CN112972766A - Silk fibroin-hydroxyapatite composite bone scaffold with high mechanical strength and preparation method thereof - Google Patents

Silk fibroin-hydroxyapatite composite bone scaffold with high mechanical strength and preparation method thereof Download PDF

Info

Publication number
CN112972766A
CN112972766A CN202110197499.XA CN202110197499A CN112972766A CN 112972766 A CN112972766 A CN 112972766A CN 202110197499 A CN202110197499 A CN 202110197499A CN 112972766 A CN112972766 A CN 112972766A
Authority
CN
China
Prior art keywords
hydroxyapatite
fibroin
solution
silk fibroin
composite bone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110197499.XA
Other languages
Chinese (zh)
Other versions
CN112972766B (en
Inventor
王卉
邵云菲
张克勤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN202110197499.XA priority Critical patent/CN112972766B/en
Publication of CN112972766A publication Critical patent/CN112972766A/en
Application granted granted Critical
Publication of CN112972766B publication Critical patent/CN112972766B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • A61L27/227—Other specific proteins or polypeptides not covered by A61L27/222, A61L27/225 or A61L27/24
    • 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
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention relates to a silk fibroin-hydroxyapatite composite bone scaffold with high mechanical strength and a preparation method thereof. The silk fibroin solution and the hydroxyapatite aqueous dispersion are subjected to ultrasonic action to form a mixed solution, and the silk fibroin/hydroxyapatite composite three-dimensional porous scaffold with high mechanical strength is rapidly and nontoxically prepared by a direct current directional electric field induction method.

Description

Silk fibroin-hydroxyapatite composite bone scaffold with high mechanical strength and preparation method thereof
Technical Field
The invention relates to the technical field of medical materials, in particular to a silk fibroin-hydroxyapatite composite bone scaffold with high mechanical strength and a preparation method thereof.
Background
Bone is the second commonly transplanted tissue worldwide, at least four million surgeries are performed each year, and bone defects bring great inconvenience to human body and life. Although bone has a certain ability to regenerate, in most cases, it is still necessary to improve the ability of bone to repair. Clinically, for the treatment of bone defects, autologous bone graft or allogeneic bone is commonly used, but there are problems of immune resistance, limited sources, and the like. In view of this, research has been made on bone tissue engineering scaffold materials that can mimic the structure and properties of natural bone. In recent years, people pay more and more attention to natural polymers due to better biocompatibility, multiple functionalities and the like, and silk fibroin is proved to have certain bone repair performance as a natural polymer with various advantages of biocompatibility, easiness in processing and molding, lower cost and the like.
Fibroin is a natural polymer material derived from silk, and is increasingly researched and applied in the field of bone tissue engineering. At present, compared with natural bone, the porous scaffold prepared from regenerated silk fibroin has poorer mechanical property and osteogenic property, and hydroxyapatite particles can be added to improve the defect so as to more effectively simulate the natural bone structure. Hydroxyapatite is a bioactive ceramic with a chemical composition and crystalline structure similar to the main constituent of inorganic substances in the human bone matrix. The previous research shows that the artificially synthesized hydroxyapatite has the same composition and similar structure as the hydroxyapatite in human skeleton, has no adverse reaction when implanted into human body, has good biocompatibility, and simultaneously shows certain osteogenic inductivity and osteoconductivity. Therefore, the scaffold with excellent mechanical property and bone repair property can be prepared by taking silk fibroin as a matrix and doping hydroxyapatite particles.
At present, the fibroin/hydroxyapatite composite bone scaffold is prepared mainly by two methods, namely, directly mechanically mixing fibroin and hydroxyapatite, and then preparing the composite bone scaffold by methods such as particle filtration, foaming, direct freeze drying and the like, and preparing a pure fibroin protein scaffold and introducing the hydroxyapatite by a biomimetic mineralization method. The preparation methods have multiple operation steps, and the obtained composite bone scaffold has poor mechanical properties and is not favorable for clinical use.
Disclosure of Invention
In order to solve the technical problems, the fibroin/hydroxyapatite composite bone scaffold is rapidly and nontoxically prepared by a direct current directional electric field induction method, the preparation period is short, the operation is simple, and the finally obtained scaffold has excellent and adjustable mechanical properties.
The invention aims to provide a preparation method of a silk fibroin-hydroxyapatite composite bone scaffold with high mechanical strength, which comprises the following steps:
s1, dispersing hydroxyapatite in water through ultrasonic action, adding a silk fibroin solution into the uniformly dispersed hydroxyapatite aqueous solution according to the mass ratio of the silk fibroin to the hydroxyapatite of 10: 0.5-5, and uniformly mixing by ultrasonic to obtain a silk fibroin/hydroxyapatite solution;
s2, inserting the two graphite plates into the silk fibroin/hydroxyapatite solution, respectively connecting the two graphite plates with the positive and negative electrodes of a direct-current power supply, performing directional electric field induction on the silk fibroin/hydroxyapatite solution to enable self-assembled nanoparticles in the silk fibroin solution to be aggregated into microparticles near the positive electrode plate, and wrapping hydroxyapatite in the microparticles to obtain the silk fibroin/hydroxyapatite composite gel;
s3, precooling the fibroin/hydroxyapatite composite gel, and freeze-drying to obtain the fibroin-hydroxyapatite composite bone scaffold.
Further, the directional electric field induction effect is to treat for 10-40 min under the voltage of 20-30V.
Further, the concentration of the silk fibroin solution is 5-10 wt%.
Further, the fibroin solution is prepared by the following method: degumming silkworm cocoons, washing with water, drying, dissolving in LiBr solution, filtering, dialyzing, and centrifuging to obtain fibroin solution.
Further, the degumming treatment is to place the silkworm cocoons into NaHCO with the weight of 0.1-1% w/v3Boiling the solution for 30-60 min.
Further, the concentration of the LiBr solution is 9-10 mol/L.
Further, the precooling is carried out for 10-20 h at the temperature of-10 to-30 ℃.
Further, the freeze drying is to freeze for 1-5 h at-80 ℃ and then freeze-dry by a freeze dryer.
The second purpose of the invention is to provide the silk fibroin-hydroxyapatite composite bone scaffold prepared by the method.
The third purpose of the invention is to provide the application of the silk fibroin-hydroxyapatite composite bone scaffold in the preparation of artificial bones.
By the scheme, the invention at least has the following advantages:
the method disclosed by the invention is simple to operate, short in preparation period, environment-friendly, safe and pollution-free, and the prepared fibroin/hydroxyapatite composite bone scaffold is excellent in mechanical property and can meet the clinical use requirements.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 is a schematic view of a fibroin/hydroxyapatite composite bone scaffold prepared under the action of an electric field;
FIG. 2 is an electron microscope image of two composite bone scaffolds;
FIG. 3 is an infrared representation of two composite bone scaffolds;
FIG. 4 is an XRD representation of two composite bone scaffolds;
FIG. 5 is a graph comparing the mechanical properties of two composite bone scaffolds;
fig. 6 is a graph comparing the mechanical properties of the electric field composite bone scaffold with a pine bone and silk fibroin/hydroxyapatite composite bone scaffold in the reference.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The method for testing the compression mechanical property of the composite bone scaffold comprises the following steps:
the stent was prepared in a cylindrical shape having dimensions of 10mm (diameter) × 8mm (height) with a polytetrafluoroethylene mold, and the sample was subjected to compression mechanical property test using a texture analyzer (TMS-PRO). The test speed was set at 10mm/min, the trigger force was 0.03N, the compression ratio was 80%, and three samples were tested per group.
Example 1:
according to the schematic diagram of fig. 1, a composite bone scaffold is prepared:
1. shearing silkworm cocoon into about 1cm2The cocoon sheets are prepared by weighing a certain amount of cocoon sheets and putting the cocoon sheets into a container containing 0.5% w/v NaHCO3Boiling the solution for 45min, washing the degummed silk with warm deionized water for 4-5 times, drying, dissolving the silk in 9.3mol/L LiBr solution, and dissolving for 1h at 60 ℃. Filtering, dialyzing, and centrifuging to obtain silk fibroin solution with final concentration of about 9 wt%.
2. Fibroin according to mass fraction: dispersing hydroxyapatite in certain water in a ratio of 10:2, adding fibroin, and ultrasonically mixing the two uniformly.
3. And (3) carrying out direct current directional electric field induction treatment (about 20-30 min) on the fibroin/hydroxyapatite solution under the voltage of 25V.
4. Taking out the fibroin/hydroxyapatite composite gel, standing at-20 deg.C overnight, freezing at-80 deg.C for 4 hr, and freeze-drying in a freeze-drying machine.
5. And taking out the freeze-dried scaffold to obtain the composite bone scaffold.
Example 2:
1. shearing silkworm cocoon into about 1cm2The cocoon sheets are prepared by weighing a certain amount of cocoon sheets and putting the cocoon sheets into a container containing 0.5% w/v NaHCO3Boiling the solution for 45min, washing the degummed silk with warm deionized water for 4-5 times, drying, dissolving the silk in 9.3mol/L LiBr solution, and dissolving for 1h at 60 ℃. Filtering, dialyzing, and centrifuging to obtain silk fibroin solution with final concentration of about 9 wt%.
2. Fibroin according to mass fraction: dispersing hydroxyapatite in certain water in a ratio of 10:1, adding fibroin, and ultrasonically mixing the two uniformly.
3. And (3) carrying out direct current directional electric field induction treatment (about 30-40 min) on the fibroin/hydroxyapatite solution under the voltage of 20V.
4. Taking out the fibroin/hydroxyapatite composite gel, standing at-20 deg.C overnight, freezing at-80 deg.C for 4 hr, and freeze-drying in a freeze-drying machine.
5. And taking out the freeze-dried scaffold to obtain the composite bone scaffold.
Example 3:
1. shearing silkworm cocoon into about 1cm2The cocoon sheets are prepared by weighing a certain amount of cocoon sheets and putting the cocoon sheets into a container containing 0.5% w/v NaHCO3Boiling the solution for 45min, washing the degummed silk with warm deionized water for 4-5 times, drying, dissolving the silk in 9.3mol/L LiBr solution, and dissolving for 1h at 60 ℃. Filtering, dialyzing, and centrifuging to obtain silk fibroin solution with final concentration of about 9 wt%.
2. Fibroin according to mass fraction: dispersing hydroxyapatite in certain water in a ratio of 10:3, adding fibroin, and ultrasonically mixing the two uniformly.
3. And (3) carrying out direct current directional electric field induction treatment (about 30-40 min) on the fibroin/hydroxyapatite solution under the voltage of 30V.
4. Taking out the fibroin/hydroxyapatite composite gel, standing at-20 deg.C overnight, freezing at-80 deg.C for 4 hr, and freeze-drying in a freeze-drying machine.
5. And taking out the freeze-dried scaffold to obtain the composite bone scaffold.
Comparative example 1:
1. shearing silkworm cocoon into about 1cm2The cocoon sheets are prepared by weighing a certain amount of cocoon sheets and putting the cocoon sheets into a container containing 0.5% w/v NaHCO3Boiling the solution for 45min, washing the degummed silk with warm deionized water for 4-5 times, drying, dissolving the silk in 9.3mol/L LiBr solution, and dissolving for 1h at 60 ℃. Filtering, dialyzing, and centrifuging to obtain silk fibroin solution with final concentration of about 9 wt%.
2. Fibroin according to mass fraction: firstly dispersing hydroxyapatite in a certain butanol solution, ultrasonically mixing uniformly, dropwise adding the mixture into a fibroin solution, and simultaneously mixing the solution uniformly.
3. And (3) putting the mixed solution at-20 ℃ overnight, freezing at-80 ℃ for 4h, and putting the frozen solution into a freeze dryer for freeze drying.
4. And taking out the freeze-dried scaffold to obtain the composite bone scaffold.
The composite bone scaffolds obtained in example 1 and comparative example 1 were compared in terms of performance, and the results were as follows:
fig. 2 is an electron micrograph of two composite bone scaffolds, showing that: the two kinds of composite bone scaffolds both present porous structures, and the butanol composite bone scaffold has uniform pore diameter and size of 50-100 μm. The aperture of the electric field composite bone scaffold is mostly concentrated in 0-50 μm, and some 200-300 μm macropores appear at the same time, thus showing a multi-stage porous structure.
Fig. 3 is an infrared characterization of two composite bone scaffolds, showing the results: the FTIR absorption peak of butanol composite bone scaffold material amide I mainly appears at 1621cm-1Here, it is shown that silk fibroin in butanol composite bone scaffold material is mainly beta-folded, and FTIR absorption peak of electric field composite bone scaffold material amide I mainly appears at 1637cm-1And (3) showing that the silk fibroin in the electric field composite bone scaffold material is mainly randomly coiled. The two kinds of composite bone supports are all 1030cm-1，600cm-1，560cm-1Has an absorption peak, which is related to PO in hydroxyapatite4 3-The groups are corresponding, which indicates that the hydroxyapatite is successfully compounded in the silk fibroin bracket.
Fig. 4 is an XRD characterization of two composite bone scaffolds, showing that: characteristic peaks appear at 26 degrees, 31.7 degrees, 33 degrees and 34 degrees of the composite bone scaffold prepared by two different methods, and respectively correspond to (002), (211), (300) and (202) crystal faces of hydroxyapatite. The results and infrared show that the silk fibroin/hydroxyapatite composite bone scaffold is successfully prepared by both methods.
Fig. 5 is a graph comparing the mechanical properties of two composite bone scaffolds, and the results show that: compared with the butanol composite bone scaffold, the compressive strength of the electric field composite bone scaffold is greatly improved.
Table 1 shows the maximum compressive strength and modulus of elasticity for two composite bone scaffolds, and the results show: compared with the butanol composite bone scaffold, the maximum compression strength and the elastic modulus of the electric field composite bone scaffold are greatly improved and respectively reach 14 times and 21 times of those of the butanol composite bone scaffold.
TABLE 1
Sample (I) Maximum compressive strength (MPa) Modulus of elasticity (MPa)
Butanol composite bone scaffold 1.75±0.18 1.35±0.17
Electric field composite bone support 24.66±0.88 28.91±3.19
Fig. 6 is a graph comparing the mechanical properties of electric field composite bone scaffolds with pine bone and some of the silk fibroin/hydroxyapatite composite bone scaffolds in the references, and the results show that: the mechanical property of the electric field composite bone scaffold is greatly improved compared with that of most references, and the mechanical property requirement of natural cancellous bone is met, so that the electric field composite bone scaffold can meet the clinical application and is an effective new strategy.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a silk fibroin-hydroxyapatite composite bone scaffold with high mechanical strength is characterized by comprising the following steps:
s1, dispersing hydroxyapatite in water through ultrasonic action, adding a silk fibroin solution into the uniformly dispersed hydroxyapatite aqueous solution according to the mass ratio of the silk fibroin to the hydroxyapatite of 10: 0.5-5, and uniformly mixing by ultrasonic to obtain a silk fibroin/hydroxyapatite solution;
s2, inserting the two graphite plates into the fibroin/hydroxyapatite solution, respectively connecting the graphite plates with the positive and negative electrodes of a direct-current power supply, performing directional electric field induction on the fibroin/hydroxyapatite solution to enable self-assembled nanoparticles in the fibroin solution to be aggregated into microparticles near the positive electrode plate, and wrapping hydroxyapatite in the microparticles to obtain fibroin/hydroxyapatite composite gel;
s3, precooling the fibroin/hydroxyapatite composite gel, and freeze-drying to obtain the fibroin-hydroxyapatite composite bone scaffold.
2. The method of claim 1, wherein the directional electric field induction is performed at a DC stabilization voltage of 20-30V for 10-40 min.
3. The method as claimed in claim 1, wherein the concentration of the silk fibroin solution is 5 to 10 wt%.
4. A method as claimed in claim 3, wherein the fibroin solution is prepared by: degumming silkworm cocoons, washing with water, drying, dissolving in LiBr solution, filtering, dialyzing, and centrifuging to obtain fibroin solution.
5. The method of claim 4, wherein the degumming treatment comprises placing the silkworm cocoons in a concentration of 0.1-1% w/v NaHCO3Boiling the solution for 30-60 min.
6. The method according to claim 4, wherein the concentration of the LiBr solution is 9-10 mol/L.
7. The method according to claim 1, wherein the pre-cooling is performed at-10 to-30 ℃ for 10 to 20 hours.
8. The method according to claim 1, wherein the freeze-drying is freeze-drying by a freeze-dryer after freezing at-80 ℃ for 1-5 h.
9. The silk fibroin-hydroxyapatite composite bone scaffold prepared by the method of any one of claims 1 to 8.
10. Use of the silk fibroin-hydroxyapatite composite bone scaffold of claim 9 for the preparation of an artificial bone.
CN202110197499.XA 2021-02-22 2021-02-22 Silk fibroin-hydroxyapatite composite bone scaffold with high mechanical strength and preparation method thereof Active CN112972766B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110197499.XA CN112972766B (en) 2021-02-22 2021-02-22 Silk fibroin-hydroxyapatite composite bone scaffold with high mechanical strength and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110197499.XA CN112972766B (en) 2021-02-22 2021-02-22 Silk fibroin-hydroxyapatite composite bone scaffold with high mechanical strength and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112972766A true CN112972766A (en) 2021-06-18
CN112972766B CN112972766B (en) 2023-02-28

Family

ID=76349284

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110197499.XA Active CN112972766B (en) 2021-02-22 2021-02-22 Silk fibroin-hydroxyapatite composite bone scaffold with high mechanical strength and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112972766B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023134090A1 (en) * 2022-01-13 2023-07-20 Shenzhen Institute Of Advanced Technology Use of a neuropeptide in treating bone-injury disease

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110171239A1 (en) * 2008-09-26 2011-07-14 Trustees Of Tufts College pH INDUCED SILK GELS AND USES THEREOF
CN106866996A (en) * 2017-03-13 2017-06-20 武汉纺织大学 A kind of fast preparation method of silk fibroin matter gel
CN107761148A (en) * 2016-08-22 2018-03-06 张贞 A kind of method that fibroin albumen hydroxyapatite coating layer is prepared in metal surface
CN110917400A (en) * 2019-12-05 2020-03-27 中山大学 Nano-hybrid silk fibroin hydrogel and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110171239A1 (en) * 2008-09-26 2011-07-14 Trustees Of Tufts College pH INDUCED SILK GELS AND USES THEREOF
CN107761148A (en) * 2016-08-22 2018-03-06 张贞 A kind of method that fibroin albumen hydroxyapatite coating layer is prepared in metal surface
CN106866996A (en) * 2017-03-13 2017-06-20 武汉纺织大学 A kind of fast preparation method of silk fibroin matter gel
CN110917400A (en) * 2019-12-05 2020-03-27 中山大学 Nano-hybrid silk fibroin hydrogel and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TUNA YUCEL等: ""Non-equilibrium silk fibroin adhesives"", 《JOURNAL OF STRUCTURAL BIOLOGY》 *
黄永利等: "电场调控载药丝素蛋白微球的制备", 《科学通报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023134090A1 (en) * 2022-01-13 2023-07-20 Shenzhen Institute Of Advanced Technology Use of a neuropeptide in treating bone-injury disease

Also Published As

Publication number Publication date
CN112972766B (en) 2023-02-28

Similar Documents

Publication Publication Date Title
EP1613796B1 (en) Concentrated aqueous silk fibroin solution and use thereof
CN106620839B (en) Scaffold material capable of promoting stem cell differentiation and preparation method and application thereof
CN107320787B (en) Porous fiber membrane material for periodontal repair and preparation method thereof
Lin et al. Characterization of electrospun nanofiber matrices made of collagen blends as potential skin substitutes
EP3011981A1 (en) A biomaterial scaffold for regenerating the oral mucosa
Sah et al. Preparation, characterization and in vitro study of biocompatible fibroin hydrogel
CN112972766B (en) Silk fibroin-hydroxyapatite composite bone scaffold with high mechanical strength and preparation method thereof
BR112016010360B1 (en) biomaterial having enhanced rubber properties through natural cross-linking of collagen and hyaluronic acid, method of preparing it, and method of using it
WO2019077312A1 (en) Single alpha chain collagens
DE102009037479A1 (en) Process for the preparation of a biocompatible and biodegradable composite material, the composite material available thereafter and its use as a medical device
CN110859992B (en) Bone repair material and preparation method thereof
JP5301565B2 (en) Biomaterial manufacturing method
CN111821513A (en) Composite hydrogel for promoting cartilage formation and preparation method and application thereof
Zhang et al. Facile preparation of mechanical reinforced and biocompatible silk gels
CN108478874B (en) Preparation method of hydroxyethyl chitosan nano composite bone scaffold material
CN103059274B (en) Aliphatic polyester/calcium carbonate composite material and its preparation method
CN114350162B (en) Gradient pore structure silk fibroin film and preparation method thereof
CN110354315B (en) Preparation method of three-dimensional porous antibacterial silk fibroin/graphene/titanium dioxide bone tissue engineering scaffold
Munadziroh et al. Physical Modification of Bovine Amniotic Membrane for Dental Application
Liu et al. Improvement of mechanical properties of zein porous scaffold by quenching/electrospun fiber reinforcement
CN113797395A (en) Nano hydroxyapatite/block copolymer composite material and preparation method thereof
CN109880152B (en) Preparation method of oriented communicated porous biomedical stent, stent prepared by preparation method and application of stent in preparation of medical products
CN110180024B (en) Composite stent and preparation method thereof
CN114870070A (en) Organic/inorganic composite three-dimensional porous nanofiber tissue engineering scaffold and preparation method and application thereof
Davoudi et al. Skin Tissue Engineering with Nanostructured Materials

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant