CN1844509A - Process for preparing porous fibroin protein materials - Google Patents
Process for preparing porous fibroin protein materials Download PDFInfo
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- CN1844509A CN1844509A CN 200610075675 CN200610075675A CN1844509A CN 1844509 A CN1844509 A CN 1844509A CN 200610075675 CN200610075675 CN 200610075675 CN 200610075675 A CN200610075675 A CN 200610075675A CN 1844509 A CN1844509 A CN 1844509A
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- solution
- fibroin
- porous
- protein materials
- water
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Abstract
This invention relates to a silk protein material with multi-holes structure preparation method, which belongs to the biological macromolecular material. Using CaCl2, water and ethanol solution as agents, their mol proportion is 1:8:2, dislysating to obtain the silk protein water solution. Under 100deg C disturbing the solution until its density is 1-600mg/ml, spinning the solution under 10-100deg C to obtain the silk protein material with multi-holes, this invention can be applied in the organization project frame, which has well application foreground.
Description
Technical field
The present invention relates to biomaterial for preparation has the new method of the porous fibroin protein materials of good biocompatibility.
Background technology
Just designed the device that first cover utilizes the injection of polymer solution under highfield, carries out spinning process as far back as Formhals in 1934, in recent years, owing to can preparing diameter effectively, it has caused that to several microns fiber people pay close attention to widely at tens nanometer.In the electrostatic spinning process, on polymer solution or melt, add the high-tension electricity of several thousand to several ten thousand volts, polymer solution or melt form the Talyor awl at spray orifice, the electric field tensile force that produces when high voltage electric field reaches certain value, after being enough to overcome the surface tension on drop surface, just can eject charged polymer solution or melt jet on the drop, this jet is further stretched in electric field then, the solvent of polymer solution jet is volatilization or melt rapid solidification fast, be collected at last on the receiver, form the fibrofelt of non-weaving cloth shape or the fiber structure of other shape.Because the product of electrostatic spinning has useful properties such as some are big such as the special list area, porosity height, therefore can be used for filtering material, aspects such as wound coating and tissue engineering bracket.
Fibroin albumen is one of component in the silk fiber, as natural biological albumen, except having excellent mechanical performance, also has excellent biological compatibility, low inflammatory reaction and favorable mechanical and physical and chemical performance are subjected to biomaterial circle extensive studies in recent years.At artificial skin, prosthetic ligament, the artifical bone, there is good prospects for application the artificial blood vessel aspect, and can be used as the medicament slow release material, enzyme immobilization material etc.In organizational project, its excellent cell growth property and slow degradability also make it be with a wide range of applications.
Organizational engineering is to utilize the principle of engineering science and life science and the emerging cross discipline that method is studied biological organic histoorgan or its function replacement thing.It integrates bioengineering, life science, Materials Science and Engineering and clinical medicine, and purpose is to repair and regeneration of damaged tissue or organ, helps patient to recover the function of damaged tissues, improves the quality of living.1987, U.S. natural science fund engineering council has proposed the definition of organizational engineering when investigation bioengineering prospect, promptly " principle of application project and biotics and method are understood institutional framework-function relationship of the mammal of normal and pathology; and develop biological tissue's substitute, and be used to repair, keep and improve the function of tissue ".The basic principle of organizational project and method are good and can progressively on the extracellular matrix of degraded and absorbed (ECM) material, be formed cell-biomaterial composites by human body with being adsorbed in a kind of biocompatibility after the amplification of the high concentration histocyte of in vitro culture.Because this material can be the three dimensions that cell provides existence, therefore help cell and obtain enough nutriments, carry out metabolism and make the three-dimensional rack growth of cell by prefabricated form.Behind this species complex implanting to human body desired area, the cell of plantation continues the hyperplasia breeding in the degraded and absorbed process of timbering material, form new respective organization with original specific function and form and organ, thereby can reach the purpose of repair tissue profile and reconstruction.
The verified support based on fibroin albumen may be widely used aspect reparation and the regenerating tissues.And that electrostatic spinning nonwoven fabric owing to have is beneficial to special list area that high-density cells and tissue cultivate is big and occupy the three-dimensional structure that porous is arranged, thereby be to be hopeful one of material forms that is applied to all kinds of organizational projects most, experimental results show that, compare with fibroin protein film, the fibroin fiber matrix more can promote the adhesion of cell.Current, be solvent or fibroin albumen and polyvinyl alcohol blending made the fibroin nonwoven fabric with hexafluoroisopropanol, Hexafluoro acetone, formic acid.
In existing electrostatic spinning fibroin albumen method, carry out electrostatic spinning with organic solvent and may cause dissolvent residual, residual solvent has cytotoxicity, and the fibration that may cause reaches the immune response with surrounding tissue; And being carried out electrostatic spinning, fibroin albumen and other polyblend also need the component of polymer in the product is got rid of complex operation.For fear of the problem and the simplification machine-shaping process of organic solvent residual, we have studied under suitable condition and directly the silk fibroin water solution electrostatic spinning have been prepared silk fibroin porous material, and have obtained success.
Summary of the invention:
The objective of the invention is in order to overcome the shortcoming that organic solvent residual in the common electrostatic spinning fibroin albumen preparation process reduces material biocompatibility and complex operation, water prepares the good porous fibroin protein materials of biocompatibility as the solvent of electrostatic spinning.
Technical scheme of the present invention is: the silk fibroin solution protein solution is stirred, make it be lower than 100 ℃ of transparent silk fibroin water solutions of high concentration that are concentrated into 1-600mg/ml, solution electrostatic spinning under 10-100 ℃, receiving range 1-100cm, voltage 50V-60KV is made porous fibroin protein materials.Utilize different receiving systems to obtain fibroin albumen nonwoven fabric, silk fibroin porous wall pipe and fiber and other material.
Specific implementation of the present invention is: with silk at 0.5% Na
2CO
3Boil 60min in the solution under 100 ℃ to remove the sericin of silk outside, the fibroin albumen after will coming unstuck repeatedly washs the back drying with distilled water, obtains pure fibroin albumen.A certain amount of fibroin albumen is dissolved in CaCl
2/ H
2O/CH
3CH
2In OH (mol ratio 1: 8: 2) ternary solution or other dense saline solution, in water dialysis three days removing calcium chloride and the ethanol in the solution, thereby filtering solution obtains pure silk fibroin water solution.This aqueous solution through stirring, is concentrated this solution in being lower than 100 ℃ scope, and obtaining concentration is the transparent high concentration silk fibroin water solution of 1-600mg/ml, and the purpose of stirring is to prevent that silk fibroin solution from solidifying in concentration process.Pour the clear solution of this high concentration into syringe, add the voltage of 50V-60KV at the syringe needle place, electrostatic spinning under 0-100 ℃, receiving range 1-100cm, receive, between syringe needle and receiving system, add the annex that changes electric-field intensity and shape with pole plate, metal bar, back and forth pass the metal bar of jet and rotation at a high speed or have the disk of sharp edges and metal framework to receive with insulator frame, make the fibroin albumen nonwoven fabric with good biocompatibility, the fibroin albumen tubing of tube wall porous and the fibroin fiber of orientation.
The fibroin porous structure material prepared with sem observation its microscopic appearance, and use Fourier transform infrared spectroscopy, X-ray diffraction, and differential scanning calorimetry is measured the structure of fibroin albumen in the material.Test result shows that fibroin albumen is mainly the random coil structure in the material, the dry state TENSILE STRENGTH is not less than 0.8MPa, elongation at break is greater than 0.8%, carry out with methyl alcohol that silk II structure increases after the post processing, material is water insoluble, the dry state TENSILE STRENGTH is greater than 1.5MPa, and elongation at break is not less than 1.6%.
Advantage of the present invention is: water can keep the fibroin albumen excellent biological compatibility as electrostatic spinning fibroin albumen solvent, and is safe, simplified preparation process simultaneously.So the application on biomedicine is significant and practical value to porous fibroin protein materials in the present invention.
The specific embodiment
Embodiment
Embodiment 1:
With silk at 0.5% Na
2CO
3100 ℃ are boiled 60min in the solution, carefully wash the back drying with the sericin of removing the silk outside and the fibroin albumen that will boil with distilled water, obtain pure fibroin albumen.1 gram fibroin albumen is dissolved in 10 milliliters CaCl
2In/water/ethanol (mol ratio 1: 8: the 2) ternary solution, this silk fibroin solution was dialysed three days in dialysis band bag, remove calcium chloride and ethanol in the solution, thereby obtain transparent silk fibroin solution.Pour solution into beaker, being lower than under 100 ℃ of water-bath heating states, use the agitator gentle agitation, volatilization concentrates.Solution concentration to 1mg/ml, is clear solution.Pour this concentrated solution into syringe subsequently, add 50V voltage at the syringe needle place, under 10 ℃, receiving range 1cm, receive with pole plate and can get the fibroin albumen nonwoven fabric, its thickness can be controlled by the spinning time.
Embodiment 2:
Prepare pure silk fibroin water solution shown in embodiment 1.
Pour solution into beaker, being lower than under 100 ℃ of water-bath heating states, use the agitator gentle agitation, volatilization concentrates.Solution concentration to 1mg/ml, is clear solution.Pour this concentrated solution into syringe subsequently, add 500V voltage at the syringe needle place, under 10 ℃, receiving range 1cm, receive the fibroin albumen tubing that can have the porous tube wall with the metal bar of different-diameter, pipe thickness can be controlled by the spinning time.
Embodiment 3:
Prepare pure silk fibroin water solution shown in embodiment 1.
Pour solution into beaker, being lower than under 100 ℃ of water-bath heating states, use the agitator gentle agitation, volatilization concentrates.Solution concentration to 200mg/ml, is clear solution.Pour this concentrated solution into syringe subsequently, add 20KV voltage, under 20 ℃, receiving range 1cm, receive the fibroin fiber that can have orientation with the metal bar of rotation at a high speed, the disk that sharp edges is arranged or metal framework at the syringe needle place.
Embodiment 4:
Prepare pure silk fibroin water solution shown in embodiment 1.
Pour solution into beaker, being lower than under 100 ℃ of water-bath heating states, use the agitator gentle agitation, volatilization concentrates.Solution concentration to 300mg/ml, is clear solution.Pour this concentrated solution into syringe subsequently, add 30V voltage at the syringe needle place, under 30 ℃, receiving range 1cm, between syringe needle and receiving system, add to change the annex of electric-field intensity and shape, and back and forth pass the fibroin fiber that jet can obtain being orientated with insulator frame.
Embodiment 5:
Prepare pure silk fibroin water solution shown in embodiment 1.
Pour solution into beaker, being lower than under 100 ℃ of water-bath heating states, use the agitator gentle agitation, volatilization concentrates.Solution concentration to 600mg/ml, is clear solution.Pour this concentrated solution into syringe subsequently, add 60KV voltage at the syringe needle place, under 100 ℃, receiving range 100cm, receive with pole plate and can get the fibroin albumen nonwoven fabric, its thickness can be controlled by the spinning time.
Embodiment 6:
Prepare pure silk fibroin water solution shown in embodiment 1.
Pour solution into beaker, being lower than under 100 ℃ of water-bath heating states, use the agitator gentle agitation, volatilization concentrates.Solution concentration to 500mg/ml, is clear solution.Pour this concentrated solution into syringe subsequently, add 50KV voltage at the syringe needle place, under 100 ℃, receiving range 90cm, receive the fibroin albumen tubing that can have the porous tube wall with the metal bar of different-diameter, pipe thickness can be controlled by the spinning time.
Embodiment 7:
Prepare pure silk fibroin water solution shown in embodiment 1.
Pour solution into beaker, being lower than under 100 ℃ of water-bath heating states, use the agitator gentle agitation, volatilization concentrates.Solution concentration to 400mg/ml, is clear solution.Pour this concentrated solution into syringe subsequently, add 40KV voltage, under 50 ℃, receiving range 60cm, receive the fibroin fiber that can have orientation with the metal bar of rotation at a high speed, the disk that sharp edges is arranged or metal framework at the syringe needle place.
Embodiment 8:
Prepare pure silk fibroin water solution shown in embodiment 1.
Pour solution into beaker, being lower than under 100 ℃ of water-bath heating states, use the agitator gentle agitation, volatilization concentrates.Solution concentration to 400mg/ml, is clear solution.Pour this concentrated solution into syringe subsequently, add 30KV voltage at the syringe needle place, under 25 ℃, receiving range 50cm, between syringe needle and receiving system, add to change the annex of electric-field intensity and shape, and back and forth pass the fibroin fiber that jet can obtain being orientated with insulator frame.
Embodiment 9:
The preparation fibroin material is shown in embodiment 1-8.
Resulting fibroin material is carried out surface treatment with plasma, further improve the growth of cell.
Claims (2)
1. the preparation method of a porous fibroin protein materials, it is characterized in that: the silk fibroin solution protein solution is stirred, make it be lower than 100 ℃ of transparent silk fibroin water solutions of high concentration that are concentrated into 1-600mg/ml, solution electrostatic spinning under 10-100 ℃, receiving range 1-100cm, voltage 50V-60KV is made porous fibroin protein materials, obtain fibroin albumen nonwoven fabric, silk fibroin porous wall pipe and fibrous material with different receiving systems.
2. the preparation method of a kind of porous fibroin protein materials as claimed in claim 1, it is characterized in that: receiving system can use pole plate, metal bar to receive, add the annex that changes electric-field intensity and shape between syringe needle and receiving system, back and forth passes the metal bar of jet and rotation at a high speed or has the disk of sharp edges and metal framework to receive with insulator frame.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610075675 CN1844509A (en) | 2006-04-18 | 2006-04-18 | Process for preparing porous fibroin protein materials |
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| CN 200610075675 CN1844509A (en) | 2006-04-18 | 2006-04-18 | Process for preparing porous fibroin protein materials |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011026323A1 (en) * | 2009-09-02 | 2011-03-10 | 南通大学 | Artificial neural implant prepared by electrostatic spinning, preparation method and special device therefor |
| CN106822992A (en) * | 2017-03-14 | 2017-06-13 | 张帆 | The preparation method of the implantation human body degradable biomaterial based on silk fibroin |
| CN111453760A (en) * | 2020-04-22 | 2020-07-28 | 安徽锦华氧化锌有限公司 | Preparation process of nano zinc oxide with antibacterial property |
-
2006
- 2006-04-18 CN CN 200610075675 patent/CN1844509A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011026323A1 (en) * | 2009-09-02 | 2011-03-10 | 南通大学 | Artificial neural implant prepared by electrostatic spinning, preparation method and special device therefor |
| GB2485252A (en) * | 2009-09-02 | 2012-05-09 | Nantong Universtiy | Artificial neural implant prepared by electrostatic spinning, preparation method and special device therefor |
| CN106822992A (en) * | 2017-03-14 | 2017-06-13 | 张帆 | The preparation method of the implantation human body degradable biomaterial based on silk fibroin |
| CN111453760A (en) * | 2020-04-22 | 2020-07-28 | 安徽锦华氧化锌有限公司 | Preparation process of nano zinc oxide with antibacterial property |
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