CN112280058A - Preparation method of fibrillated silk chitosan composite material - Google Patents
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Abstract
The invention provides a preparation method of a fibrillating fibroin chitosan composite material, which comprises the following steps: s1, preparing a chitosan solution: dissolving chitosan at a certain temperature by using low-concentration organic acid as a solvent to obtain a chitosan solution; s2, preparation of a fibroin solution: dissolving regenerated silk fibroin by using organic acid with a certain concentration as a solvent at a certain temperature to obtain a silk fibroin solution; s3, preparing a chitosan and fibroin mixed solution: adding high-concentration organic acid into the chitosan solution prepared in the step S1 to enable the organic acid content of the solution to reach the preset concentration, adding a proper amount of silk fibroin solution into the chitosan solution, and uniformly stirring and defoaming to obtain a mixed solution; s4, preparing a chitosan/silk fibroin material: preparing the mixed solution prepared in the step S3 into a specific shape, and then removing acid to obtain the chitosan/silk fibroin material. The silk fibroin chitosan material with a fibrillating structure is prepared by adjusting the adding mode of high-concentration acid and blending with fibroin.
Description
Technical Field
The invention relates to the technical field of chitosan material preparation, in particular to a preparation method of a fibrillating fibroin chitosan composite material.
Background
The chitosan is light yellow powder in a general state, and can be prepared into a semitransparent semicrystalline solid material after being dissolved and dried in dilute acid. As a safe, nontoxic and biodegradable natural high polymer, the macromolecular structure of the chitosan contains a large amount of free amino and hydroxyl active groups, and the groups can be combined with heavy metal ions, so that the effect of adsorbing the heavy metal ions in the solution is achieved, the chitosan is an excellent heavy metal adsorption raw material, and meanwhile, the chitosan has the advantages of low preparation cost, wide source, good heavy metal adsorption effect, greenness, no pollution and the like, and has attracted extensive attention of researchers.
In order to solve the problems of poor mechanical property of the chitosan material in a water absorption state, low material structure compactness and porosity, unstable adsorption effect in a slightly acidic environment and the like, researchers carry out a series of improvement and research on chitosan, and the improvement modes are roughly divided into two types: the chitosan is modified by physical or chemical means, and is blended and modified with the chitosan by adding specific substances.
The silk fibroin is one of two main components of silk, the outer part of the silk fibroin is wrapped by sericin, and insoluble silk fibroin is prepared by degumming treatment, wherein the content of the insoluble silk fibroin accounts for about 70% of the content of the silk. The silk fibroin which is a natural high molecular protein contains 18 amino acids such as alanine, glycine, serine and the like, and has the excellent characteristics of good biocompatibility, cell adhesion, reproducibility, safety, no toxicity, no body immunogen reaction, degradability, easy absorption and the like, so that the silk fibroin is widely developed and applied in the research field of biological medical materials (such as biological scaffolds, cell carriers and the like). The invention blends silk fibroin and chitosan, introduces natural high-molecular protein silk fibroin which is safe, nontoxic and biodegradable to carry out blending modification, and aims to solve the problems of poor wet mechanical strength, easy dissolution, high expansion degree and the like of chitosan.
Disclosure of Invention
The technical problem to be solved is as follows: the invention aims to provide a preparation method of a fibrillating fibroin chitosan composite material, wherein firstly, chitosan dissolution with dilute acid as a solvent is the first premise for preparing the chitosan material, but fibroin which is a reinforcing component can be gelled under the condition of too low acid concentration, so that the subsequent material preparation is not facilitated.
The technical scheme is as follows: a preparation method of a fibrillating fibroin chitosan composite material comprises the following steps:
s1 preparation of chitosan solution: dissolving chitosan at a certain temperature by using low-concentration organic acid as a solvent to obtain a chitosan solution;
s2 preparation of the fibroin solution: dissolving regenerated silk fibroin by using organic acid with a certain concentration as a solvent at a certain temperature to obtain a silk fibroin solution;
s3, preparing a chitosan and fibroin mixed solution: adding high-concentration organic acid into the chitosan solution prepared in the step S1 to enable the organic acid content of the solution to reach the preset concentration, adding a proper amount of silk fibroin solution into the chitosan solution, and uniformly stirring and defoaming to obtain a mixed solution;
s4, preparing a chitosan/silk fibroin material: preparing the mixed solution prepared in the step S3 into a specific shape, and then removing acid to obtain the chitosan/silk fibroin material.
Preferably, the organic acid in step S1 is aliphatic organic acid and aromatic organic acid, and the organic acid includes any one or a combination of two or more of mono-, di-or polycarboxylic acid.
Preferably, the organic acid in step S1 is one or a combination of two or more of formic acid, acetic acid, lactic acid and citric acid.
Preferably, the concentration of the low-concentration organic acid in step S1 is 1-10wt%, the temperature is 20-70 deg.C, and the concentration of the chitosan solution is 0.5-5 wt%.
Preferably, the organic acid in step S2 is formic acid, the concentration of formic acid is 80-100wt%, the temperature is 20-70 deg.C, and the concentration of fibroin solution is 1-30 wt%.
Preferably, the regenerated silk fibroin of step S2 is prepared by the following method:
s1, dissolving pure silk cellulose fibers in a CaCl 2/formic acid mixed solution to obtain a ternary solution;
s2, casting the ternary solution into a film, drying, and dialyzing to remove CaCl2 contained in the film to obtain the regenerated silk fibroin.
Preferably, the content of the organic acid in step S3 is 30-98%, and the mass ratio of the silk fibroin solution to the chitosan solution is 1-9: 9-1.
Preferably, the shape in step S4 comprises a fiber, a film, a three-dimensional scaffold, or a gel.
Has the advantages that: the silk fibroin chitosan material of the invention has the following advantages:
1. the invention firstly dissolves chitosan with dilute acid, and high-concentration acid is added for mixing after dissolution, the concentration of acid in the obtained chitosan solution system reaches a certain concentration, and silk fibroin can not be gelled when being blended with silk fibroin solution at a later stage, thereby being beneficial to the implementation of subsequent processes;
2. the composite material prepared by the invention has the advantages that the fibroin and the chitosan are uniformly blended, and the compatibility among the components is good; the chitosan composite membrane has an obvious vertical fibril structure, which is formed by self-assembly of fibroin short fibers in a formic acid-calcium chloride dissolving system, and shows the improvement effect of the addition of fibroin on the aspects of the mechanical property and the like of a chitosan membrane.
Drawings
FIG. 1 is a stress-strain curve of different concentrations of formic acid or acetic acid dissolved chitosan membrane;
FIG. 2 is a SEM of a formic acid-solubilized chitosan membrane;
FIG. 3 is a graph of the effect of formic acid concentration on the mechanical properties of a blended film when blended;
FIG. 4 is a graph of the effect of post-treatment on the mechanical properties of blended films;
FIG. 5 shows the fibroin and chitosan blend membranes at different times, wherein the SF/CS membranes with SF/CS mass ratio of 4:6 at 1, 2, 3 and 4 times of 1050, 5000, 20000 and 30000 times of the membranes in the figure.
Detailed Description
Example 1
The preparation of chitosan solution with formic acid as solvent includes the following steps:
s1, respectively weighing a proper amount of chitosan, adding the chitosan into a solvent with formic acid concentration (1%, 2%, 3%, 4%, 5%) for dissolving, and stirring at the temperature of 30 ℃ to prepare formic acid solution with the specified chitosan concentration (0.5%, 1%, 1.5%, 2%, 2.5%, 3%);
and S2, standing and defoaming the dissolved chitosan solution for 30min, pouring the dissolved solution into a plastic dish by adopting a tape casting method, naturally volatilizing and drying for 24h at room temperature, and forming a film.
S3, the dried chitosan membrane is soaked in 0.5% sodium hydroxide solution for 2h to neutralize the residual acid in the membrane. And then repeatedly washing the membrane by using deionized water, soaking the membrane in the deionized water to remove redundant sodium hydroxide residues, and finally drying the membrane at room temperature for later use.
Example 2
The preparation of chitosan solution with acetic acid as solvent includes the following steps:
s1, respectively weighing a proper amount of chitosan, adding the chitosan into a solvent with acetic acid concentration (1%, 2%, 3%, 4%, 5%) for dissolving, and stirring at the temperature of 30 ℃ to prepare a formic acid solution with the specified chitosan concentration (0.5%, 1%, 1.5%, 2%, 2.5%, 3%);
and S2, standing and defoaming the dissolved chitosan solution for 30min, pouring the dissolved solution into a plastic dish by adopting a tape casting method, naturally volatilizing and drying for 24h at room temperature, and forming a film.
S3, the dried chitosan membrane is soaked in 0.5% sodium hydroxide solution for 2h to neutralize the residual acid in the membrane. And then repeatedly washing the membrane by using deionized water, soaking the membrane in the deionized water to remove redundant sodium hydroxide residues, and finally drying the membrane at room temperature for later use.
As can be seen from fig. 1 and 2, through comparative analysis of mechanical properties and structural characteristics of chitosan films prepared by dissolving two acids, it was determined that, compared with chitosan films prepared by dissolving chitosan with acetic acid, chitosan films prepared by dissolving chitosan with formic acid have a fibrillated structure, have higher breaking strength, but have relatively lower elongation. The difference of contrast formic acid and acetic acid as chitosan solvents is integrated, and formic acid is selected as a proper solvent of chitosan in consideration of the application aspect of the solvent and the introduction of organic matters in the subsequent blending test of chitosan and fibroin. In the examples that follow, formic acid was chosen as the organic solvent.
Example 3
S1, preparing 3% formic acid to dissolve chitosan, stirring at a constant speed at 30 ℃, adding 98% formic acid into the chitosan solution after the chitosan powder is completely dissolved, and uniformly stirring for later use until the formic acid content in the solution reaches a predetermined concentration (30%, 40%, 50%, 60%, 70%, 98%).
S2, directly dissolving regenerated silk fibroin by 98% formic acid, uniformly stirring at 30 ℃ until the silk fibroin is completely dissolved, quickly pouring a proper amount of silk fibroin solution into the high-speed stirred chitosan solution to enable the silk fibroin and the chitosan in the blending system to reach a proper ratio (0: 10, 2:8, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1 and 10: 0), stirring at a rotating speed for 5min, and then standing for defoaming; s3, pouring the blend solution after standing and defoaming into a plastic dish by adopting a tape casting method, and drying the blend solution at a proper temperature (30 ℃, 50 ℃, 70 ℃ and natural drying) to form a film.
S4, soaking the dried blend membrane part in absolute ethyl alcohol for 30min as a control group (ethanol treatment before neutralization, ethanol treatment after neutralization and no ethanol treatment), and then airing for later use.
S5, soaking the whole treated blend membrane in 0.5 percent sodium hydroxide solution for 30min to neutralize the residual acid in the membrane. And then repeatedly washing the membrane by using deionized water, soaking the membrane in 1000mL of deionized water for 24h to remove redundant sodium hydroxide residues, and finally drying the membrane at room temperature for later use.
As can be seen from the combination of FIG. 3, within a certain range, the mechanical properties of the film prepared from the solution with lower formic acid content are relatively poor, and the mechanical properties of the film prepared from the blended solution with higher formic acid content are better;
TABLE 1 statistics of mechanical properties of blended membranes made of fibroin and chitosan in different proportions
Combining table 1 and fig. 4, it can be seen from table 1 and fig. 4 that, when the content of silk element (SF) in the blended film is less than that of Chitosan (CS), as the ratio of silk element to chitosan in the blended film (SF: CS =5:5, 4:6, 3:7, 2:8, 1:9, 0: 10) decreases, the breaking strength of the blended film gradually increases, the elongation at break first increases (SF: CS =5:5, 4:6, 3: 7) and then decreases (SF: CS =3:7, 2:8, 1:9, 0: 10), and the young's modulus first decreases (SF: CS =5:5, 4:6, 3: 7) and then increases (SF: CS =3:7, 2:8, 1:9, 0: 10). Analysis shows that the change of the mechanical property is related to the distribution state of chitosan and fibroin in the blended film, when the content of chitosan is gradually increased, the blended film structure which is originally dominated by the silk fibroin aggregation state structure is gradually disturbed by the chitosan, and the Young modulus is reduced; with the further increase of the content, a more regular crystal structure is formed among the chitosan in the blending film, the mechanical property is improved, and the Young modulus is improved. It can be seen from the data in the figures and tables that the young modulus of silk fibroin is much higher than that of chitosan, which is probably because the crystallinity of silk fibroin is higher than that of chitosan, so when the chitosan structure is the dominant structure of the blend membrane, the uniformly distributed silk fibroin part has a promotion effect on the mechanical properties of the blend membrane.
TABLE 2 statistics of mechanical properties of blend membranes made at different drying temperatures
It can be seen from table 2 that the breaking strength and breaking elongation of the blended film basically follow the decrease with the increase of temperature, the elongation at 50 ℃ increases, the young's modulus increases with the temperature (20 ℃ -30 ℃) and then decreases (30 ℃ -50 ℃), the modulus at 70 ℃ increases greatly, and the mechanical properties at various temperatures are greatly different.
In the post-treatment of the chitosan and fibroin blended film, the processes of neutralizing acid and desalting are involved, and as can be seen from fig. 4, the breaking strength and elongation at break of the blended film soaked in ethanol for 30min before neutralization treatment are the largest, and the breaking strength and elongation at break of the blended film directly neutralized without ethanol treatment are the smallest, while the breaking strength and elongation at break of the blended film subjected to neutralization treatment and thick soaking in ethanol are the smallest. And with reference to fig. 5, it can be seen from fig. 5 that SF and CS in the SF/CS film prepared by the above method are uniformly blended, and the compatibility between the components is good. Meanwhile, the tearing section of the SF/CS film can show an obvious vertical fibril structure, which is a fibril structure formed by self-assembly of fibroin short fibers in a formic acid-calcium chloride dissolving system, and explains the improvement effect of fibroin addition on the aspects of chitosan film mechanical property and the like to a certain extent.
Claims (8)
1. A preparation method of a fibrillating fibroin chitosan composite material is characterized by comprising the following steps:
s1 preparation of chitosan solution: dissolving chitosan at a certain temperature by using low-concentration organic acid as a solvent to obtain a chitosan solution;
s2 preparation of the fibroin solution: dissolving regenerated silk fibroin by using organic acid with a certain concentration as a solvent at a certain temperature to obtain a silk fibroin solution;
s3, preparing a chitosan and fibroin mixed solution: adding high-concentration organic acid into the chitosan solution prepared in the step S1 to enable the organic acid content of the solution to reach the preset concentration, adding a proper amount of silk fibroin solution into the chitosan solution, and uniformly stirring and defoaming to obtain a mixed solution;
s4, preparing a chitosan/silk fibroin material: preparing the mixed solution prepared in the step S3 into a specific shape, and then removing acid to obtain the chitosan/silk fibroin material.
2. The method of claim 1, wherein the fibrillating silk fibroin chitosan composite material is prepared by the following steps: in step S1, the organic acid is aliphatic organic acid and aromatic organic acid, and the organic acid includes one or a combination of two or more of mono-, di-or polycarboxylic acid.
3. The method of claim 2, wherein the fibrillating silk fibroin chitosan composite material is prepared by the following steps: in step S1, the organic acid is one or a combination of two or more of formic acid, acetic acid, lactic acid, and citric acid.
4. The method of claim 1, wherein the fibrillating silk fibroin chitosan composite material is prepared by the following steps: in step S1, the concentration of the low-concentration organic acid is 1-10wt%, the temperature is 20-70 ℃, and the concentration of the chitosan solution is 0.5-5 wt%.
5. The method of claim 1, wherein the fibrillating silk fibroin chitosan composite material is prepared by the following steps: in step S2, the organic acid is formic acid with concentration of 80-100wt%, temperature of 20-70 deg.C, and silk fibroin solution concentration of 1-30 wt%.
6. The method of claim 1, wherein the regenerated silk fibroin of step S2 is prepared by the following steps:
s1, dissolving pure silk cellulose fiber in CaCl2Obtaining ternary solution from the mixed solution of formic acid;
s2, casting the ternary solution into a film, drying, and dialyzing to remove CaCl contained in the film2And obtaining regenerated silk fibroin.
7. The method of claim 1, wherein the fibrillating silk fibroin chitosan composite material is prepared by the following steps: in the step S3, the content of the organic acid is 30-98%, and the mass ratio of the silk fibroin solution to the chitosan solution is 1-9: 9-1.
8. The method of claim 1, wherein the fibrillating silk fibroin chitosan composite material is prepared by the following steps: the shape in step S4 includes a fiber, a film, a three-dimensional scaffold, or a gel.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004131647A (en) * | 2002-10-11 | 2004-04-30 | National Institute Of Agrobiological Sciences | Composite of silk protein with chitosan and method for producing the same |
| RU2270209C1 (en) * | 2004-11-25 | 2006-02-20 | Государственное образовательное учреждение высшего профессионального образования "Санкт-Петербургский государственный университет технологии и дизайна" (СПГУТД) | Method of manufacturing porous material from fibroin/chitosan mixture |
| CN103436985A (en) * | 2013-07-22 | 2013-12-11 | 苏州三和开泰花线织造有限公司 | Preparation method of silk fibroin/chitosan blend nanofiber |
| CN107012525A (en) * | 2017-06-01 | 2017-08-04 | 合肥创沃科技有限公司 | A kind of preparation method of the composite regenerated cellulose tissue repair materials of chitosan |
| CN110229384A (en) * | 2019-06-19 | 2019-09-13 | 安徽农业大学 | Silver-colored diamine oxime Cellulose/Chitosan/fibroin composite aerogel of a kind of load and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004131647A (en) * | 2002-10-11 | 2004-04-30 | National Institute Of Agrobiological Sciences | Composite of silk protein with chitosan and method for producing the same |
| RU2270209C1 (en) * | 2004-11-25 | 2006-02-20 | Государственное образовательное учреждение высшего профессионального образования "Санкт-Петербургский государственный университет технологии и дизайна" (СПГУТД) | Method of manufacturing porous material from fibroin/chitosan mixture |
| CN103436985A (en) * | 2013-07-22 | 2013-12-11 | 苏州三和开泰花线织造有限公司 | Preparation method of silk fibroin/chitosan blend nanofiber |
| CN107012525A (en) * | 2017-06-01 | 2017-08-04 | 合肥创沃科技有限公司 | A kind of preparation method of the composite regenerated cellulose tissue repair materials of chitosan |
| CN110229384A (en) * | 2019-06-19 | 2019-09-13 | 安徽农业大学 | Silver-colored diamine oxime Cellulose/Chitosan/fibroin composite aerogel of a kind of load and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIWEI HUANG ET AL.: "Facile preparation of a strong chitosan-silk biocomposite film" * |
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