CN114539564B - Preparation method of rapid-gel silk fibroin-based strong hydrogel - Google Patents
Preparation method of rapid-gel silk fibroin-based strong hydrogel Download PDFInfo
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- 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
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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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
Abstract
The invention provides a preparation method of a quick-gelling silk fibroin-based strong hydrogel, which comprises the steps of cleaning degummed silk with deionized water, drying, dissolving and dialyzing to obtain a silk fibroin solution; and then adding a cross-linking agent into the silk fibroin solution for chemical cross-linking, uniformly mixing with a gelatin solution, and standing for a certain time under the low-temperature condition to obtain the silk fibroin/gelatin hydrogel. Through the combined use of chemical crosslinking and physical crosslinking, the high-efficiency combination between the silk fibroin and the gelatin is realized, and the integration of high performance and controllability is realized; by utilizing the salt solution to induce the molecular structure of the silk fibroin and the gelatin, the mechanical property of the hydrogel is improved. The hydrogel prepared by the preparation method has the advantages of uniform three-dimensional porous structure, high elasticity, strong mechanical property, good biocompatibility and biodegradability.
Description
Technical Field
The invention relates to the technical field of biological materials, in particular to a preparation method of a rapid-gel silk fibroin-based strong hydrogel.
Background
The gel is a form between solid and liquid, and can be classified into elastic gel and inelastic gel according to the properties of dispersed particles and the characteristics of the inter-particle connection when forming a gel structure. The hydrogel is an elastic gel formed by a polymer compound solution, takes water as a dispersion medium, can absorb and hold a large amount of water, has a crosslinked network structure, is formed by crosslinking a hydrophilic polymer compound through ionic bonds, covalent bonds, hydrogen bonds and the like, and has the characteristics of a polymer electrolyte and a three-dimensional structure. Hydrogels have a higher water content and a larger number of internal void structures, and their interconnected porous structures provide channels for the transport of water, nutrients, drugs, etc., provide a good environment for the migration and proliferation of cells, are considered to be good materials for encapsulation and delivery of cells and bioactive molecules, and can be used in tissue engineering, cell therapy, etc.
Silk fibroin is a natural polymer protein extracted from silk, and its internal structure is divided into a crystalline region and an amorphous region. The antiparallel beta-sheet structure forms a crystallization area, the irregular curled structure belongs to an amorphous area, the crystallization area is generally and uniformly dispersed in the amorphous area, molecular chains in the amorphous area and the microcrystalline area are orderly arranged along the direction of the long axis of the silk fiber, and the silk fiber has good mechanical property and soft luster based on the staggered existence of the crystallization area and the amorphous area and the oriented arrangement of macromolecules. The physicochemical properties of silk fibroin are determined by influencing the molecular conformation according to the arrangement sequence of amino acids. Silk fibroin possesses good physical and mechanical properties, adjustable biodegradability and excellent biocompatibility. At present, silk fibroin is widely applied to the fields of tissue engineering, regenerative medicine and the like. In the prior art, silk fibroin hydrogel gel prepared by physical crosslinking is slow, and has poor structural stability and poor mechanical property; the silk fibroin hydrogel prepared by a chemical crosslinking method has poor elasticity, and the defects limit the application of the silk fibroin hydrogel in fields of regenerative medicine, tissue engineering and the like. Therefore, it is of great importance to find a method for preparing silk fibroin hydrogels that have both excellent mechanical properties and biocompatibility.
Chinese patent application No. 200910025440.1, publication No. 2012, month 07, 25, entitled "method for preparing a silk fibroin hydrogel", discloses a method for preparing a silk fibroin hydrogel. In the method, silk is degummed, dissolved and dialyzed to obtain silk fibroin solution with the mass concentration of 1-30%; then, carrying out ultrasonic oscillation treatment at 37 ℃ to obtain silk fibroin hydrogel; finally, pouring the treated silk fibroin solution into a mould, and standing at room temperature for 5 minutes to obtain the silk fibroin solution. In the technical scheme, the silk fibroin hydrogel is prepared by adopting an ultrasonic oscillation method, silk fibroin molecules are physically crosslinked under the action of ultrasonic waves, and silk fibroin forms a beta-sheet crystalline structure, but the formed silk fibroin hydrogel is very hard and brittle, and the strength and flexibility of the formed silk fibroin hydrogel cannot meet the application requirements of subsequent high-strength high-toughness silk fibroin materials.
Chinese patent application No. 201810662604.0, publication date 2020, month 06 and 02, and patent entitled "double network crosslinked cellulose/silk fibroin high strength hydrogel and preparation and application thereof" discloses double network crosslinked cellulose/silk fibroin high strength hydrogel and preparation and application thereof. In the technical scheme, the cellulose solution, the silk fibroin solution and the epichlorohydrin are uniformly mixed, and crosslinked under the stirring condition to obtain a crosslinked solution; centrifuging the crosslinking solution to remove bubbles, pouring the crosslinking solution into a mold, and reacting and solidifying to obtain the low-density chemical crosslinking cellulose/silk fibroin hydrogel; placing the obtained cellulose/silk fibroin hydrogel in a carbon dioxide incubator for atmosphere physical crosslinking; washing with running water to obtain the double-network crosslinked cellulose/silk fibroin high-strength hydrogel. Although the technical scheme can prepare high-strength hydrogel, an alkali solution and a toxic organic solution are needed in the preparation process, the preparation process is complex, and the time needed by the gel is long.
In view of the above, there is a need to devise an improved method for preparing a rapid gelling silk fibroin-based strong hydrogel to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a preparation method of a rapid gel silk fibroin-based strong hydrogel, which is simple and convenient to prepare, high in gel speed, strong in mechanical property and high in elasticity.
In order to achieve the above object, the present invention provides a method for preparing a rapid gel silk fibroin-based strong hydrogel, comprising the steps of:
s1, preparing a silk fibroin solution: cleaning degummed silk with deionized water, and drying to obtain dry silk; dissolving the dry silk and performing dialysis treatment to obtain a silk fibroin solution I;
s2, preparing silk fibroin-based hydrogel: adding a cross-linking agent into the silk fibroin solution I obtained in the step S1 to carry out chemical cross-linking to obtain a silk fibroin solution II subjected to chemical cross-linking, and uniformly mixing the silk fibroin solution II with a gelatin solution to obtain a mixed solution III; and standing the mixed solution III at a low temperature to obtain the silk fibroin/gelatin hydrogel.
Preferably, the preparation method of the rapid gel silk fibroin-based strong hydrogel further comprises the following steps:
s3, sequentially soaking the silk fibroin/gelatin hydrogel obtained in the step S2 in (NH) 4 ) 2 SO 4 And (3) obtaining the silk fibroin-based hydrogel in the solution and deionized water.
Preferably, the (NH 4 ) 2 SO 4 The mass fraction of the solution is 10-20%.
Preferably, the silk fibroin/gelatin hydrogel is immersed in (NH 4 ) 2 SO 4 The time in the solution is 10-12 h.
Preferably, the mass fraction of the silk fibroin solution I is 5-10%, and the mass fraction of the gelatin solution is 5-20%.
Preferably, the volume of the silk fibroin solution II mixed with the gelatin solution is (1-2): (0.5-2).
Preferably, the dialysis treatment is carried out at a temperature of 0-4 ℃ for 24-72 hours.
Preferably, in step S2, the low temperature condition is 0 to 4 ℃, and the time of standing under the low temperature condition is 3 to 10min.
Preferably, the cross-linking agent is one or more of MES, NHS and EDC.
Preferably, in step S3, the silk fibroin/gelatin hydrogel is soaked in deionized water for 24-96 hours.
The beneficial effects of the invention are as follows:
1. according to the preparation method of the rapid gel silk fibroin-based strong hydrogel, disclosed by the invention, the double-crosslinked high-strength hydrogel with a three-dimensional crosslinked network structure is prepared by taking gelatin and silk fibroin as raw materials through the processes of blending, chemical crosslinking, low-temperature treatment and the like.
2. According to the preparation method of the silk fibroin-based strong hydrogel for the quick gel, provided by the invention, the regulation and control on the mechanical strength of the hydrogel are realized by adjusting experimental conditions, so that the controllable preparation of the gel is realized, and the requirements of hydrogels with different mechanical strengths in actual needs are met; the structure of the silk fibroin and the gelatin is regulated and controlled by fully utilizing the salt solution, so that the mechanical property of the prepared hydrogel is improved, and the hydrogel can meet the application requirements; the combination between the silk fibroin and the gelatin is realized by carrying out chemical crosslinking on the silk fibroin and then carrying out physical crosslinking on the silk fibroin, and meanwhile, the chemical crosslinking and the non-covalent physical crosslinking are combined, so that the integrated preparation with high performance and controllability can be effectively realized.
3. The preparation method of the rapid gel silk fibroin-based strong hydrogel provided by the invention realizes the regulation and control of the mechanical strength of the hydrogel by adjusting the crosslinking mode and the proportion content of the two components used in the experimental process, realizes the controllable preparation of the gel, meets the requirements of hydrogels with different mechanical strengths in actual needs, has the advantages of rapidness, mild preparation conditions and simple preparation process, and has important significance in the controllable preparation of the high-strength functionalized hydrogel.
Drawings
FIG. 1 is an SEM image of a hydrogel prepared in example 1 of a method of preparing a rapid gel silk fibroin-based strong hydrogel of the present invention;
FIG. 2 is an SEM image of the hydrogel obtained in example 2;
FIG. 3 is an SEM image of the hydrogel obtained in comparative example 2;
FIG. 4 is an SEM image of the hydrogel prepared in comparative example 3;
fig. 5 is a stress-strain curve of hydrogels prepared in examples 1 to 2 and comparative examples 1 to 3 according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The preparation method of the silk fibroin-based strong hydrogel for quick gel provided by the invention comprises the following steps:
s1, preparing a silk fibroin solution: washing degummed silk with deionized water, and drying at 60deg.C to obtain dry silk; dissolving the dry silk and performing dialysis treatment to obtain a silk fibroin solution I;
s2, preparing silk fibroin-based hydrogel: adding a cross-linking agent into the silk fibroin solution I prepared in the step S1 for cross-linking treatment to obtain a silk fibroin solution II subjected to chemical cross-linking, and uniformly mixing the silk fibroin solution II and a gelatin solution to obtain a mixed solution III; and standing the mixed solution III at a low temperature to obtain the silk fibroin/gelatin hydrogel.
S3, soaking the silk fibroin/gelatin hydrogel obtained in the step S2 in (NH) in sequence 4 ) 2 SO 4 And (3) preparing the silk fibroin-based hydrogel in the solution and deionized water.
Wherein, in step S1, the degumming process includes the steps of:
s11, immersing 100g of mulberry silk in 5L of sodium carbonate solution with the mass fraction of 0.1%, boiling for 30min at the temperature of 98-100 ℃, taking out cocoons after boiling each time, and washing with deionized water;
s12, adding the silkworm cocoons washed in the step S1 into newly prepared 5L of sodium carbonate solution with the mass fraction of 0.1%, boiling for 30min at the temperature of 98-100 ℃, and repeating the steps for three times.
Specifically, in the step S1, the temperature of the dialysis treatment is 0-4 ℃ and the time is 24-72 hours; the mass fraction of the silk fibroin solution I is 5-10%, and the drying treatment time is 72 hours.
Specifically, in the step S2, the chemical crosslinking time is 5-10 min; silk fibroin solution II and gelatin solution according to the volume ratio (1-2): (0.5-2) and evenly mixing.
And step S2, the mixed solution III is injected into a mould, and the mould is placed at a low temperature of 0-4 ℃ for 3-10 min to prepare the silk fibroin/gelatin hydrogel.
Wherein, in the step S2, the added cross-linking agent is one or more of fatty acid Methyl Ester Sulfonate (MES), N-hydroxysuccinimide (NHS) and dichloroethane (EDC); the mass fraction of the gelatin solution is 5-20%.
Specifically, in step S3, (NH 4 ) 2 SO 4 The mass fraction of the solution is 10-20%, and the silk fibroin/gelatin hydrogel is soaked in (NH) 4 ) 2 SO 4 The time in the solution is 10-12 h, and the (NH) 4 ) 2 SO 4 The volume of the solution was 100mL, silk fibroin/MingThe time for soaking the glue gel in deionized water is 24-96 hours.
Example 1
Immersing 100g of silk in 5L of 0.1% sodium carbonate solution, boiling for 30min at 98-100 ℃, taking out cocoons after boiling each time, and washing with deionized water; and then adding the cleaned cocoons into 5L of sodium carbonate solution with the mass fraction of 0.1%, repeating the steps for three times until the cocoons are degummed, fully washing the cocoons with deionized water, and drying the cocoons in an oven at 60 ℃ for 72 hours to obtain the pure silk fibroin fibers.
Then, dissolving 5g of the prepared pure silk fibroin fibers in 25mL of lithium bromide solution to obtain silk fibroin solution with the mass fraction of 5%, and dialyzing the silk fibroin solution at 4 ℃ for 72 hours; after the dialysis is finished, MES accounting for 20% of the mass of the silk fibroin solution, NHS accounting for 20% of the mass of the silk fibroin solution and EDC accounting for 10% of the mass of the silk fibroin solution are added into the silk fibroin solution to be used as a cross-linking agent for chemical cross-linking for 5min, so that a cross-linked silk fibroin solution is obtained; then, adding gelatin solution with the mass fraction of 10% into the silk fibroin solution after the crosslinking treatment, wherein the volume ratio of the silk fibroin solution to the gelatin solution is 1:1, after being uniformly mixed, injecting the mixed solution into a mould, and putting the mould into a refrigerator, and standing for 3min at the temperature of 4 ℃ to prepare the silk fibroin/gelatin hydrogel; finally, the prepared silk fibroin/gelatin hydrogel was immersed in 100mL (NH 4 ) 2 SO 4 For 12h to enhance the mechanical properties of the hydrogel, soaking the obtained hydrogel in deionized water for 72h to remove the (NH) adsorbed on the inner and surface of the hydrogel 4 ) 2 SO 4 The SEM image of the prepared hydrogel is shown in figure 1, and the hydrogel can be seen to have a three-dimensional pore structure, and the pore size is uniform and dense.
Example 2
Example 2 differs from example 1 only in that: the obtained silk fibroin/gelatin hydrogel is free of (NH) 4 ) 2 SO 4 Soaking in the solution, and the rest stepsThe steps are substantially the same as those of example 1, and will not be described again. The SEM image of the resulting hydrogel is shown in FIG. 2, and it can be seen from the image that the hydrogel has a three-dimensional pore structure with uniform pore size, and the pore size is increased as compared with the hydrogel prepared in example 1.
Comparative example 1
Comparative example 1 differs from example 1 only in that: the silk fibroin solution is subjected to chemical crosslinking by MES/NHS/EDC and then is directly frozen in a refrigerator at 4 ℃ for 3min to obtain silk fibroin hydrogel, and the rest steps are basically the same as those of the embodiment 1 and are not repeated here.
Comparative example 2
Comparative example 2 differs from example 1 only in that: directly mixing the prepared silk fibroin solution with gelatin solution according to the volume ratio of 1:1 to obtain a mixed solution of a silk fibroin solution and a gelatin solution, then adding the mixed solution into an injection mold, and freezing the injection mold in a refrigerator at 4 ℃ for 10min, wherein the rest steps are basically the same as those of the embodiment 1, and the description thereof is omitted. The SEM image of the obtained hydrogel is shown in fig. 3, and it can be seen from fig. 3 that the interior of the hydrogel has a three-dimensional pore structure, and the pore size is uniform and the pore structure is dense.
Comparative example 3
Comparative example 3 differs from example 1 only in that: directly injecting the prepared silk fibroin solution into a mold, drying in an oven at 60 ℃ for 72 hours, and basically carrying out the other steps as in the embodiment 1, so that the description is omitted. The SEM image of the prepared hydrogel is shown in fig. 4, and the inside of the hydrogel is in a three-dimensional pore structure, the pore size distribution is uneven, and cracks in the inside of the material can be observed in the field of view of a lens; the stress strain curves of the hydrogels prepared in examples 1 to 2 and comparative examples 1 to 3 are shown in fig. 5, from which it can be seen that the hydrogels prepared by applying the method of example 1 have the highest strength, and the strength of the hydrogels of comparative examples 2 and 3 is almost 0.
Examples 3 to 7
Examples 3 to 7 differ from example 1 only in that: the volume ratio of the chemically crosslinked silk fibroin solution to the gelatin solution was set to be different, and the rest of the steps were basically the same as those of example 1, and will not be described in detail herein, and the strength of the silk fibroin/gelatin hydrogel prepared at different volume ratios is shown in table 1: as can be seen from the data in the table, the hydrogels produced had the highest strength when the volume ratio of silk fibroin solution to gelatin solution after chemical crosslinking was 1:1.
TABLE 1 setting of the volume ratio of examples 3 to 7 and the strength of the silk fibroin/gelatin hydrogels prepared under these conditions
Examples 8 to 12
Examples 8 to 12 differ from example 1 only in that: the mass fraction of the silk fibroin solution was set to be different from that of the gelatin solution, and the rest of the steps were basically the same as those of example 1, and will not be described in detail herein, and the strength of the silk fibroin/gelatin hydrogel prepared by the different mass fraction ratios is shown in table 2: as can be seen from the data in the table, when the mass fraction of both the silk fibroin solution and the gelatin solution is 5%: at 10%, the hydrogel produced had the highest strength.
TABLE 2 mass fraction settings of examples 8-12 and strength of silk fibroin/gelatin hydrogels prepared under these conditions
The mechanism of formation of silk fibroin-based hydrogels is described below:
in the presence of a cross-linking agent, the residues of the silk fibroin react with the cross-linking agent to promote the combination of the fibrin and the cross-linking agent in a chemical bond mode; then adding gelatin solution into the silk fibroin solution after chemical crosslinking, standing at low temperature, converting silk fibroin from irregular structure to beta-sheet structure at low temperature, and simultaneously, interpenetrating between silk fibroin solution and gelatin solution to form macromolecular structure, under the two actions, gelation can be rapidly realized, and silk fibroin/Ming is preparedGlue gel; when the silk fibroin/gelatin hydrogel is immersed in (NH) 4 ) 2 SO 4 When in solution, due to (NH) 4 ) 2 SO 4 Chain entanglement, hydrophobic interactions, and microphase separated domains in the hydrogel network may be induced within the hydrogel, thereby promoting improved mechanical properties of the hydrogel.
Those skilled in the art will appreciate that (NH) 4 ) 2 SO 4 The mass fraction of (2) may be 10% or 20%, which is not limited herein, and may be set according to actual needs.
In summary, the preparation method of the rapid gel silk fibroin-based strong hydrogel provided by the invention prepares the double-crosslinked high-strength hydrogel with a three-dimensional crosslinked network structure by taking gelatin and silk fibroin as raw materials through the processes of blending, chemical crosslinking, low-temperature treatment and the like, and the prepared hydrogel has the characteristics of strong mechanical property and high elasticity; the mechanical strength of the hydrogel is regulated and controlled by adjusting experimental conditions, so that the controllable preparation of the hydrogel is realized, and the requirements of the hydrogel with different mechanical strengths in actual needs are met; the influence of the salt solution on the structure of the silk fibroin and the gelatin is fully utilized, so that the mechanical property of the prepared hydrogel is further improved, and the hydrogel is more suitable for application; by combining chemical crosslinking and non-covalent physical crosslinking, high performance and controllability integration is effectively achieved. Compared with the scheme of preparing the hydrogel in the prior art, the method can realize rapid gelation, the hydrogel can be formed for only 3min, and meanwhile, the method provided by the invention has the advantages of wide raw material sources, mild and green preparation conditions, rapidness and simple preparation process, and has important significance in the controllable preparation of the high-strength functional hydrogel.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (4)
1. The preparation method of the rapid-gel silk fibroin-based strong hydrogel is characterized by comprising the following steps:
s1, preparing a silk fibroin solution: washing degummed silk with deionized water, and drying to obtain dry silk; dissolving the dry silk and performing dialysis treatment to obtain a silk fibroin solution I;
s2, preparing silk fibroin-based hydrogel: adding a cross-linking agent into the silk fibroin solution I obtained in the step S1 to carry out chemical cross-linking to obtain a silk fibroin solution II subjected to chemical cross-linking, and uniformly mixing the silk fibroin solution II with a gelatin solution to obtain a mixed solution III; standing the mixed solution III at a low temperature to obtain silk fibroin/gelatin hydrogel;
the mass fraction of the silk fibroin solution I is 5-10%, and the mass fraction of the gelatin solution is 5-20%; the volume of the silk fibroin solution II and the gelatin solution is (1-2): (0.5-2); the low temperature condition is 0-4 ℃, and the standing time is 3-10 min under the low temperature condition; the cross-linking agent is one or more of MES, NHS and EDC;
s3, sequentially soaking the silk fibroin/gelatin hydrogel obtained in the step S2 in (NH) 4 ) 2 SO 4 Obtaining silk fibroin-based hydrogel in the solution and deionized water; said (NH) 4 ) 2 SO 4 The mass fraction of the solution is 10-20%.
2. The method of preparing a rapid gelling silk fibroin-based strong hydrogel according to claim 1, wherein the silk fibroin/gelatin hydrogel is immersed in (NH 4 ) 2 SO 4 The time in the solution is 10-12 hours.
3. The method for preparing the rapid gel silk fibroin-based strong hydrogel according to claim 1, wherein the dialysis treatment is performed at a temperature of 0-4 ℃ for 24-72 hours.
4. The method for preparing a rapid gel silk fibroin-based strong hydrogel according to claim 1, wherein in step S3, the soaking time of the silk fibroin/gelatin hydrogel in deionized water is 24h to 96h.
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