CN107185036B - Micro-nanofiber three-dimensional chitosan scaffold and preparation method thereof - Google Patents
Micro-nanofiber three-dimensional chitosan scaffold and preparation method thereof Download PDFInfo
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- CN107185036B CN107185036B CN201710434323.5A CN201710434323A CN107185036B CN 107185036 B CN107185036 B CN 107185036B CN 201710434323 A CN201710434323 A CN 201710434323A CN 107185036 B CN107185036 B CN 107185036B
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 43
- 239000002121 nanofiber Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 5
- 210000001519 tissue Anatomy 0.000 description 6
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000021164 cell adhesion Effects 0.000 description 2
- 230000024245 cell differentiation Effects 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 description 1
- 229920001287 Chondroitin sulfate Polymers 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical group O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229940059329 chondroitin sulfate Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002062 molecular scaffold Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000035755 proliferation 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
- A61L27/14—Macromolecular materials
- A61L27/20—Polysaccharides
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- 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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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Dispersion Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a micro-nanofiber three-dimensional chitosan scaffold and a preparation method thereof. The coexistence microstructure of the micro-nano fibers endows the scaffold with good biocompatibility and mechanical strength. The preparation method is simple in process, and compared with a chitosan bracket prepared by a traditional binary solvent, the chitosan bracket is typically characterized in that the chitosan bracket is microscopically in the form of micro-nano fibers.
Description
Technical Field
The invention relates to a micro-nanofiber three-dimensional chitosan scaffold and a preparation method thereof, belonging to the technical field of biomedical materials.
Background
The chitosan is a natural alkaline polysaccharide which has a structure similar to that of chondroitin sulfate in a human body, and the alkalinity brought by amino groups enables the chitosan to have the characteristics of antibiosis, antiphlogosis and the like. The tissue engineering scaffold prepared from chitosan has good mechanical properties and is beneficial to proliferation and differentiation of cells, so that the scaffold has important application in the field of tissue engineering materials. The common chitosan solvent is acetic acid water solution, and the prepared chitosan scaffold has a microstructure of several tens to hundreds of microns of sheet-shaped sponge with good mechanical strength and biological performance (Biomaterials, 1999;20: 1133-1142). Hutch and the like disclose a preparation method of a three-dimensional ordered porous chitosan scaffold material (CN 101366972), which can be used for repairing bone tissues. The chitosan scaffold has the disadvantage that the sheet-shaped microstructure thereof is not favorable for cell adhesion and penetration, which is very unfavorable for degradable tissue engineering scaffolds. Research shows that the nano fibrous scaffold has higher specific surface area and is beneficial to cell adhesion and differentiation. But the mechanical strength of the pure nano fiber is lower, and the mechanical load of the stent implantation process cannot be born. In contrast, the micron fiber scaffold has better mechanical properties. Thus, having a microstructure of both nano and micro fibers in the scaffold can overcome the contradiction between biocompatibility and mechanical properties. At present, researchers mostly adopt an electrostatic spinning method to prepare micro-nanofibers, and the method has the advantages that the diameter of the fibers can be controlled in a certain range, but the electrostatic spinning method can only obtain a two-dimensional film, and the preparation time is long. The traditional phase separation method for preparing the chitosan three-dimensional tissue engineering scaffold is generally a sheet-shaped honeycomb structure, and the dimension of the chitosan three-dimensional tissue engineering scaffold is usually dozens of micrometers. As the chitosan molecules have strong intermolecular force and have high viscosity after being dissolved in acid, the concentration of the chitosan needs to be very low for obtaining the micro-nano fiber structure, but the prepared scaffold has no mechanical strength and cannot be used as a tissue engineering scaffold.
Disclosure of Invention
The invention mainly assumes that a binary solvent system consisting of water and acetic acid in the traditional phase separation preparation method is changed, a novel ternary solvent system consisting of an organic solvent, the water and the acetic acid is added, the intermolecular force of chitosan is changed, and the chitosan is promoted to form micro-nano fibers in the freezing process, so that the micro-nano fiber three-dimensional chitosan scaffold is obtained.
The preparation method of the micro-nanofiber three-dimensional chitosan scaffold is specifically as follows.
(1) Preparing a ternary mixed solvent of acetic acid, tetrahydrofuran and water.
(2) Adding chitosan, and electromagnetically stirring to dissolve for 24 hours.
(3) And (4) after the solution is subjected to sample separation, placing the solution at low temperature for freezing and forming.
(4) And (5) freeze-drying for 48 hours by using a freeze dryer to obtain the micro-nanofiber three-dimensional chitosan scaffold.
The sample prepared by the method is in a white foam shape, and the three-dimensional shape of the sample can be adjusted by adopting different containers and sample dividing volumes in sample dividing. The coexistence microstructure of the micro-nano fibers endows the scaffold with good biocompatibility and mechanical strength. The preparation method has the advantages of simple process, low cost and good support formability. Compared with the chitosan scaffold prepared by the traditional binary solvent, the chitosan scaffold is characterized by showing the shape of micro-nano fibers on a microscopic scale.
Detailed Description
The present invention will be further described with reference to specific examples, but the implementation of the present invention is not limited to these examples.
Example 1: 1ml, 5ml and 94ml of acetic acid, tetrahydrofuran and water are respectively taken and mixed evenly. 0.5g of chitosan with the molecular weight of 10 ten thousand is weighed and dissolved for 24 hours by electromagnetic stirring. After the chitosan is completely dissolved, the chitosan solution is sampled into a container, the container is frozen at the temperature of minus 80 ℃ for more than 12 hours for forming, and the micro-nanofiber three-dimensional chitosan scaffold can be obtained after the micro-nanofiber three-dimensional chitosan scaffold is freeze-dried in a freeze dryer for 48 hours.
Example 2: respectively taking 10ml, 20ml and 70ml of acetic acid, tetrahydrofuran and water, and uniformly mixing. 3g of chitosan with the molecular weight of 40 ten thousand is weighed and dissolved for 24 hours by electromagnetic stirring. After the chitosan is completely dissolved, the chitosan solution is divided into samples and put into a container, the samples are frozen and molded under the temperature of-196 ℃ (in liquid nitrogen), and the samples are frozen and molded in a freeze dryer for 48 hours to obtain the micro-nanofiber three-dimensional chitosan scaffold.
Claims (4)
1. A preparation method of a micro-nanofiber three-dimensional chitosan scaffold is characterized by dissolving chitosan in a ternary mixed solvent of acetic acid, tetrahydrofuran and water, carrying out sample separation, carrying out freeze forming at a certain temperature, and carrying out freeze drying in a freeze dryer to obtain the micro-nanofiber three-dimensional chitosan scaffold.
2. The method for preparing the micro-nanofiber three-dimensional chitosan scaffold according to claim 1, wherein the molecular weight of the chitosan is 10-40 ten thousand, and the mass volume concentration of the chitosan is 0.5-3%.
3. The preparation method of the micro-nanofiber three-dimensional chitosan scaffold as claimed in claim 1, wherein the volume ratio of acetic acid in the ternary mixed solvent is between 1 and 10%, the volume ratio of tetrahydrofuran is between 5 and 20%, and the volume ratio of water is between 70 and 94%.
4. The method for preparing the micro-nanofiber three-dimensional chitosan scaffold according to claim 1, wherein the freezing forming temperature is between-80 ℃ and-196 ℃.
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CN107185036A CN107185036A (en) | 2017-09-22 |
CN107185036B true CN107185036B (en) | 2020-03-31 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102747453A (en) * | 2012-07-05 | 2012-10-24 | 四川大学 | Porous superfine polymer fiber and preparation method thereof |
CN103285424A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Three-dimensional fiber-based aerogel tissue engineering scaffold and preparation method thereof |
CN105641744A (en) * | 2016-02-27 | 2016-06-08 | 青岛大学 | Nano-micro multi-scale chitosan and polylactic acid composite scaffold and preparation method thereof |
WO2017075554A1 (en) * | 2015-10-29 | 2017-05-04 | Golfetto Michael | Methods freeze drying and composite materials |
-
2017
- 2017-06-09 CN CN201710434323.5A patent/CN107185036B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102747453A (en) * | 2012-07-05 | 2012-10-24 | 四川大学 | Porous superfine polymer fiber and preparation method thereof |
CN103285424A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Three-dimensional fiber-based aerogel tissue engineering scaffold and preparation method thereof |
WO2017075554A1 (en) * | 2015-10-29 | 2017-05-04 | Golfetto Michael | Methods freeze drying and composite materials |
CN105641744A (en) * | 2016-02-27 | 2016-06-08 | 青岛大学 | Nano-micro multi-scale chitosan and polylactic acid composite scaffold and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
添加剂聚乙二醇对壳聚糖超滤膜结构和性能的影响;刘强,孟范平,姚瑞华,张爱静;《膜科学与技术》;20100228;第24页左栏第1-3段、实验部分、讨论部分 * |
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