CN117024779A - High-strength silk protein physical hydrogel and preparation method and application thereof - Google Patents
High-strength silk protein physical hydrogel and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 40
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims abstract description 39
- 235000012209 glucono delta-lactone Nutrition 0.000 claims abstract description 34
- 239000000182 glucono-delta-lactone Substances 0.000 claims abstract description 34
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- 238000004132 cross linking Methods 0.000 claims abstract description 27
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
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Abstract
The invention relates to a high-strength silk protein physical hydrogel, and a preparation method and application thereof. The method takes natural cocoons as raw materials, prepares high-concentration silk protein solution through processes of degumming, dissolving, desalting, concentrating and the like, and prepares silk protein hydrogel by taking glucono delta-lactone as a protein denaturant. Meanwhile, the silk protein molecular chain is converted into beta-sheet under the limited condition by adding calcium chloride, so that a beta-sheet crystal region with small and uniform size is formed as a physical crosslinking point, and finally the high-strength silk protein physical crosslinking hydrogel is obtained. Compared with the prior art, the preparation conditions of the invention are green and mild, the raw materials are nontoxic and harmless, and the economic cost is low. The prepared silk protein hydrogel has good biocompatibility, is degradable, has excellent mechanical properties, can reach more than 2MPa in both elastic modulus and compression modulus, and has wide application prospect in the fields of biomedical materials and the like.
Description
Technical Field
The invention belongs to the technical field of biological materials and hydrogels, and particularly relates to a high-strength silk fibroin physical hydrogel, and a preparation method and application thereof.
Background
The mulberry silk protein is prepared into silk protein base materials with different properties in the past decades due to good biocompatibility and controllable biodegradability, and is applied to various fields of biomedical, sensing, photoelectric materials and the like. From the prior art, the mechanical strength of the physical cross-linked hydrogel formed by silk proteins is limited, and the application of the physical cross-linked hydrogel in some scenes needing a certain mechanical strength is greatly limited. Although the mechanical properties of silk proteins can be improved by using a chemical crosslinking method, solving the problem of residual chemical crosslinking agents is always a difficult point of researchers in the field, and if unreacted chemical crosslinking agents cannot be completely removed, the greatest advantages of non-toxic, harmless and good biocompatibility of silk proteins are greatly affected. Patent application CN115671388A discloses an injectable microsphere gel of silk protein and a preparation method thereof, comprising: preparing regenerated silk protein solution, including degumming, dissolving and purifying mulberry silk, and obtaining regenerated silk protein solution with target molecular weight through molecular weight screening; preparing an aqueous solution of silk protein microspheres by adding ethanol into the regenerated silk protein solution, freezing, thawing and the like; drying the two solutions prepared by the steps to obtain the redispersible powder of the silk protein microspheres; and dispersing the silk protein microsphere redispersible powder into a solvent, and adding a gel inducer to prepare the silk protein microsphere gel. Although patent application CN114680324a relates to glucono-delta-lactone and tricalcium phosphate, which can improve the gel speed and gel strength of soy protein, the glucono-delta-lactone and tricalcium phosphate act as coagulants.
The polymer hydrogel is a material which is formed by interconnecting polymers in a water-dispersing medium so as to form a three-dimensional reticular space structure. Since hydrogels contain a large amount of water, they have good flexibility, similar to biological tissues. Meanwhile, the hydrogel can not be dissolved in a liquid environment and can maintain certain mechanical properties. The characteristics lead the hydrogel to have wide application prospect in the biomedical field, in particular to the tissue engineering field. Natural polymer hydrogels have incomparable advantages over synthetic polymers in biomedical applications due to their excellent biocompatibility. However, most of the conventional natural polymer hydrogels have weak mechanical properties, and therefore, the conventional natural polymer hydrogels can only be applied to scenes with low requirements on mechanical properties, such as drug delivery and water-absorbing materials, and further application is severely limited. At present, a chemical crosslinking method is commonly used for improving the mechanical properties of natural polymer hydrogel, and although the natural polymer hydrogel has a certain effect, the use of a chemical crosslinking agent does not bring about some potential unsafe factors. Therefore, the natural polymer physical crosslinked hydrogel with simple development process, low cost and excellent mechanical property has great practical value in the biomedical field.
Disclosure of Invention
Based on the problem of poor mechanical properties of biomacromolecule hydrogel in the prior art, the invention aims to provide a silk protein physical hydrogel with simple preparation and excellent mechanical properties, and a preparation method and application thereof.
The aim of the invention can be achieved by the following technical scheme:
in one aspect, the invention provides a method for preparing a high-strength silk protein physical hydrogel, comprising the following steps:
s1: preparation of silk fibroin solution: degumming, dissolving, filtering, desalting and concentrating the mulberry silk to obtain a silk protein aqueous solution;
s2: preparation of silk fibroin/glucono delta-lactone/calcium chloride solution: taking the silk protein solution in the step S1, adding a glucono delta-lactone solution and a calcium chloride solution into the silk protein solution, and removing bubbles from the silk protein/gluco delta-lactone/calcium chloride solution after uniform mixing;
s3: preparation of silk protein gel: pouring the silk fibroin/glucono delta-lactone/calcium chloride solution in the step S2 into a mould, standing at room temperature to form initial hydrogel, and soaking the prepared initial hydrogel in deionized water to remove free calcium chloride to obtain the silk fibroin physical crosslinking hydrogel.
Further, the degumming agent used in the degumming process of the silkworm silk in the step S1 is one or more of sodium carbonate, sodium bicarbonate, boric acid-borax buffer solution, mosaic soap, urea, succinic acid and enzyme.
Further, the desalting in the step S1 is one or more of dialysis, chromatography, ultrafiltration and chromatographic separation.
Further, the concentration of the silk protein solution in step S1 is 3-40wt%, preferably 6-35wt%;
still further, the concentration of the high concentration regenerated silk protein solution is more preferably 8 to 30wt%, still more preferably 10 to 25wt%.
Further, the concentration of the glucono delta-lactone in the mixed solution in the step S2 is 0.001 to 10mol/L, preferably 0.01 to 1mol/L, and more preferably 0.05 to 0.5mol/L.
Further, the concentration of the calcium chloride in the mixed solution in step S2 is 0.01 to 20wt%, preferably 0.1 to 15wt%, and more preferably 1 to 10wt%.
Further, the silk fibroin/glucono delta-lactone/calcium chloride solution in step S3 is allowed to stand for 1 to 96 hours, preferably 24 to 48 hours; the initial hydrogel is soaked for 0.5-10 hours, preferably 1-5 hours.
The invention also provides a high-strength silk protein physical hydrogel which is obtained based on the preparation method.
The high-strength silk protein physical hydrogel prepared by the invention has a compression modulus of 1-3MPa and a compression strength of 0.5-2MPa when compressed by 60%.
The high-strength silk protein physical hydrogel prepared by the invention has the elastic modulus of 1-3MPa, the breaking strength of 0.1-1MPa and the breaking elongation of 50-150%.
The invention further provides application of the high-strength silk fibroin physical hydrogel in the fields of preparation of biomedical materials, sensing and photoelectric materials.
Compared with the prior art, the invention adopts nontoxic glucono delta-lactone as a protein denaturant, and utilizes the hydrolysis of the glucono delta-lactone to ensure that the solution environment is slowly converted into acidity, thereby inducing the conversion of a silk protein molecular chain into beta-sheet conformation to prepare the silk protein hydrogel. Meanwhile, calcium chloride is added, and the aggregation of silk protein molecular chains is limited by using the chelation of calcium ions on the silk protein molecular chains, so that the growth of a beta-sheet crystal region is prevented from being excessively large, and a beta-sheet crystal region with small and uniform size is formed as a physical crosslinking point, and finally, the high-strength silk protein physical crosslinking hydrogel is obtained.
The invention has the following advantages:
(1) The invention adopts the glucono delta-lactone and the calcium chloride which have low economic cost and no toxicity even if a small amount of residue exists.
(2) The invention can control the size of the physical crosslinking area (namely beta-folding area) in the silk fibroin gel by the addition of calcium chloride in the hydrogel forming process, thereby regulating and controlling the mechanical property of the obtained silk fibroin hydrogel.
(3) The silk fibroin physical crosslinking gel prepared by the invention has excellent mechanical properties, including tensile strength and compressive strength, which are superior to those of the traditional silk fibroin physical crosslinking hydrogel.
(4) The preparation method is simple and feasible, is environment-friendly and has low cost, and the prepared silk protein physical crosslinking gel keeps the degradation performance due to the formation of chemical bonds; meanwhile, the raw materials are wide in source, and the method has a certain promotion effect on resources and environmental protection, has popularization and application values, and is beneficial to realizing large-scale industrial production.
(5) The silk protein physical crosslinking gel prepared by the invention has wide application prospect in the fields of biomedical, sensing, photoelectric materials and the like.
Drawings
FIG. 1 is a graph showing the performance of the high strength silk fibroin physically crosslinked hydrogel prepared in example 1.
FIG. 2 is a scanning electron microscope image of the high strength silk fibroin physically crosslinked hydrogel prepared in example 1 after lyophilization.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
The mechanical property test of the silk fibroin physically crosslinked hydrogel was performed on an electronic universal materials tester (Instron 5966) using 500N sensors. The compressed sample was a 10mm cube with a compression rate of 5mm/min. The stretched sample was a rectangle of 30mm by 10mm (thickness of 2 mm), the distance between the clamps was 20mm, and the stretching rate was 15mm/min.
Example 1
The preparation method of the high-strength silk protein physical crosslinking hydrogel comprises the following steps:
adding a calcium chloride solution into a silk protein solution with the concentration of 15wt%, and then adding a glucono delta-lactone solution, so that the concentration of silk protein in the final silk protein/glucono delta-lactone/calcium chloride mixed solution is 10wt%, the concentration of glucono delta-lactone is 0.15mol/L, and the concentration of calcium chloride is 7.5wt%. Casting the silk fibroin/glucolactone/calcium chloride mixed solution in a mould, standing for 24 hours at room temperature to form initial hydrogel, soaking the initial hydrogel in deionized water for 4 hours to remove free calcium chloride, and obtaining the silk fibroin physical crosslinking hydrogel.
Through mechanical compression test, the compression modulus of the silk fibroin physical crosslinking hydrogel is 2.7MPa, and the compression strength at 60% compression is 1.2MPa; the elastic modulus is 2.1MPa, the breaking strength is 0.5MPa, and the breaking elongation is 124%.
Example 2
Adding a calcium chloride solution into a silk protein solution with the concentration of 20wt%, and then adding a glucono delta-lactone solution to ensure that the concentration of silk protein in the final silk protein/glucono delta-lactone/calcium chloride mixed solution is 16wt%, the concentration of glucono delta-lactone is 0.45mol/L, and the concentration of calcium chloride is 5wt%. Casting the silk fibroin/glucolactone/calcium chloride mixed solution in a mould, standing for 32 hours at room temperature to form initial hydrogel, soaking the initial hydrogel in deionized water for 3 hours to remove free calcium chloride, and obtaining the silk fibroin physical crosslinking hydrogel. The compression modulus of the silk fibroin physical crosslinking hydrogel is 2.1MPa, and the compression strength of the silk fibroin physical crosslinking hydrogel at 60% compression is 1.1MPa; the elastic modulus is 2.0MPa, the breaking strength is 0.4MPa, and the breaking elongation is 102%.
Example 3
Adding a calcium chloride solution into a silk protein solution with the concentration of 21wt%, and then adding a glucono delta-lactone solution to ensure that the concentration of silk protein in the final silk protein/glucono delta-lactone/calcium chloride mixed solution is 15wt%, the concentration of glucono delta-lactone is 0.3mol/L, and the concentration of calcium chloride is 2.5wt%. Casting the silk fibroin/glucolactone/calcium chloride mixed solution in a mould, standing for 48 hours at room temperature to form initial hydrogel, soaking the initial hydrogel in deionized water for 8 hours to remove free calcium chloride, and obtaining the silk fibroin physical crosslinking hydrogel. The compression modulus of the silk fibroin physical crosslinking hydrogel is 1.9MPa, and the compression strength of the silk fibroin physical crosslinking hydrogel at 60% compression is 1.1MPa; the elastic modulus is 2.0MPa, the breaking strength is 0.4MPa, and the breaking elongation is 94%.
Example 4
Adding a calcium chloride solution into a silk protein solution with the concentration of 12wt%, and then adding a glucono delta-lactone solution to ensure that the concentration of silk protein in the final silk protein/glucono delta-lactone/calcium chloride mixed solution is 10wt%, the concentration of glucono delta-lactone is 0.06mol/L, and the concentration of calcium chloride is 1wt%. Casting the silk fibroin/glucolactone/calcium chloride mixed solution in a mould, standing for 48 hours at room temperature to form initial hydrogel, soaking the initial hydrogel in deionized water for 2 hours to remove free calcium chloride, and obtaining the silk fibroin physical crosslinking hydrogel. The compression modulus of the silk fibroin physical crosslinking hydrogel is 1.2MPa, and the compression strength of the silk fibroin physical crosslinking hydrogel at 60% compression is 0.8MPa; the elastic modulus is 1.4MPa, the breaking strength is 0.3MPa, and the breaking elongation is 63%.
Comparative example 1
In a silk protein solution with the concentration of 15wt%, no calcium chloride solution is added, and only the glucono delta-lactone solution is added, so that the concentration of silk protein in the final silk protein/glucono delta-lactone mixed solution is 10wt% and the concentration of glucono delta-lactone is 0.15mol/L. Casting the silk fibroin/glucolactone mixed solution in a mould, standing for 48 hours at room temperature to form initial hydrogel, and soaking the initial hydrogel in deionized water for 8 hours to obtain the silk fibroin physical crosslinking hydrogel. The compression modulus of the silk fibroin physical crosslinking hydrogel is 0.9MPa, and the compression strength of the silk fibroin physical crosslinking hydrogel at 60% compression is 0.6MPa; the elastic modulus is 1.0MPa, the breaking strength is 0.2MPa, and the breaking elongation is 45%.
As shown in Table 1, it can be seen that the high strength silk fibroin physically crosslinked hydrogel of example 1 has excellent mechanical properties, including tensile strength and compressive strength, superior to those of conventional silk fibroin physically crosslinked hydrogels.
TABLE 1 mechanical Properties of silk fibroin solutions of different concentrations
| Compression modulus (MPa) | Modulus of elasticity (MPa) | Breaking strength (MPa) | Elongation at break | |
| Example 1 | 2.7 | 2.1 | 0.5 | 124％ |
| Example 2 | 2.1 | 2.0 | 0.4 | 102％ |
| Example 3 | 1.9 | 2.0 | 0.4 | 94％ |
| Example 4 | 1.2 | 1.4 | 0.3 | 63％ |
| Comparative example 1 | 0.9 | 1.0 | 0.2 | 45％ |
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the high-strength silk protein physical crosslinking hydrogel is characterized by comprising the following steps of:
s1: preparing a silk protein aqueous solution;
s2: preparation of silk fibroin/glucono delta-lactone/calcium chloride solution: taking the high-concentration regenerated silk protein solution prepared in the step S1, adding a glucono delta-lactone solution and a calcium chloride solution into the high-concentration regenerated silk protein solution, uniformly mixing the silk protein solution, the glucono delta-lactone solution and the calcium chloride solution, and removing bubbles;
s3: preparation of silk protein gel: pouring the silk fibroin/glucono delta-lactone/calcium chloride solution in the step S2 into a mould, standing at room temperature to form initial hydrogel, and soaking the prepared initial hydrogel in deionized water to remove free calcium chloride to obtain the silk fibroin physical crosslinking hydrogel.
2. The method for preparing a high-strength silk protein physically cross-linked hydrogel according to claim 1, wherein the concentration of glucono delta-lactone in the mixed solution in the step S2 is 0.001-10mol/L.
3. The method for producing a high-strength silk protein physically crosslinked hydrogel according to claim 1 or 2, wherein the concentration of glucono delta-lactone in the mixed solution in step S2 is preferably 0.01-1mol/L, and more preferably 0.05-0.5mol/L.
4. The method for producing a high-strength silk protein physically crosslinked hydrogel according to claim 1, wherein the concentration of calcium chloride in the mixed solution in step S2 is 0.01-20wt%, preferably 0.1-15wt%, and more preferably 1-10wt%.
5. The method for preparing a high-strength silk fibroin physically cross-linked hydrogel according to claim 1, wherein the silk fibroin/glucono delta lactone/calcium chloride solution in step S3 is allowed to stand for 1-96 hours, and the initial hydrogel is soaked for 0.5-10 hours.
6. The method for preparing a high-strength silk fibroin physically cross-linked hydrogel according to claim 5, wherein the silk fibroin/glucono delta lactone/calcium chloride solution in step S3 is allowed to stand for 24-48 hours, and the initial hydrogel is preferably soaked for 1-5 hours.
7. A high strength silk protein physically cross-linked hydrogel, characterized in that it is obtained by the preparation method according to any one of claims 1-6.
8. The high strength silk fibroin physically crosslinked hydrogel according to claim 7 having a compression modulus of 1-3MPa and a compression strength of 0.5-2MPa at 60% compression.
9. The high strength silk fibroin physically crosslinked hydrogel according to claim 7, having an elastic modulus of 1-3MPa, a breaking strength of 0.1-1MPa, and an elongation at break of 50-150%.
10. Use of the high strength silk fibroin physically cross-linked hydrogel according to claim 7 in the preparation of biomedical materials, sensing and optoelectronic materials.
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