CN115748239A - Preparation method of high-strength and flexible hydroxyapatite-coated silicon dioxide composite fiber membrane - Google Patents
Preparation method of high-strength and flexible hydroxyapatite-coated silicon dioxide composite fiber membrane Download PDFInfo
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- CN115748239A CN115748239A CN202211579282.6A CN202211579282A CN115748239A CN 115748239 A CN115748239 A CN 115748239A CN 202211579282 A CN202211579282 A CN 202211579282A CN 115748239 A CN115748239 A CN 115748239A
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- fiber membrane
- hydroxyapatite
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- flexible
- silicon dioxide
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000012528 membrane Substances 0.000 title claims abstract description 81
- 239000000835 fiber Substances 0.000 title claims abstract description 68
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 57
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 18
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 20
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000005312 bioglass Substances 0.000 claims description 13
- 238000010041 electrostatic spinning Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 claims description 9
- 229940052299 calcium chloride dihydrate Drugs 0.000 claims description 9
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims description 9
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 9
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 9
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 229940073589 magnesium chloride anhydrous Drugs 0.000 claims description 4
- 229960002816 potassium chloride Drugs 0.000 claims description 4
- 229960002668 sodium chloride Drugs 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 230000002188 osteogenic effect Effects 0.000 abstract 1
- 238000009987 spinning Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 239000011550 stock solution Substances 0.000 description 11
- 210000000988 bone and bone Anatomy 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 210000000963 osteoblast Anatomy 0.000 description 6
- 230000033558 biomineral tissue development Effects 0.000 description 5
- 230000003592 biomimetic effect Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 102000005789 Vascular Endothelial Growth Factors Human genes 0.000 description 3
- 108010019530 Vascular Endothelial Growth Factors Proteins 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- -1 silicon ions Chemical class 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- 102000007350 Bone Morphogenetic Proteins Human genes 0.000 description 2
- 108010007726 Bone Morphogenetic Proteins Proteins 0.000 description 2
- 229920000249 biocompatible polymer Polymers 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 229940112869 bone morphogenetic protein Drugs 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000008279 sol Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 206010058314 Dysplasia Diseases 0.000 description 1
- 108010041308 Endothelial Growth Factors Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NGFMICBWJRZIBI-JZRPKSSGSA-N Salicin Natural products O([C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@H](CO)O1)c1c(CO)cccc1 NGFMICBWJRZIBI-JZRPKSSGSA-N 0.000 description 1
- 108010073929 Vascular Endothelial Growth Factor A Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NGFMICBWJRZIBI-UHFFFAOYSA-N alpha-salicin Natural products OC1C(O)C(O)C(CO)OC1OC1=CC=CC=C1CO NGFMICBWJRZIBI-UHFFFAOYSA-N 0.000 description 1
- 230000033115 angiogenesis Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004759 cyclic silanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 210000002889 endothelial cell Anatomy 0.000 description 1
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- 239000002360 explosive Substances 0.000 description 1
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- 210000002950 fibroblast Anatomy 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 210000003470 mitochondria Anatomy 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 210000003463 organelle Anatomy 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 230000004819 osteoinduction Effects 0.000 description 1
- 210000005259 peripheral blood Anatomy 0.000 description 1
- 239000011886 peripheral blood Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- NGFMICBWJRZIBI-UJPOAAIJSA-N salicin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=CC=C1CO NGFMICBWJRZIBI-UJPOAAIJSA-N 0.000 description 1
- 229940120668 salicin Drugs 0.000 description 1
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- 235000013619 trace mineral Nutrition 0.000 description 1
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- 230000029663 wound healing Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention belongs to the technical field of preparation of inorganic non-metallic materials, and provides a preparation method of a high-strength and flexible hydroxyapatite-coated silicon dioxide composite fiber membrane. The preparation method provided by the invention is safe and stable, HAs no pollution, easily obtained raw materials, easy operation, simple equipment and higher yield, and the process adopted in coating HA is mild and simple, so that the excellent mechanical property of the silicon dioxide fiber membrane can not be damaged, and the osteogenic activity of the obtained HA-coated silicon dioxide composite fiber membrane is improved on the basis of the high strength and flexibility of the original silicon dioxide fiber membrane.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic non-metallic materials, and particularly relates to an HA-coated silicon dioxide composite fiber membrane and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The silicon dioxide is a nontoxic, tasteless and pollution-free inorganic nonmetallic material widely distributed in nature, and has the advantages of good temperature resistance, excellent corrosion resistance,Low heat conductivity coefficient, good insulation property, stable chemical property and the like, and is widely applied in various fields. In biomedical applications, silica is also a biological material with great potential for development. When the silicon dioxide is degraded by contact with body fluid, a large amount of silicon ions are released, and the silicon dioxide is made of orthosilicic acid (Si (OH) 4 ) Exist in the form of (1). Silicon is an essential trace element in the normal growth and development of organisms and causes dysplasia in bone and cartilage when there is a long-term deficiency of salicin in the diet. In osteoblasts, the content of silicon is similar to that of magnesium and phosphorus, and the silicon is distributed in mitochondria or other organelles. The silicon ions released by the calcium silicate promote the expression of endothelial growth factor (VEGF) in the blood vessels of fibroblasts and endothelial cells, resulting in VEGF promoting the expression of Bone Morphogenetic Protein (BMP). Researchers have also found that silicon ions, in addition to promoting osteogenesis, also up-regulate vascular endothelial growth factor, thereby promoting angiogenesis.
The hydroxyapatite has good biocompatibility with hard tissues of human bodies, skin tissues, muscle tissues and the like, is safe and nontoxic when being implanted into the bodies, and can guide the growth of bones. I.e. new bone can climb along the surface of the implant or the inner through pores from the joint of the implant and the original bone. Due to the chemical composition and the appropriate porosity similar to those of natural bones, the material HAs good biocompatibility, osteoinductivity and osteoconductivity, stable chemical properties and high mechanical strength, can induce the formation of new capillaries, and HA is generally used as an ideal material for repairing biological bones to realize good combination with host bones and promote the generation of peripheral blood vessels.
The electrostatic spinning technology is a method for effectively preparing fiber materials, and has very high application prospects in the fields of energy, catalysis, filtration and biomedicine. The composite nanofiber prepared by electrostatic spinning has porosity and layering, and can improve the growth and invasion capacity and other performances of tissues. The electrostatic spinning technology is used for preparing inorganic fiber two-dimensional materials for biomedical engineering, and the inorganic fiber two-dimensional materials cannot be realized for most of biological ceramic materials because of the problems of complex process, low mechanical strength and the like.
Currently, some researchers in the world (Surrao, denver C, et al, ACTA BIOMATER,2012,8 (11), 3997-4006 liu, xingzhi, et al, biomaterials,2021,276, 121037) electrospinning biocompatible polymers to prepare bone repair scaffolds for biomaterial research, but these biocompatible polymers suffer from poor bioactivity, lack of promotion of osteo-induction, and too rapid degradation.
Disclosure of Invention
Aiming at the existing problems, the invention provides an HA-coated silicon dioxide composite fiber membrane and a preparation method and application thereof. The preparation method provided by the invention is safe and stable, HAs no pollution, easily obtained raw materials, easy operation, simple equipment and higher yield, and the prepared HA-coated silicon dioxide composite fiber membrane HAs excellent flexibility and strength and wide application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a method for preparing a high-strength and flexible hydroxyapatite-coated silica composite fiber membrane, comprising:
mixing SiO 2 Immersing the fiber membrane into 10 times of SBF mineralized liquid, standing in the presence of sodium bicarbonate, and washing after HA deposition is finished to obtain HA-coated SiO 2 A fibrous membrane;
the SBF mineralized liquid comprises: sodium chloride, potassium chloride, calcium chloride dihydrate, magnesium chloride hexahydrate and anhydrous sodium dihydrogen phosphate.
The silicon dioxide is a good target material combined with electrostatic spinning, and the silicon dioxide can be hydrolyzed and condensed by using an organic silicon monomer under certain conditions to generate spinnable silica sol, so that the use of spinning-aid polymers is reduced, and the deterioration of mechanical properties in the subsequent heat treatment process is avoided; secondly, the phase of the target product is amorphous silica, so that the problem of stress concentration caused by the generation of a crystalline phase is avoided, and the obtained silica fiber membrane has high strength and flexibility.
Therefore, on the basis of the high-strength and flexible silicon dioxide fibrous membrane, HA is coated on the silicon dioxide fibrous membrane by a biomimetic mineralization method, so that the defect of low biological activity of the silicon dioxide fibrous membrane is overcome, and the application prospect is exciting.
In a second aspect of the present invention, there is provided a hydroxyapatite-coated silica composite fibrous membrane prepared by the above method.
The invention has the advantages of
(1) The invention utilizes a biomimetic mineralization method to prepare the silica composite fiber membrane coated with HA on the basis of the flexible and high-strength silica fiber membrane, and firstly utilizes the spinnability of silica sol under certain hydrolysis conditions to prepare the high-strength and flexible silica fiber membrane; secondly, immersing the prepared fiber membrane into 10 times of SBF mineralized stock solution prepared in advance, adding a certain amount of sodium bicarbonate to destroy the metastable balance and promote the generation of calcium phosphate precipitate, and depositing a layer of clustered HA on the silicon dioxide fiber to obtain a silicon dioxide composite fiber membrane coated with the HA;
(2) The method optimizes the process parameters, and the obtained HA-coated silicon dioxide composite fiber membrane HAs excellent bioactivity on the basis of high flexibility and tensile strength under the optimized process parameter condition, so that the method HAs extremely high operability and practicability and widens the application of the HA-coated silicon dioxide composite fiber membrane in bone repair materials, drug carriers and wound healing;
(3) The method has the advantages of easily available raw materials and low cost; the equipment is simple and the operation is convenient; compared with the existing preparation method, the technical scheme of the application has the advantages that the environmental protection, stability and safety are improved, the used raw materials are non-toxic and pollution-free, the reaction can be carried out stably, explosive substances cannot be generated in the reaction process, toxic gas cannot be generated, the green production concept is met, and the preparation method has wide medical production prospect and practical application value.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, are included to provide a further understanding of the application, and the description of the exemplary embodiments and illustrations of the application are intended to explain the application and are not intended to limit the application.
FIG. 1 is a scanning electron micrograph of a bioglass fiber membrane prepared in examples 1,2,3 and 4 of the present invention.
FIG. 2 is a scanning electron micrograph of osteoblast adhesion of bioglass fiber membranes prepared in examples 1,2,3 and 4 of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
Aiming at the problems of the current HA/silica composite material introduced by the background technology, the invention provides a method for preparing a two-dimensional, flexible and high-strength HA-coated silica composite fiber membrane. According to the method, firstly, an organic silicon monomer is used as a silicon source, hydrolysis is carried out under a certain acidic condition, electrostatic spinning is carried out by utilizing the excellent spinnability of the organic silicon monomer, then the obtained silicon dioxide fiber film precursor is subjected to high-temperature heat treatment, and the silicon dioxide fiber film can be obtained after furnace cooling. Secondly, by utilizing the principle of biomimetic mineralization, the silicon dioxide fiber membrane is immersed into 10 times of SBF mineralization liquid, a precipitator is added to promote calcium phosphate to be separated out, and the HA-coated silicon dioxide composite fiber membrane is obtained after standing for a period of time.
Specifically, the method comprises the following specific steps:
s1, adding an organic silicon monomer into ethanol and uniformly mixing;
s2, adding acid into the solution obtained in the step S1 for hydrolysis reaction, and uniformly mixing to obtain bioglass sol;
s3, heating and evaporating the silica sol obtained in the step S2 to a proper viscosity;
s4, performing electrostatic spinning on the silica sol obtained in the step S3;
s5, performing electrostatic spinning in the step S4 to obtain SiO 2 Carrying out high-temperature treatment on the fiber film precursor to obtain a silicon dioxide fiber film;
s6, completely dissolving sodium chloride, potassium chloride, calcium chloride dihydrate, magnesium chloride hexahydrate and anhydrous sodium dihydrogen phosphate into deionized water in sequence, uniformly mixing, and preparing 10 times of SBF stock solution;
s7, adding a certain amount of sodium bicarbonate into the 10 times of SBF stock solution obtained in the S6 to obtain 10 times of SBF mineralized solution;
s8, siO obtained in the S5 2 Immersing the fiber membrane into 10 times of SBF mineralized liquid, and standing for 20 hours;
s9, coating the SiO of the HA in the S8 2 Washing the fiber membrane for multiple times to obtain HA-coated SiO 2 A fibrous membrane.
The possible principles of the method of the invention are as follows: the molar ratio of silicon to water in the organosilicon monomer is 1: about 2, a chain silane molecular structure shown in formula (1) can be formed during hydrolysis, and a ring molecule shown in formula (2) can be formed when the amount of the silicon source is far less than that of water. In the bioglass system, the molecular structure of chain silane is utilized to ensure that the silica sol has equivalent spinnability, so that a high-strength and flexible silica fiber membrane is prepared without depending on a spinning-aid polymer. Secondly, by utilizing the principle of biomimetic mineralization, a large amount of HA can be deposited under the favorable condition of high specific surface area of the original silicon dioxide fibrous membrane to simulate human bones to compound hydroxyapatite crystals by taking collagen fibers as templates, so that a cluster-shaped HA-coated silicon dioxide fibrous membrane two-dimensional flexible material is formed.
In some embodiments, in S1, tetraethoxysilane is selected as an organic silicon monomer, the raw material is green and non-toxic, the price is low, and the hydrolysate does not contain harmful components, so that the raw material is a good industrial raw material. Because the ethyl orthosilicate is insoluble in water, the amount of ethanol used is half the volume of the ethyl orthosilicate, which helps to dissolve the ethyl orthosilicate in water during the hydrolysis reaction.
In some embodiments, s2. The molar ratio of the amount of water contained in the acid solution to the ethyl orthosilicate is from 1.8 to 2.4. If the amount of water is too small, the hydrolytic polycondensation reaction is not carried out to a degree that sufficient chain silane molecules are formed to support the continuity of spinning; if the amount of water is too large, cyclic silane molecules are easily formed, and the spinnability is also reduced.
In some embodiments, S3. The mixture is evaporated to a viscosity of 1-10 Pa · s, and if the viscosity is less than the range, the jet continuity is not high, and a fiber membrane with better mechanical property cannot be obtained; if the viscosity is higher than this range, the degree of conversion of the sol into a gel becomes too large, and the spinnability is greatly reduced.
In some embodiments, if the voltage adopted in s4 is lower than 12Kv, the electric field force during spinning is too weak, and the efficiency is low; and if the pressure is higher than 20Kv, the stress of the system is unbalanced, and the spinning consistency is influenced.
In some embodiments, S5. The temperature of the medium-high temperature heat treatment is 600-800 ℃, and the obtained silica fiber membrane has better mechanical property at the temperature.
In some examples, the concentrations of sodium chloride, potassium chloride, calcium chloride dihydrate, magnesium chloride hexahydrate, and anhydrous sodium dihydrogen phosphate in s6. Were 1000,5,25,5,10mm, respectively, and the concentrations of the respective raw materials were ensured not to affect the dissolution from each other.
In some embodiments, in s7, the concentration of the sodium bicarbonate added is 5-50mM, and if the concentration is too low, the deposition of HA cannot be guaranteed; if the concentration is too high, the mineralized liquid immediately generates precipitation in the solution in a short time and does not cover the matrix.
In some embodiments, S8, the mass ratio of the added silica fiber membrane to the 10-fold SBF mineralized liquid is 0.001-0.01. If the amount of the mineralized liquid is too small, the deposited HA is insufficient; if the amount is too large, the mineralized liquid will be wasted. If the standing time is too short, the deposited HA is insufficient; too long a time will result in excessive deposition.
In some embodiments, the number of washes in s9. Is 3 each for deionized water and ethanol, and too few of a number of washes may result in ionic residues.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
(1) Adding 30ml of tetraethoxysilane into 30ml of absolute ethyl alcohol, and mixing and stirring for 20 minutes;
(2) 5ml of hydrochloric acid (0.01M) is dripped into the mixed solution, and the mixture is mixed and stirred for 20 minutes to obtain silica sol;
(3) Heating the obtained silica sol to 80 ℃ and evaporating the silica sol until the viscosity is 3Pa & s;
(4) Spinning the obtained spinning solution in an electrostatic spinning machine at the voltage of 18Kv and the speed of 0.0015mm/s and the working distance of 15cm;
(5) Treating the biological glass fiber film precursor obtained by spinning in a muffle furnace for 5 hours at the temperature of 600 ℃ to obtain a silicon dioxide fiber film;
(6) Completely dissolving 116.8860g of sodium chloride, 0.7456 g of potassium chloride, 7.3508g of calcium chloride dihydrate, 2.0330g of magnesium chloride hexahydrate and 2.3996g of anhydrous sodium dihydrogen phosphate into 2L of deionized water in sequence, and uniformly mixing to prepare 10 times of SBF stock solution;
(7) Adding 0.168g of sodium bicarbonate into 200ml of 10 times of SBF stock solution to obtain 10 times of SBF mineralized solution;
(8) Mixing 1gSiO 2 Immersing the fiber membrane into 10 times of SBF mineralized liquid, standing for 15 hours to obtain SiO coated with HA 2 A fibrous membrane;
(9) SiO to be coated with HA 2 The fiber membranes were washed 3 times each with deionized water and ethanol.
The scanning electron micrograph of the bioglass fiber membrane prepared in this example is shown in (1) of fig. 1.
The scanning electron micrograph of osteoblast adhesion of the bioglass fiber membrane prepared in this example is shown in (1) of FIG. 2.
From this, it is understood that the HA-coated silica composite fiber membrane obtained by the present invention HAs both excellent biological activity and high flexibility and tensile strength.
Example 2
(1) Adding 30ml of tetraethoxysilane into 30ml of absolute ethyl alcohol, and mixing and stirring for 20 minutes;
(2) 5ml of hydrochloric acid (0.02M) is dripped into the mixed solution, and the mixture is mixed and stirred for 20 minutes to obtain silica sol;
(3) Heating the obtained silica sol to 80 ℃ and evaporating the silica sol until the viscosity is 2.6 pas;
(4) Spinning the obtained spinning solution in an electrostatic spinning machine at the voltage of 18Kv, the speed of 0.0015mm/s and the working distance of 15cm;
(5) Treating the biological glass fiber membrane precursor obtained by spinning in a muffle furnace for 5 hours at the temperature of 600 ℃ to obtain a silicon dioxide fiber membrane;
(6) Completely dissolving 116.8860g of sodium chloride, 0.7456 g of potassium chloride, 7.3508g of calcium chloride dihydrate, 2.0330g of magnesium chloride hexahydrate and 2.3996g of anhydrous sodium dihydrogen phosphate into 2L of deionized water in sequence, and uniformly mixing to prepare 10 times of SBF stock solution;
(7) Adding 0.336g of sodium bicarbonate into 200ml of 10 times of SBF stock solution to obtain 10 times of SBF mineralized solution;
(8) 1gSiO 2 Immersing the fibrous membrane into 10 times of SBF mineralized liquid, standing for 15 hours to obtain SiO coated with HA 2 A fibrous membrane;
(9) SiO to be coated with HA 2 The fiber membranes were washed 3 times each with deionized water and ethanol.
The scanning electron micrograph of the bioglass fiber membrane prepared in this example is shown in (2) of fig. 1.
The scanning electron micrograph of osteoblast adhesion of the bioglass fiber membrane prepared in this example is shown in (2) of fig. 2.
Example 3
(1) Adding 30ml of tetraethoxysilane into 30ml of absolute ethyl alcohol, and mixing and stirring for 20 minutes;
(2) 5ml of hydrochloric acid (0.01M) is dripped into the mixed solution, and the mixture is mixed and stirred for 20 minutes to obtain silica sol;
(3) Heating the obtained silica sol to 80 ℃ and evaporating the silica sol until the viscosity is 6Pa & s;
(4) Spinning the obtained spinning solution in an electrostatic spinning machine at the voltage of 18Kv and the speed of 0.0015mm/s and the working distance of 15cm;
(5) Treating the biological glass fiber membrane precursor obtained by spinning in a muffle furnace for 5 hours at the temperature of 600 ℃ to obtain a silicon dioxide fiber membrane;
(6) Completely dissolving 116.8860g of sodium chloride, 0.7456 g of potassium chloride, 7.3508g of calcium chloride dihydrate, 2.0330g of magnesium chloride hexahydrate and 2.3996g of anhydrous sodium dihydrogen phosphate into 2L of deionized water in sequence, and uniformly mixing to prepare 10 times of SBF stock solution;
(7) Adding 0.504g of sodium bicarbonate into 200ml of 10 times of SBF stock solution to obtain 10 times of SBF mineralized solution;
(8) 1gSiO 2 Immersing the fibrous membrane into 10 times of SBF mineralized liquid, standing for 15 hours to obtain SiO coated with HA 2 A fibrous membrane;
(9) SiO to be coated with HA 2 The fiber membranes were washed 3 times each with deionized water and ethanol.
The scanning electron micrograph of the bioglass fiber membrane prepared in this example is shown in (3) of fig. 1.
The scanning electron micrograph of osteoblast adhesion of the bioglass fiber membrane prepared in this example is shown in (3) of fig. 2.
Example 4
(1) Adding 30ml of tetraethoxysilane into 30ml of absolute ethyl alcohol, and mixing and stirring for 20 minutes;
(2) 5ml of hydrochloric acid (0.015M) is taken and dripped into the mixed solution, and the mixture is mixed and stirred for 20 minutes to obtain silica sol;
(3) Heating the obtained silica sol to 80 ℃ and evaporating the silica sol until the viscosity is 5 Pa.s;
(4) Spinning the obtained spinning solution in an electrostatic spinning machine at the voltage of 18Kv and the speed of 0.0015mm/s and the working distance of 15cm;
(5) Treating the biological glass fiber membrane precursor obtained by spinning in a muffle furnace for 5 hours at the temperature of 600 ℃ to obtain a silicon dioxide fiber membrane;
(6) Completely dissolving 116.8860g of sodium chloride, 0.7456 g of potassium chloride, 7.3508g of calcium chloride dihydrate, 2.0330g of magnesium chloride hexahydrate and 2.3996g of anhydrous sodium dihydrogen phosphate into 2L of deionized water in sequence, and uniformly mixing to prepare 10 times of SBF stock solution;
(7) Adding 0.672g of sodium bicarbonate into 200ml of 10 times of SBF stock solution to obtain 10 times of SBF mineralized solution;
(8) 1gSiO 2 Immersing the fiber membrane into 10 times of SBF mineralized liquid, standing for 15 hours to obtain SiO coated with HA 2 A fibrous membrane;
(9) SiO to coat HA 2 The fibrous membrane was washed 3 times each with deionized water and ethanol.
The scanning electron micrograph of the bioglass fiber membrane prepared in this example is shown in (4) of fig. 1.
The scanning electron micrograph of the osteoblast adhesion of the bioglass fiber membrane prepared in this example is shown in (4) of fig. 2.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a high-strength and flexible hydroxyapatite-coated silicon dioxide composite fiber membrane is characterized by comprising the following steps:
mixing SiO 2 Immersing the fibrous membrane into 10 times of SBF mineralized liquid, standing in the presence of sodium bicarbonate, and washing after HA deposition is finished to obtain HA-coated SiO 2 A fibrous membrane;
the SBF mineralized liquid comprises: sodium chloride, potassium chloride, calcium chloride dihydrate, magnesium chloride hexahydrate and anhydrous sodium dihydrogen phosphate.
2. The method of preparing a high strength and flexible hydroxyapatite coated silica composite fiber membrane according to claim 1, wherein the SiO is 2 The mass ratio of the fiber membrane to the SBF mineralized liquid which is 10 times of the weight of the fiber membrane is 0.001-0.01.
3. The method for preparing a high-strength and flexible hydroxyapatite-coated silica composite fiber membrane according to claim 1, wherein the concentration of the sodium bicarbonate is 5 to 50mM.
4. The method for preparing a high-strength and flexible hydroxyapatite-coated silica composite fiber film according to claim 1, wherein the standing time is 12 to 36 hours.
5. The method for preparing a high-strength and flexible hydroxyapatite-coated silica composite fibrous membrane according to claim 1, wherein the washing is performed 3 times each of the deionized water and the ethanol.
6. The method for preparing a high-strength and flexible hydroxyapatite-coated silica composite fiber membrane according to claim 1, wherein the molar ratio of the sodium chloride, the potassium chloride, the calcium chloride dihydrate, the magnesium chloride hexahydrate, and the anhydrous sodium dihydrogen phosphate is 1000:5 to 10:25 to 30:5 to 10:10 to 15.
7. The method of preparing a high strength and flexible hydroxyapatite coated silica composite fiber membrane according to claim 1, wherein the SiO is 2 The preparation method of the fiber membrane comprises the following steps:
adding an organic silicon monomer into ethanol, and uniformly mixing to obtain an organic silicon alcohol solution;
adding acid into the organic silicon alcohol solution for hydrolysis reaction, and uniformly mixing to obtain silica sol;
heating and evaporating the silica sol until the viscosity is 1-10 Pa.s, and then carrying out electrostatic spinning to obtain SiO 2 A fiber film precursor;
subjecting the SiO 2 And carrying out high-temperature treatment on the fiber film precursor to obtain the silicon dioxide fiber film.
8. The method for preparing a high-strength and flexible hydroxyapatite-coated silica composite fiber membrane according to claim 1, wherein the voltage of the electrospinning is 12 to 20Kv;
or the temperature of the high-temperature heat treatment is 600-800 ℃.
9. A hydroxyapatite coated silica composite fibre membrane prepared by the method of any one of claims 1 to 8.
10. The hydroxyapatite-coated silica composite fibrous membrane according to claim 9, wherein the hydroxyapatite-coated silica composite fibrous membrane is used for preparing a bioglass fibrous membrane material.
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