CN112876711B - High-strength silk protein nanofiber membrane and preparation method thereof - Google Patents
High-strength silk protein nanofiber membrane and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-strength silk fibroin nanofiber membrane and a preparation method thereof, wherein a high-crystal silk fibroin nanofiber aqueous solution is freeze-dried to obtain silk fibroin nanofiber freeze-dried powder; dissolving in formic acid solution to obtain fibroin nanofiber formic acid solution, and volatilizing to form a membrane to obtain the fibroin nanofiber membrane. The high-crystal silk protein nanofiber adopted by the method has a beta-sheet crystallization structure and good stability, can still keep the original secondary structure and nanofiber morphology after being dissolved in formic acid, and greatly improves the tensile mechanical property of the prepared membrane material due to the optimization of non-covalent action. The invention realizes the transformation of mechanical properties from fragility to toughness through simple solvent conversion, shows high tensile mechanical strength in dry state and wet state, respectively reaches 69.2-76.9 MPa and 13.5-14.6 MPa, and is carried out at normal temperature and normal pressure, and the preparation method is simple and easy to implement.
Description
Technical Field
The invention belongs to the technical field of high-strength biological materials, and particularly relates to a high-strength silk protein nanofiber membrane and a preparation method thereof.
Background
High strength materials have been the focus of research in the field of materials due to their excellent properties and wide range of applications. The natural high-strength material is self-assembled into a complex micro-nano structure by optimizing the non-covalent action among components, so that the material has excellent performance. For example, cellulose in plants, chitin in arthropod bones, silk protein in animal silks, etc. all form nanofibers of different sizes, and form functional materials with high strength, rigidity, and toughness by optimizing non-covalent interactions such as hydrogen bonds, static electricity, hydrophobic interactions, etc. Therefore, the key step of forming the high-strength material is to regulate and control the supermolecular assembly of the nanofiber unit on the micro-nano scale.
Silk, as a typical natural high-strength material, has attracted a great deal of attention in the fields of textiles, regenerative medicine, intelligent industry, and the like. The silk protein can be prepared into various material forms, such as fibers, membranes, hydrogels, scaffolds, microspheres and the like, and can be widely applied to the fields of tissue engineering, flexible electronic devices, drug delivery and the like. However, unlike natural silk fibres, regenerated silk protein materials often suffer from a breakdown of the hierarchical structure, resulting in poor mechanical properties. Although researchers improve the performance of the regenerated silk protein material by regulating beta-sheet content, optimizing an orientation structure, preparing a composite material and other different methods, a certain mechanical improvement effect is achieved, the further improvement of the mechanical property is still limited by the lack of the nanofiber elements and the loss of an assembly structure.
In recent years, researchers have implemented the reconstitution of silk fibroin nanofibers by various strategies. However, complex and harsh preparation conditions, such as ethanol treatment and ultrasonic dispersion, limit the hierarchical structure assembly and further functional optimization thereof. Based on the application requirements in the biomedical field, the uniform and stable nano-fiber formed under the simulated natural conditions of normal temperature and pressure and the like is an ideal choice for obtaining a supermolecular structure with higher mechanical performance.
However, since the silk protein nanofibers have high charge density, effective non-covalent interaction between the nanofibers is inhibited, and the formed regenerated silk nanofiber membrane is fragile and fragile, and even cannot be measured by a traditional stretching model.
Disclosure of Invention
In view of the above, the present invention aims to provide a high-strength silk fibroin nanofiber membrane and a preparation method thereof, wherein the nanofiber membrane prepared by the method has high tensile strength.
The invention provides a preparation method of a high-strength silk protein nanofiber membrane, which comprises the following steps:
s1: freeze-drying the high-crystal silk fibroin nanofiber aqueous solution to obtain silk fibroin nanofiber freeze-dried powder; the crystallinity of silk protein fiber in the high-crystal silk protein nano fiber aqueous solution is more than or equal to 40 percent, the diameter is 10-30 nm, and the length is 200-2000 nm;
s2: dissolving the silk fibroin nanofiber freeze-dried powder in a formic acid solution to obtain a silk fibroin nanofiber formic acid solution;
s3: and volatilizing formic acid in the silk protein nanofiber formic acid solution to form a membrane, thereby obtaining the silk protein nanofiber membrane.
Preferably, in step S1, the high crystalline silk protein nanofiber aqueous solution is prepared according to the following method:
concentrating the fibroin aqueous solution to a first fibroin solution with the concentration of 8-12 wt%;
concentrating the first silk protein solution to a second silk protein solution with the concentration of 16-24%;
and adding water to dilute the second silk protein solution to the concentration of 0.01-4 wt%, and carrying out sealed incubation to obtain the high-crystal silk protein nanofiber solution.
Preferably, the concentration of the high crystal silk protein nanofiber aqueous solution is 0.01-4 wt%.
Preferably, in the step S2, the concentration of the silk fibroin nanofiber formic acid solution is 1-20 wt%.
Preferably, in the step S2, the dissolving time is 0.1 to 24 hours.
Preferably, in the step S2, the dissolving temperature is 4 to 80 ℃.
Preferably, in the step S3, the film forming temperature is 4 to 60 ℃.
Preferably, in the step S3, the film forming time is 2 to 72 hours.
The invention provides a high-strength silk protein nanofiber membrane prepared by the preparation method of the technical scheme.
The high-crystal silk protein nanofiber adopted by the method provided by the invention has a beta-sheet crystal structure and good stability, can still keep the original secondary structure and nanofiber appearance after being dissolved in formic acid, and greatly improves the tensile mechanical property of the prepared membrane material due to the optimization of non-covalent action. The invention realizes the transformation of mechanical properties from brittleness to toughness through simple solvent transformation, shows high tensile mechanical strength in dry state and wet state, reaches 69.2-76.9 MPa and 13.5-14.6 MPa respectively, and is carried out at normal temperature and normal pressure, and the preparation method is simple and easy to implement.
Drawings
FIG. 1 is an atomic force microscope photograph showing the silk fibroin nanofibers prepared in example 1 of the present invention dissolved in water (a) and formic acid (b), respectively;
FIG. 2 is a digital photograph of the silk fibroin nanofiber aqueous solution (a) and the silk fibroin nanofiber formic acid solution (b) prepared in example 1 of the present invention, respectively cast into films;
FIG. 3 is an infrared spectrum of the aqueous solution film of silk protein nanofiber (SNF-H2O) and the formic acid film of silk protein nanofiber (SNF-FA) prepared in example 1 of the present invention;
fig. 4 is a stress-strain curve diagram of the silk protein nanofiber membrane prepared in example 1 of the present invention in dry and wet states.
Detailed Description
The invention provides a preparation method of a high-strength silk protein nanofiber membrane, which comprises the following steps:
s1: freeze-drying the high-crystal silk fibroin nanofiber aqueous solution to obtain silk fibroin nanofiber freeze-dried powder; the crystallinity of silk protein fiber in the high-crystal silk protein nano fiber aqueous solution is more than or equal to 40 percent, the diameter is 10-30 nm, and the length is 200-2000 nm;
s2: dissolving the silk fibroin nanofiber freeze-dried powder in a formic acid solution to obtain a silk fibroin nanofiber formic acid solution;
s3: and volatilizing formic acid in the silk protein nanofiber formic acid solution to form a membrane, thus obtaining the silk protein nanofiber membrane.
The high-crystal silk protein nanofiber adopted by the method provided by the invention has a beta-sheet crystal structure and good stability, can still keep the original secondary structure and nanofiber appearance after being dissolved in formic acid, and greatly improves the tensile mechanical property of the prepared membrane material due to the optimization of non-covalent action. The invention realizes the transformation of mechanical property from fragility to toughness through simple solvent transformation, shows high tensile mechanical strength under dry state and wet state, respectively 76.9MPa and 14.6MPa, and is carried out at normal temperature and normal pressure, and the preparation method is simple and easy to implement. The method for reducing the charge repulsion force, optimizing the non-covalent effect and regulating the mechanical property by formic acid provides experimental basis for mechanical regulation of other materials, and can be widely applied to the field of high-strength material preparation.
The invention freezes the high crystal silk protein nano fiber water solution to obtain the silk protein nano fiber freeze-dried powder. In the present invention, the high crystalline silk protein nanofiber aqueous solution is preferably prepared according to the following method:
concentrating the fibroin aqueous solution to a first fibroin solution with the concentration of 8-12 wt%;
concentrating the first silk protein solution to a second silk protein solution with the concentration of 16-24%;
and adding water to dilute the second silk protein solution to a concentration of 0.01-4 wt%, and carrying out sealed incubation to obtain the high-crystal silk protein nanofiber solution.
In the invention, the concentration of the high-crystal silk protein nanofiber aqueous solution is 0.01-4%; in specific embodiments, the concentration of the high crystalline silk protein nanofiber aqueous solution is 0.5%, 1%, 2%, or 4%.
After obtaining the silk fibroin nanofiber freeze-dried powder, the silk fibroin nanofiber freeze-dried powder is dissolved in formic acid solution to obtain silk fibroin nanofiber formic acid solution. In the invention, the concentration of the silk fibroin nanofiber formic acid solution is 1-20 wt%. In specific embodiments, the concentration of the silk fibroin nanofiber formic acid solution is 4 wt%, 1 wt%, 2 wt%, or 10 wt%. The method adopts the amount of formic acid to regulate the concentration of the formic acid solution of the silk protein nanofibers, and further regulates the non-covalent interaction between the silk protein nanofibers to realize the conversion of the mechanical properties of the material, thereby obtaining the high-strength silk protein membrane material. The method for reducing the charge repulsion force, optimizing the non-covalent effect and regulating the mechanical property by formic acid provides an experimental basis for mechanical regulation of other materials, and can be widely applied to the field of preparation of high-strength materials.
In the invention, the dissolving temperature is 4-80 ℃, and the dissolving time is 0.1-24 h; in specific embodiments, the dissolution temperature is 60 ℃, 20 ℃, 4 ℃, 40 ℃ or 10 ℃; the time is 0.5h, 24h, 1h, 4h or 12 h. The preparation method realizes the transformation of mechanical properties from fragility to toughness through solvent conversion, can be carried out at normal temperature and normal pressure, and is simple and easy to implement.
After obtaining the silk fibroin nano fiber formic acid solution, the invention volatilizes formic acid in the silk fibroin nano fiber formic acid solution into a film to obtain the silk fibroin nano fiber film.
In the invention, the film forming temperature is 4-60 ℃; the film forming time is 2-72 h; in specific embodiments, the film forming temperature is 60 ℃, 40 ℃, 30 ℃ or 20 ℃; the time is 2h, 4h, 24h, 48 or 72 h.
The invention provides a high-strength silk protein nanofiber membrane prepared by the preparation method of the technical scheme.
The thickness of the high-strength silk protein nanofiber membrane is 33 μm, 35 μm, 40 μm, 38 μm or 30 μm.
The invention adopts the following method to test the tensile strength of the high-strength silk protein nanometer:
the test was carried out using a universal tester (Instron 5967, sample length: 20 mm; tensile speed: 10mm/min) at 25. + -. 0.5 ℃ and a relative humidity of 60. + -. 5%. The samples were equilibrated in a constant temperature and humidity chamber (25. + -. 0.5 ℃ C., 60. + -. 5% humidity) for 24 hours in the dry state, soaked in 0.01M phosphate-buffered saline (PBS) for 1 hour in the wet state, and then the mechanical properties were measured.
In order to further illustrate the present invention, the following examples are provided to describe a high strength silk protein nanofiber membrane and a method for preparing the same in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Freeze-drying 0.5% silk fibroin nanofiber aqueous solution to obtain silk fibroin nanofiber freeze-dried powder;
(2) dissolving the silk fibroin nanofiber freeze-dried powder in a formic acid solution at 60 ℃ for 0.5h to obtain a 10% silk fibroin nanofiber formic acid solution;
(3) volatilizing the solvent formic acid for 2h at 60 ℃ by using 10% silk protein nanofiber formic acid solution to prepare the silk protein nanofiber membrane with the thickness of 30 microns.
FIG. 1 is an atomic force microscope photograph showing the silk fibroin nanofibers prepared in example 1 of the present invention dissolved in water (a) and formic acid (b), respectively; as can be seen from fig. 1: the silk fibroin in the formic acid solution in the aqueous solution is in the shape of the nanofiber; the length of the nano-fibers in the aqueous solution is distributed in the range of 200-1000 nm, the length of the nano-fibers in the formic acid is reduced to 50-200 nm, and the shorter fiber length provides more opportunities for interaction among the fibers.
Fig. 2 is a digital photograph of the silk fibroin nanofiber aqueous solution (a) and the silk fibroin nanofiber formic acid solution (b) prepared in example 1 of the present invention, which are respectively cast into films, wherein the silk fibroin film prepared in the aqueous solution system is very broken, but the silk fibroin film prepared in the formic acid system shows an intact morphology, indicating that the enhancement of the non-covalent effect between nanofibers reverses the film-forming property of the film.
FIG. 3 shows a silk fibroin nanofiber aqueous solution film (SNF-H) prepared in example 1 of the present invention2O) andan infrared spectrum of a silk protein nanofiber formate membrane (SNF-FA); as can be seen from fig. 3: both membranes have beta-sheet secondary structures, and stable fiber units are provided for realizing supramolecular assembly;
FIG. 4 is a stress-strain curve of a Silk Fibroin nanofiber membrane prepared in example 1 of the present invention in dry and wet states, and a control group is a conventional Silk Fibroin membrane (SF-MA) treated with methanol, and the preparation method is shown in Flexibility Regeneration of Silk fiber in Vitro (Biomacromolecules 2012,13, 2148-2153); as can be seen from fig. 4: the silk protein nanofiber membrane provided by the invention shows high tensile mechanical strength under dry state and wet state, and the tensile mechanical strength is 76.9MPa and 14.6MPa respectively.
TABLE 1 Zeta potential values of the films prepared in example 1
As can be seen from table 1: after the nanofibers are dissolved in formic acid, the zeta potential is changed from-35.1 mV to 9.0mV, and the decrease of the absolute value of the potential shows the decrease of the charge repulsion force, which is beneficial to the promotion of the non-covalent interaction between the nanofibers.
Example 2:
(1) freeze-drying the 2% silk fibroin nanofiber aqueous solution to obtain silk fibroin nanofiber freeze-dried powder;
(2) dissolving the silk fibroin nanofiber freeze-dried powder in a formic acid solution at 20 ℃ for 1h to obtain a 2% silk fibroin nanofiber formic acid solution;
(3) volatilizing the solvent formic acid for 72h at 20 ℃ by using a 2% silk protein nanofiber formic acid solution to prepare a silk protein nanofiber membrane with the thickness of 38 mu m.
The tensile mechanical strength of the silk protein nanofiber membrane prepared in example 2 in dry state and wet state is 69.2MPa and 13.5MPa respectively.
Example 3:
(1) freeze-drying the 2% silk fibroin nanofiber aqueous solution to obtain silk fibroin nanofiber freeze-dried powder;
(2) dissolving the fibroin nanofiber freeze-dried powder in formic acid solution at 4 ℃ for 24h to obtain 2% fibroin nanofiber formic acid solution;
(3) volatilizing the solvent formic acid for 48h at 30 ℃ by using a 2% silk protein nanofiber formic acid solution to prepare the silk protein nanofiber membrane with the thickness of 40 mu m.
The tensile mechanical strength of the silk protein nanofiber membrane prepared in example 3 in dry state and wet state is 72.5MPa and 14.0MPa respectively.
Example 4:
(1) freeze-drying 4% silk protein nano-fiber water solution to obtain silk protein nano-fiber freeze-dried powder;
(2) dissolving the silk fibroin nanofiber freeze-dried powder in a formic acid solution at 40 ℃ for 4 hours to obtain a 4% silk fibroin nanofiber formic acid solution;
(3) volatilizing the solvent formic acid for 24h at 40 ℃ by using a 4% silk protein nanofiber formic acid solution to prepare a silk protein nanofiber membrane with the thickness of 35 mu m.
The tensile mechanical strength of the silk protein nanofiber membrane prepared in example 4 in dry state and wet state is 76.5MPa and 13.7MPa respectively.
Example 5:
(1) freeze-drying 1% silk protein nanofiber aqueous solution to obtain silk protein nanofiber freeze-dried powder;
(2) dissolving the silk fibroin nanofiber freeze-dried powder in a formic acid solution at 10 ℃ for 12 hours to obtain a 1% silk fibroin nanofiber formic acid solution;
(3) volatilizing the solvent formic acid for 4h at 60 ℃ by using 1% silk protein nanofiber formic acid solution to prepare the silk protein nanofiber membrane with the thickness of 33 mu m.
The tensile mechanical strength of the silk protein nanofiber membrane prepared in example 5 in dry state and wet state was 75.8MPa and 14.0MPa, respectively.
From the above embodiments, the present invention provides a method for preparing a high-strength silk protein nanofiber membrane, comprising the following steps: s1: freeze-drying the high-crystal silk fibroin nanofiber aqueous solution to obtain silk fibroin nanofiber freeze-dried powder; the crystallinity of silk protein fiber in the high-crystal silk protein nano fiber aqueous solution is more than or equal to 40 percent, the diameter is 10-30 nm, and the length is 200-2000 nm; s2: dissolving the silk fibroin nanofiber freeze-dried powder in a formic acid solution to obtain a silk fibroin nanofiber formic acid solution; s3: and volatilizing formic acid in the silk protein nanofiber formic acid solution to form a membrane, thereby obtaining the silk protein nanofiber membrane. The high-crystal silk protein nanofiber adopted by the method provided by the invention has a beta-sheet crystal structure and good stability, can still keep the original secondary structure and nanofiber appearance after being dissolved in formic acid, and greatly improves the tensile mechanical property of the prepared membrane material due to the optimization of non-covalent action. The invention realizes the transformation of mechanical properties from brittleness to toughness through simple solvent transformation, shows high tensile mechanical strength in dry state and wet state, reaches 69.2-76.9 MPa and 13.5-14.6 MPa respectively, and is carried out at normal temperature and normal pressure, and the preparation method is simple and easy to implement. The method for reducing the charge repulsion force, optimizing the non-covalent effect and regulating the mechanical property by formic acid provides experimental basis for mechanical regulation of other materials, and can be widely applied to the field of high-strength material preparation.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (3)
1. A preparation method of a high-strength silk protein nanofiber membrane comprises the following steps:
s1: freeze-drying the high-crystal silk fibroin nanofiber aqueous solution to obtain silk fibroin nanofiber freeze-dried powder; the crystallinity of silk protein fiber in the high-crystal silk protein nano fiber aqueous solution is more than or equal to 40 percent, the diameter is 10-30 nm, and the length is 200-2000 nm;
in the step S1, the concentration of the high crystal silk protein nanofiber aqueous solution is 0.01-4 wt%;
s2: dissolving the silk fibroin nanofiber freeze-dried powder in a formic acid solution to obtain a silk fibroin nanofiber formic acid solution;
in the step S2, the concentration of the silk fibroin nanofiber formic acid solution is 1-20 wt%; the dissolving time is 0.1-24 h; the dissolving temperature is 4-80 ℃;
s3: volatilizing formic acid in the silk protein nanofiber formic acid solution to form a membrane to obtain a silk protein nanofiber membrane; the film forming temperature is 4-60 ℃; the film forming time is 2-72 h.
2. The method as claimed in claim 1, wherein in step S1, the aqueous solution of high crystalline silk protein nanofibers is prepared by the following method:
concentrating the fibroin aqueous solution to a first fibroin solution with the concentration of 8-12 wt%;
concentrating the first silk protein solution to a second silk protein solution with the concentration of 16-24%;
and adding water to dilute the second silk protein solution to a concentration of 0.01-4 wt%, and carrying out sealed incubation to obtain the high-crystal silk protein nanofiber solution.
3. A high-strength silk protein nanofiber membrane prepared by the preparation method of any one of claims 1-2.
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| WO2006130117A1 (en) * | 2005-06-03 | 2006-12-07 | National University Of Singapore | Novel polymer blends and applications for their use in hollow polymer fibers |
| CN106310349A (en) * | 2014-12-12 | 2017-01-11 | 苏州大学 | Regenerated fibroin protein gel mask |
| CN107080859A (en) * | 2017-05-02 | 2017-08-22 | 丝纳特（苏州）生物科技有限公司 | A kind of silk-fibroin sponge and preparation method thereof |
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| CN106928729B (en) * | 2017-03-27 | 2019-08-30 | 广西科技大学 | A kind of nanometer silver antimicrobial regenerated silk fibroin material and preparation method thereof |
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| WO2006130117A1 (en) * | 2005-06-03 | 2006-12-07 | National University Of Singapore | Novel polymer blends and applications for their use in hollow polymer fibers |
| CN106310349A (en) * | 2014-12-12 | 2017-01-11 | 苏州大学 | Regenerated fibroin protein gel mask |
| CN107080859A (en) * | 2017-05-02 | 2017-08-22 | 丝纳特（苏州）生物科技有限公司 | A kind of silk-fibroin sponge and preparation method thereof |
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