPa, oxygen index (OI) 28, can
Applied with functionalization bone renovating material is prepared.
Embodiment three
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；By silk
Fibroin fiber is dissolved in strontium chloride formic acid solution（3wt%）In, obtain silk fibroin protein solution（14wt%）；Add macromolecular material
Formic acid solution B；Regenerated silk fibroin film containing strontium is dried to obtain after mixing；
（2）In the presence of ammonium carbonate or ammonium hydrogen carbonate, will contain strontium regenerated silk fibroin film and insert carries out mineralising in closed container
Treatment, obtains mineralising film；Strontium chloride, fibroin albumen, the mass ratio of macromolecular material are 7: 80: 30；Mineralising treatment temperature be
50 DEG C, the time is 40 hours, and relative humidity is 60%；
（3）Mineralising film is placed in 0.5 hour in deionized water；Then dried process obtains strontium carbonate modified fibroin composite；
The dried process is that room temperature is placed 0.5 hour, and then 60 DEG C are heated 2 hours, and last 90 DEG C are heated 50 seconds.
The fracture of composite materials intensity 80MPa of above-mentioned preparation, elongation at break 7%；Young's modulus 4.5GPa, oxygen index (OI) 28,
Can be applied in functionalization bone renovating material is prepared.
Example IV
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；By silk
Fibroin fiber is dissolved in strontium chloride formic acid solution（4wt%）In, obtain silk fibroin protein solution（16wt%）；Add macromolecular material
Formic acid solution B；Regenerated silk fibroin film containing strontium is dried to obtain after mixing；
（2）In the presence of ammonium carbonate or ammonium hydrogen carbonate, will contain strontium regenerated silk fibroin film and insert carries out mineralising in closed container
Treatment, obtains mineralising film；Strontium chloride, fibroin albumen, the mass ratio of macromolecular material are 6: 80: 30；Mineralising treatment temperature be
40 DEG C, the time is 40 hours, and relative humidity is 50%；
（3）Mineralising film is placed in 1 hour in deionized water；Then dried process obtains strontium carbonate modified fibroin composite；Institute
Dried process is stated for room temperature is placed 0.5 hour, then 60 DEG C are heated 2 hours, and last 90 DEG C are heated 40 seconds.
The fracture of composite materials intensity 70MPa of above-mentioned preparation, elongation at break 6.1%；Young's modulus 4.6GPa, oxygen index (OI)
28, can be applied in functionalization bone renovating material is prepared.
Embodiment five
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；By silk
Fibroin fiber is dissolved in strontium chloride formic acid solution（5wt%）In, obtain silk fibroin protein solution（18wt%）；Add macromolecular material
Formic acid solution C；Regenerated silk fibroin film containing strontium is dried to obtain after mixing；
（2）In the presence of ammonium carbonate or ammonium hydrogen carbonate, will contain strontium regenerated silk fibroin film and insert carries out mineralising in closed container
Treatment, obtains mineralising film；Strontium chloride, fibroin albumen, the mass ratio of macromolecular material are 8: 80: 30；Mineralising treatment temperature be
60 DEG C, the time is 40 hours, and relative humidity is 40%；
（3）Mineralising film is placed in 1 hour in deionized water；Then dried process obtains strontium carbonate modified fibroin composite；Institute
Dried process is stated for room temperature is placed 0.5 hour, then 60 DEG C are heated 2 hours, and last 90 DEG C are heated 50 seconds.
The fracture of composite materials intensity 93MPa of above-mentioned preparation, elongation at break 6%；Young's modulus 4.7GPa, oxygen index (OI) 28,
Can be applied in functionalization bone renovating material is prepared.
Embodiment six
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；By silk
Fibroin fiber is dissolved in strontium chloride formic acid solution（3wt%）In, obtain silk fibroin protein solution（20wt%）；Add macromolecular material
Formic acid solution C；Regenerated silk fibroin film containing strontium is dried to obtain after mixing；
（2）In the presence of ammonium carbonate or ammonium hydrogen carbonate, will contain strontium regenerated silk fibroin film and insert carries out mineralising in closed container
Treatment, obtains mineralising film；Strontium chloride, fibroin albumen, the mass ratio of macromolecular material are 5: 80: 30；Mineralising treatment temperature be
40 DEG C, the time is 40 hours, and relative humidity is 40%；
（3）Mineralising film is placed in 0.5 hour in deionized water；Then dried process obtains strontium carbonate modified fibroin composite；
The dried process is that room temperature is placed 0.5 hour, and then 60 DEG C are heated 2 hours, and last 90 DEG C are heated 30 seconds.
The fracture of composite materials intensity 89MPa of above-mentioned preparation, elongation at break 8.9%；Young's modulus 4.8GPa, oxygen index (OI)
28, can be applied in functionalization bone renovating material is prepared.
Claims (10)
1. a kind of preparation method of strontium carbonate modified fibroin composite, it is characterised in that comprise the following steps：
（1）Macromolecular material is dissolved into macromolecular material formic acid solution is obtained in formic acid；
（2）Fibroin fiber is obtained after natural silk degumming treatment；The fibroin fiber is dissolved in strontium chloride formic acid solution,
Obtain silk fibroin protein solution；Add macromolecular material formic acid solution；Regenerated silk fibroin film containing strontium is dried to obtain after mixing；
（3）In the presence of ammonium carbonate or ammonium hydrogen carbonate, will contain strontium regenerated silk fibroin film and insert carries out mineralising in closed container
Treatment, obtains mineralising film；
（4）Mineralising film is placed in deionized water；Then dried process obtains strontium carbonate modified fibroin composite.
2. the preparation method of strontium carbonate modified fibroin composite according to claim 1, it is characterised in that：The silk is
One or more in mulberry silk, tussah silk, ricinus silk.
3. the preparation method of strontium carbonate modified fibroin composite according to claim 1, it is characterised in that：The strontium chloride
In formic acid solution, strontium chloride concentration is 1-5wt%；In the silk fibroin protein solution, fibroin albumen concentration is 10-20wt%.
4. the preparation method of strontium carbonate modified fibroin composite according to claim 1, it is characterised in that：At the mineralising
The temperature of reason is 40~60 DEG C, and the time is 40~60 hours；The relative humidity of the mineralising treatment is 40~60%.
5. the preparation method of strontium carbonate modified fibroin composite according to claim 1, it is characterised in that：Strontium chloride, silk
Fibroin, the mass ratio of macromolecular material are（5~8）∶80∶30.
6. the preparation method of strontium carbonate modified fibroin composite according to claim 1, it is characterised in that：Mineralising film is put
0.5~1 hour in deionized water；The dried process is that room temperature is placed 0.5 hour, and then 60 DEG C are heated 2 hours, last 90
DEG C heating 30~50 seconds.
7. the preparation method of strontium carbonate modified fibroin composite according to claim 1, it is characterised in that：The high score
The preparation method of sub- material is that trimethylene carbonate, acrylate trimethylolethane cyclic carbonate ester are dissolved in into dichloromethane
In, stir 8~15 minutes；It is subsequently adding trimethyl phosphite and double（Double trimethyl silicon substrates）The dichloromethane solution of amine zinc,
Stirring 20~35 minutes；Propilolic alcohol is subsequently adding, is stirred 30~45 minutes；Then reaction 40~55 hours is sealed in 40 DEG C, so
Glacial acetic acid terminating reaction is used afterwards, reaction solution is precipitated in ice ether, sediment vacuum drying is obtained into macromolecular material.
8. the preparation method of strontium carbonate modified fibroin composite according to claim 7, it is characterised in that：Trimethylene carbon
It is acid esters, acrylate trimethylolethane cyclic carbonate ester, trimethyl phosphite, double（Double trimethyl silicon substrates）Amine zinc, propilolic alcohol
Mass ratio be 100: 80: 20: 0.1:（5~8）；The concentration of the macromolecular material formic acid solution is 5~8wt%.
9. the carbonic acid that prepared by the preparation method of any one strontium carbonate modified fibroin composite according to claim 1-8
Strontium modified fibroin composite；The strontium carbonate exists with nano bar-shape, a diameter of 10~200 nm of strontium carbonate rod, a length of 10
~100 μm.
10. application of the strontium carbonate modified fibroin composite in bone renovating material is prepared described in claim 9.
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| CN107419350A (en) * | 2017-07-16 | 2017-12-01 | 长沙秋点兵信息科技有限公司 | Preparation method of silk fiber with good hygroscopicity |
| CN107419349A (en) * | 2017-07-16 | 2017-12-01 | 长沙秋点兵信息科技有限公司 | Process for preparing high-mechanical-property fabric from silk |
| CN108774807A (en) * | 2018-01-30 | 2018-11-09 | 苏州口腔医院有限公司 | A kind of fibroin fiber composite material and preparation method that mixing strontium and application |
| CN112452152A (en) * | 2020-11-17 | 2021-03-09 | 江苏通用环保集团有限公司 | Mineralized modified cellulose composite forward osmosis membrane material and preparation method thereof |
| CN116999614A (en) * | 2023-07-19 | 2023-11-07 | 江西理工大学 | A kind of SrCO3/polymer composite bone scaffold and preparation method |
| CN116999614B (en) * | 2023-07-19 | 2025-04-08 | 江西理工大学 | SrCO3Polymer composite bone scaffold and preparation method thereof |
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