CN104497327A - Fibroin hyaluronic acid composite membrane with hygroscopic property and without cross-linking agent and preparation - Google Patents
Fibroin hyaluronic acid composite membrane with hygroscopic property and without cross-linking agent and preparation Download PDFInfo
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- CN104497327A CN104497327A CN201410785771.6A CN201410785771A CN104497327A CN 104497327 A CN104497327 A CN 104497327A CN 201410785771 A CN201410785771 A CN 201410785771A CN 104497327 A CN104497327 A CN 104497327A
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Abstract
The invention relates to a fibroin hyaluronic acid composite membrane with hygroscopic property and without a cross-linking agent and a preparation method. The method comprises the following steps: firstly, preparing a silk fibroin water solution; then preparing a fibroin hyaluronic acid composite membrane; directly mixing the silk fibroin water solution with hyaluronic acid powder, so as to obtain a hyaluronic acid/silk fibroin mixed solution; pouring a certain amount of mixed solution into a vessel with a polystyrene base, standing and defoaming; and slowly drying the solution in a constant-temperature drying oven at 37 DEG C, so as to form a film. The prepared fibroin hyaluronic acid composite membrane has good structure stability; the thickness of the film is 0.1-0.2mm; the hygroscopic property is 50%; the tensile strength is 5.5MPa; and the elongation at break is 140%.
Description
Technical field
The present invention relates to a kind of preparation of fibroin hyaluronic acid composite membrane, be specifically related to a kind of to there is fibroin hyaluronic acid composite membrane that good absorptive cross-linking agent-free exists and preparation method thereof.The invention belongs to technical field of biological material, prepared material can be widely used in the soft tissue repair such as skin, blood vessel, periosteum.
Background technology
Silk fibroin and hyaluronic acid all belong to right source, and the two all has good biocompatibility, are widely used in the preparation of various tissue renovation material.Silk fibroin is a kind of protein, form primarily of aminoacid sequence, there is the several functions such as amino, carboxyl group, multiple secondary structure is formed under different conditions by hydrogen bond action, as random coil, alpha-helix, beta sheet etc., thus there is multiple different performance, therefore there is good workability and modified.Hyaluronic acid is a kind of acidic mucopolysaccharide, extensively exists in human body skin, has fabulous moisture-keeping function, is the best material of the occurring in nature moisture retention that finds at present, is called as desirable natural moisturizing factor.Therefore, in conjunction with the advantage of these two kinds of materials, can prepare and there is good structural stability and absorptive natural biologic material, for soft tissue repair.Because hyaluronic acid is soluble in water, current most fibroin hyaluronic acid composite all needs to use linking agent, as genipin, and carbodiimide etc.If a kind of method not using linking agent can be found, directly prepare constitutionally stable fibroin hyaluronic acid composite, for its application in technical field of biological material and industrialization, all there is very important effect.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of fibroin hyaluronic acid composite membrane and the preparation with the existence of water-absorbent cross-linking agent-free.
There is a preparation method for the fibroin hyaluronic acid composite membrane that water-absorbent cross-linking agent-free exists, it is characterized in that, comprise the steps:
(1) preparation of silk fibroin water solution: silk cocoon being put into mass percent concentration is stir in the sodium carbonate solution of 0.5%, boil the silk gum on 60 minutes removing silk cocoon surfaces, after washing with water, at 60 DEG C, drying prepares fibroin fiber, the fibroin fiber of drying is dissolved in a solvent, at 80 DEG C, be dissolved into silk fibroin protein solution, through dialysis, filter obtained silk fibroin water solution;
(2) preparation of fibroin hyaluronic acid composite membrane: directly silk fibroin water solution and hyaluronic acid powder are mixed to get hyaluronic acid/silk fibroin mixing solutions, then mixing solutions is poured in the vessel of polystyrene substrate with a certain amount of, standing and defoaming, is slowly dried to film in the thermostatic drying chamber then solution being placed in 37 DEG C.
Solvent in described step (1) is the one in calcium chloride/water/ethanol ternary solvent, lithium bromide water solution, nitrocalcite/methanol/water ternary solvent.
Hyaluronan molecule amount in described step (2) is 4000-10000 kDa.
Hyaluronic acid in described step (2) and silk fibroin quality are than being 0.5%-7%.
There is the fibroin hyaluronic acid composite membrane that water-absorbent cross-linking agent-free exists, it is characterized in that, prepare according to above-mentioned arbitrary described method; This composite membrane thickness reaches 0.1-0.2mm, and water-absorbent reaches 50%, and tensile strength reaches 5.5MPa, and elongation at break reaches 140%, and this material vascular endothelial growth factor release rate reached 1.5% in 1 hour, within 12 hours, reached 13%, reached 25% in 96 hours.
Material prepared by the present invention can be widely used in the soft tissue repair such as skin, blood vessel, periosteum.
Tool of the present invention has the following advantages: (1) preparation method is simple, easily realizes volume production; (2) do not use any linking agent in preparation process, preparing environment is the aqueous solution, and temperature is 37 DEG C, environmental protection; (3) do not use any aftertreatment technology after having prepared, save preparation cost; (4) the fibroin hyaluronic acid composite membrane that the method is prepared has good structural stability, water absorbing properties, mechanical property and medicine-releasing performance.
Accompanying drawing explanation
Accompanying drawing 1 is the scanning electron microscope (SEM) photograph of embodiment 2 fibroin hyaluronic acid composite membrane;
Accompanying drawing 2 is the infared spectrum of embodiment 2 fibroin hyaluronic acid composite membrane;
Accompanying drawing 3 is the VEGF release profiles of embodiment 2 fibroin hyaluronic acid composite membrane.
Embodiment
Below by way of specific embodiment, technical scheme of the present invention is further described.Following embodiment further illustrates of the present invention, and do not limit the scope of the invention.
embodiment 1:
The preparation of silk fibroin water solution: 40g silk cocoon being put into 8L mass percent concentration is stir in the sodium carbonate solution of 0.5%, boil the silk gum on 60 minutes removing silk cocoon surfaces, be soaked in distilled water again and repeatedly clean up, at 60 DEG C, drying prepares fibroin fiber, the fibroin fiber of drying being dissolved in mol ratio is in the calcium chloride/water/ethanol ternary solvent of 1:8:2, at 80 DEG C, stirring and dissolving becomes silk fibroin protein solution, obtains pure silk fibroin water solution through dialysis, filtering and impurity removing.
embodiment 2:
Step 1 as described in Example 1; Step 2: be 5% according to hyaluronic acid and fibroin mass ratio, the hyaluronic acid powder that the silk fibroin water solution directly step 1 obtained and molecular weight are 6kDa mixes, stir until obtain homogeneous hyaluronic acid/silk fibroin mixing solutions, mixing solutions 8mL being poured over diameter is in the vessel of polystyrene substrate of 5mm, standing and defoaming, then thermostatic drying chamber inner drying solution being placed in 37 DEG C becomes film, and the scanning electron microscope (SEM) photograph of gained fibroin hyaluronic acid composite membrane, infared spectrum and VEGF release profiles are respectively as accompanying drawing 1, accompanying drawing 2, accompanying drawing 3.Fibroin hyaluronic acid composite membrane has fine and close pattern, and do not observe the existence that is separated, its Stability Analysis of Structures is described, infared spectrum further demonstrate that it has stable beta sheet structure.This composite membrane of VEGF release profiles surface has slow VEGF release performance.In addition, after testing, thickness reaches about 0.2mm, and water-absorbent reaches about 50%, and tensile strength reaches about 5.5MPa, and elongation at break reaches about 140%.
embodiment 3:
Step 1 as described in Example 1; Step 2: be 0.5% according to hyaluronic acid and fibroin mass ratio, the hyaluronic acid powder that the silk fibroin water solution directly step 1 obtained and molecular weight are 10kDa mixes, stir until obtain homogeneous hyaluronic acid/silk fibroin mixing solutions, mixing solutions 8mL being poured over diameter is in the vessel of polystyrene substrate of 5mm, standing and defoaming, then thermostatic drying chamber inner drying solution being placed in 37 DEG C becomes film, obtains fibroin hyaluronic acid composite membrane.
embodiment 4:
Step 1 as described in Example 1; Step 2: be 7% according to hyaluronic acid and fibroin mass ratio, the hyaluronic acid powder that the silk fibroin water solution directly step 1 obtained and molecular weight are 4kDa mixes, stir until obtain homogeneous hyaluronic acid/silk fibroin mixing solutions, mixing solutions 8mL being poured over diameter is in the vessel of polystyrene substrate of 5mm, standing and defoaming, then thermostatic drying chamber inner drying solution being placed in 37 DEG C becomes film, obtains fibroin hyaluronic acid composite membrane.
embodiment 5:
Step 1 as described in Example 1; Step 2: be 5% according to hyaluronic acid and fibroin mass ratio, the hyaluronic acid powder that the silk fibroin water solution directly step 1 obtained and molecular weight are 4kDa mixes, stir until obtain homogeneous hyaluronic acid/silk fibroin mixing solutions, mixing solutions 10mL being poured over diameter is in the vessel of polystyrene substrate of 5mm, standing and defoaming, then thermostatic drying chamber inner drying solution being placed in 37 DEG C becomes film, obtains fibroin hyaluronic acid composite membrane.
Claims (5)
1. there is a preparation method for the fibroin hyaluronic acid composite membrane that water-absorbent cross-linking agent-free exists, it is characterized in that, comprise the steps:
(1) preparation of silk fibroin water solution: silk cocoon being put into mass percent concentration is stir in the sodium carbonate solution of 0.5%, boil the silk gum on 60 minutes removing silk cocoon surfaces, after washing with water, at 60 DEG C, drying prepares fibroin fiber, the fibroin fiber of drying is dissolved in a solvent, at 80 DEG C, be dissolved into silk fibroin protein solution, through dialysis, filter obtained silk fibroin water solution;
(2) preparation of fibroin hyaluronic acid composite membrane: directly silk fibroin water solution and hyaluronic acid powder are mixed to get hyaluronic acid/silk fibroin mixing solutions, then mixing solutions is poured in the vessel of polystyrene substrate with a certain amount of, standing and defoaming, is slowly dried to film in the thermostatic drying chamber then solution being placed in 37 DEG C.
2. there is the preparation method of the fibroin hyaluronic acid composite membrane that water-absorbent cross-linking agent-free exists as claimed in claim 1, it is characterized in that: the solvent in described step (1) is the one in calcium chloride/water/ethanol ternary solvent, lithium bromide water solution, nitrocalcite/methanol/water ternary solvent.
3. there is the preparation method of the fibroin hyaluronic acid composite membrane that water-absorbent cross-linking agent-free exists as claimed in claim 1, it is characterized in that: the hyaluronan molecule amount in described step (2) is 4000-10000 kDa.
4. there is the preparation method of the fibroin hyaluronic acid composite membrane that water-absorbent cross-linking agent-free exists as claimed in claim 1, it is characterized in that: the hyaluronic acid in described step (2) and silk fibroin quality are than being 0.5%-7%.
5. have the fibroin hyaluronic acid composite membrane that water-absorbent cross-linking agent-free exists, it is characterized in that, according to above-mentioned arbitrary claim, method prepares; This composite membrane thickness reaches 0.1-0.2mm, and water-absorbent reaches 50%, and tensile strength reaches 5.5MPa, and elongation at break reaches 140%, and this material vascular endothelial growth factor release rate reached 1.5% in 1 hour, within 12 hours, reached 13%, reached 25% in 96 hours.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106420371A (en) * | 2016-11-17 | 2017-02-22 | 温州医科大学 | Skin-care fibroin hydrogel and preparation method thereof |
| CN106983870A (en) * | 2017-06-04 | 2017-07-28 | 陈泽勇 | A kind of combination drug carrier and preparation method thereof |
| CN107778506A (en) * | 2017-11-23 | 2018-03-09 | 湖北工程学院 | A kind of degradable film material, its preparation method and application |
| CN108671133A (en) * | 2018-05-15 | 2018-10-19 | 苏州先蚕丝绸有限公司 | Functional natural silk breast patch |
| CN113522049A (en) * | 2021-07-15 | 2021-10-22 | 浙江理工大学桐乡研究院有限公司 | Method for concentrating silk fibroin solution by using selective permeation imbibition membrane |
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| CN101856510A (en) * | 2010-05-14 | 2010-10-13 | 浙江理工大学 | Preparation method of composite nano-fiber support material of silk fibroin and calcium silicate |
| CN103341209A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin nanofiber membrane and preparation method thereof |
| CN103341214A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin membrane and preparation method thereof |
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- 2014-12-18 CN CN201410785771.6A patent/CN104497327A/en active Pending
Patent Citations (3)
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| CN101856510A (en) * | 2010-05-14 | 2010-10-13 | 浙江理工大学 | Preparation method of composite nano-fiber support material of silk fibroin and calcium silicate |
| CN103341209A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin nanofiber membrane and preparation method thereof |
| CN103341214A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin membrane and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106420371A (en) * | 2016-11-17 | 2017-02-22 | 温州医科大学 | Skin-care fibroin hydrogel and preparation method thereof |
| CN106420371B (en) * | 2016-11-17 | 2020-08-07 | 温州医科大学 | Silk fibroin hydrogel for skin care and preparation method thereof |
| CN106983870A (en) * | 2017-06-04 | 2017-07-28 | 陈泽勇 | A kind of combination drug carrier and preparation method thereof |
| CN107778506A (en) * | 2017-11-23 | 2018-03-09 | 湖北工程学院 | A kind of degradable film material, its preparation method and application |
| CN107778506B (en) * | 2017-11-23 | 2020-06-30 | 湖北工程学院 | Degradable film material, preparation method and application thereof |
| CN108671133A (en) * | 2018-05-15 | 2018-10-19 | 苏州先蚕丝绸有限公司 | Functional natural silk breast patch |
| CN113522049A (en) * | 2021-07-15 | 2021-10-22 | 浙江理工大学桐乡研究院有限公司 | Method for concentrating silk fibroin solution by using selective permeation imbibition membrane |
| CN113522049B (en) * | 2021-07-15 | 2023-02-03 | 浙江理工大学桐乡研究院有限公司 | Method for concentrating silk fibroin solution by using selective permeation imbibition membrane |
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