CN114539564A - Preparation method of rapid-gelling silk fibroin-based strong hydrogel - Google Patents
Preparation method of rapid-gelling silk fibroin-based strong hydrogel Download PDFInfo
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Abstract
The invention provides a preparation method of a rapid-gelling silk fibroin-based strong hydrogel, which comprises the steps of cleaning degummed silk with deionized water, drying, dissolving and dialyzing to prepare 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 at a low temperature to obtain the silk fibroin/gelatin hydrogel. By the combined use of chemical crosslinking and physical crosslinking, the efficient combination between silk fibroin and gelatin is realized, and the integration of high performance and controllability is realized; the salt solution is used for inducing the molecular structures of the fibroin and the gelatin, so that 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-gelling silk fibroin-based strong hydrogel.
Background
Gels are in a form between solid and liquid and are classified into elastic gels and non-elastic gels according to the nature of the dispersed particles and the nature of the connection between the particles when the gel structure is formed. The hydrogel is an elastic gel formed by a high molecular compound solution, takes water as a dispersion medium, can absorb and retain a large amount of water, has a cross-linked network structure, is formed by cross-linking hydrophilic high molecular compounds through ionic bonds, covalent bonds, hydrogen bonds and the like, and has the characteristics of a high polymer electrolyte and a three-dimensional structure. The hydrogel has higher water content and more internal void structures, the interconnected porous structures provide channels for the transportation of water, nutrients, medicines and the like, provide a good environment for the migration and proliferation of cells, are considered to be good materials for the encapsulation and transmission of cells and bioactive molecules, and can be used for tissue engineering, cell treatment and the like.
Silk fibroin is a natural high molecular protein extracted from silk, and its internal structure is divided into crystalline region and amorphous region. The anti-parallel beta-folding structures form a crystallization area, the irregular curling structures belong to an amorphous area, the crystallization area is generally relatively and uniformly dispersed in the amorphous area, molecular chains in the amorphous area and the microcrystalline area are orderly arranged along the direction of a 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 the influence of the arrangement order of amino acids on the molecular conformation. The silk fibroin has 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, the silk fibroin hydrogel prepared by physical crosslinking has slow gel speed, poor structural stability and poor mechanical property; the silk fibroin hydrogel prepared by a chemical crosslinking method has poor elasticity, and the application of the silk fibroin hydrogel in the fields of regenerative medicine, tissue engineering and the like is limited due to the defects. Therefore, the method for preparing the silk fibroin hydrogel with excellent mechanical properties and biocompatibility is very important.
Chinese patent application No. 200910025440.1, published on 2012/07/25/month, entitled "a method for preparing silk fibroin hydrogel" discloses a method for preparing silk fibroin hydrogel. In the method, the silk of the family silks is subjected to degumming, dissolution and dialysis treatment to obtain a silk fibroin solution with the mass concentration of 1-30%; then, carrying out ultrasonic oscillation treatment at 37 ℃ to obtain silk fibroin hydrogel; and finally, pouring the treated silk fibroin solution into a mold, 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 subjected to biological crosslinking under the action of ultrasonic waves, and the silk fibroin forms a beta-folded crystal structure, but the formed silk fibroin hydrogel is very hard and brittle, and cannot meet the application requirements of subsequent high-strength and high-toughness silk fibroin materials.
Chinese patent application No. 201810662604.0, published on 2020, 06, 02, 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 stirring to obtain a crosslinked solution; centrifuging the crosslinking solution to remove bubbles, pouring the crosslinking solution into a mold, and reacting and curing 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; and washing with running water to obtain the double-network cross-linked cellulose/silk fibroin high-strength hydrogel. Although the technical scheme can prepare the high-strength hydrogel, the preparation process needs to use an alkali solution and a toxic organic solution, the preparation process is complex, and the time required for gelation is long.
In view of the above, there is a need to design an improved method for preparing a rapid-gelling silk fibroin-based strong hydrogel to solve the above problems.
Disclosure of Invention
The invention aims to provide a preparation method of a rapid-gelling silk fibroin-based strong hydrogel with simple and convenient preparation, high gelling speed, strong mechanical property and high elasticity.
In order to realize the purpose, the invention provides a preparation method of a rapid-gelling silk fibroin-based strong hydrogel, which comprises the following steps:
s1, preparation of the fibroin solution: cleaning the degummed silk with deionized water, and drying to obtain dry silk; dissolving the dry silk and dialyzing to prepare a silk fibroin solution I;
s2, preparation of silk fibroin-based hydrogel: adding a cross-linking agent into the silk fibroin solution I obtained in the step S1 for chemical cross-linking to obtain a chemically cross-linked silk fibroin solution II, 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 silk fibroin-based strong hydrogel for rapid gelation further comprises the following steps:
s3, sequentially soaking the silk fibroin/gelatin hydrogel obtained in the step S2 in (NH)4)2SO4And (3) obtaining the silk fibroin-based hydrogel in the solution and deionized water.
Preferably, said (NH)4)2SO4Mass fraction of solutionThe number of the particles is 10 to 20%.
Preferably, the silk fibroin/gelatin hydrogel is soaked in (NH)4)2SO4The 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 temperature of the dialysis treatment is 0-4 ℃ and the time is 24-72 h.
Preferably, in step S2, the low temperature condition is 0 to 4 ℃, and the standing time under the low temperature condition is 3 to 10 min.
Preferably, the crosslinking agent is one or more of MES, NHS and EDC.
Preferably, in step S3, the soaking time of the silk fibroin/gelatin hydrogel in deionized water is 24 to 96 hours.
The invention has the beneficial effects that:
1. according to the preparation method of the rapid-gelling silk fibroin-based strong hydrogel, the gelatin and the silk fibroin are used as raw materials, and the hydrogel with a double-crosslinking high-strength three-dimensional crosslinking net structure is prepared through 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 rapid gelation, provided by the invention, the mechanical strength of the hydrogel is regulated and controlled by adjusting experimental conditions so as to realize controllable preparation of the gel, and the requirements of the hydrogel with different mechanical strengths in actual needs are met; the salt solution is fully utilized to regulate and control the structures of the fibroin and the gelatin, so that the mechanical property of the prepared hydrogel is improved, and the hydrogel can better meet the application requirement; the combination of silk fibroin and gelatin is realized by firstly carrying out chemical crosslinking on silk fibroin and then carrying out physical crosslinking on the silk fibroin and gelatin, and meanwhile, the chemical crosslinking and the non-covalent physical crosslinking are combined, so that the high-performance and controllable integrated preparation can be effectively realized.
3. The preparation method of the rapid-gelling silk fibroin-based strong hydrogel provided by the invention realizes 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 controllable preparation of the gel, meets the requirements of actual requirements on hydrogels with different mechanical strengths, has the advantages of rapidness, mild preparation conditions and simple preparation process, and has important significance in controllable preparation of high-strength functional hydrogels.
Drawings
FIG. 1 is an SEM image of a hydrogel prepared in example 1 of the preparation method of a rapidly gelling silk fibroin-based strong hydrogel according to the present invention;
FIG. 2 is an SEM photograph of the hydrogel prepared in example 2;
FIG. 3 is an SEM photograph of the hydrogel prepared in comparative example 2;
FIG. 4 is an SEM photograph of a hydrogel prepared in comparative example 3;
FIG. 5 is a stress-strain graph of the hydrogels prepared in examples 1 to 2 of the present invention and comparative examples 1 to 3.
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 with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be 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 capable of rapidly gelling, provided by the invention, comprises the following steps:
s1, preparation of the fibroin solution: cleaning degummed silk with deionized water, and drying at 60 deg.C to obtain dry silk; dissolving the dry silk and dialyzing to prepare a silk fibroin solution I;
s2, preparation of 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 chemically cross-linked silk fibroin solution II, 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 prepare the silk fibroin/gelatin hydrogel.
S3, sequentially soaking the silk fibroin/gelatin hydrogel obtained in the step S2 in (NH)4)2SO4And (3) adding the solution and deionized water to prepare the silk fibroin-based hydrogel.
In step S1, the degumming process includes the following steps:
s11, soaking 100g of mulberry silk into 5L of 0.1% sodium carbonate solution, boiling for 30min at the temperature of 98-100 ℃, taking out the silkworm cocoons after each boiling, and washing with deionized water;
s12, adding the silkworm cocoons cleaned in the step S1 into a newly-prepared 5L of sodium carbonate solution with the mass fraction of 0.1%, boiling for 30min at 98-100 ℃, and repeating the steps for three times.
Specifically, in step S1, the temperature of the dialysis treatment is 0-4 ℃ and the time is 24-72 h; the mass fraction of the silk fibroin solution I is 5-10%, and the drying time is 72 h.
Specifically, in step S2, the chemical crosslinking time is 5-10 min; the silk fibroin solution II and the gelatin solution are mixed according to the volume ratio (1-2): (0.5-2) mixing uniformly.
And in the step S2, the mixed solution III is injected into a mold, and the mold is placed at a low temperature of 0-4 ℃ for standing for 3-10 min to obtain the silk fibroin/gelatin hydrogel.
Wherein, in 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)2SO4The mass fraction of the solution is 10-20%, and the silk fibroin/gelatin hydrogel is soaked in (NH)4)2SO4The time in the solution is 10-12 h, and the (NH) is adopted4)2SO4The volume of the solution is 100mL, and the time for soaking the silk fibroin/gelatin hydrogel in deionized water is 24-96 h.
Example 1
Soaking 100g of silk into 5L of 0.1% sodium carbonate solution, boiling at 98-100 deg.C for 30min, taking out cocoon after each boiling, and cleaning with deionized water; and then, adding the cleaned silkworm cocoons into 5L of 0.1 mass percent sodium carbonate solution, repeating the steps for three times until the silkworm cocoons are degummed, fully washing the silkworm cocoons with deionized water, and drying the silkworm cocoons in an oven for 72 hours at the temperature of 60 ℃ to obtain the pure silk fibroin fibers.
Then, 5g of the prepared pure silk fibroin fiber is dissolved in 25mL of lithium bromide solution to obtain silk fibroin solution with the mass fraction of 5%, and then the silk fibroin solution is dialyzed for 72 hours at 4 ℃; after dialysis, adding MES (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 into the silk fibroin solution as a crosslinking agent for chemical crosslinking, wherein the crosslinking time is 5min, so as to obtain a crosslinked silk fibroin solution; then, adding a gelatin solution with the mass fraction of 10% into the silk fibroin solution after the cross-linking treatment, wherein the volume ratio of the silk fibroin solution to the gelatin solution is 1:1, after uniformly mixing, injecting the mixed solution into a mold, placing the mold into a refrigerator, and standing the mold for 3min at the temperature of 4 ℃ to prepare silk fibroin/gelatin hydrogel; finally, the prepared silk fibroin/gelatin waterSoaking the gel in 15% 100mL (NH)4)2SO4Soaking for 12h to enhance the mechanical property of the hydrogel, and soaking the hydrogel in deionized water for 72h to remove (NH) adsorbed in and on the hydrogel4)2SO4The silk fibroin-based strong hydrogel is prepared, and the SEM image of the prepared hydrogel is shown in figure 1, wherein the hydrogel is in a three-dimensional porous structure and is uniform and dense in pore size.
Example 2
Example 2 differs from example 1 only in that: the prepared silk fibroin/gelatin hydrogel is Not (NH)4)2SO4The soaking treatment in the solution, and the rest steps are basically the same as the example 1, and are not repeated. The SEM photograph of the hydrogel thus obtained is shown in FIG. 2, in which it can be seen that the hydrogel had a three-dimensional pore-like structure and uniform pore size, and the pore size was increased as compared with the hydrogel obtained in example 1.
Comparative example 1
Comparative example 1 differs from example 1 only in that: the 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 the fibroin hydrogel, and the rest steps are basically the same as those in the embodiment 1 and are not repeated.
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 the silk fibroin solution and the gelatin solution, then adding the mixed solution into an injection mold, and carrying out freezing treatment in a refrigerator at 4 ℃ for 10min, wherein the rest steps are basically the same as those in the embodiment 1 and are not repeated. The SEM image of the hydrogel is shown in FIG. 3, and it can be seen from FIG. 3 that the hydrogel has a three-dimensional pore structure inside, uniform pore size and dense pore structure.
Comparative example 3
Comparative example 3 differs from example 1 only in that: the prepared silk fibroin solution is directly injected into a mould and is dried in an oven for 72 hours at the temperature of 60 ℃, and the rest steps are basically the same as the embodiment 1 and are not repeated. The SEM image of the prepared hydrogel is shown in FIG. 4, and from FIG. 4, the hydrogel is seen to be internally provided with three-dimensional pore-shaped structures, the pore size distribution is not uniform, and cracks can be observed in the material in the visual field of a lens; the stress-strain curves of the hydrogels obtained in examples 1 to 2 and comparative examples 1 to 3 are shown in fig. 5, from which it can be seen that the hydrogel obtained by applying the method of example 1 has 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 differently, the remaining steps were substantially the same as in example 1, and are not repeated herein, and the strength of the silk fibroin/gelatin hydrogel prepared at different volume ratios is shown in table 1: it can be seen from the data in the table that when the volume ratio of the silk fibroin solution after chemical crosslinking to the gelatin solution is 1:1, the hydrogel obtained has the highest strength.
TABLE 1 volume ratio settings of examples 3-7 and strength of 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 and the mass fraction of the gelatin solution are different, the rest steps are basically the same as those in example 1, and are not repeated here, and the strength of the silk fibroin/gelatin hydrogel prepared under different mass fraction ratios is shown in table 2: as can be seen from the data in the table, when the mass fraction of the silk fibroin solution and the gelatin solution is 5%: at 10%, the hydrogel obtained had the highest strength.
TABLE 2 Mass fraction settings of examples 8-12 and Strength of Silk fibroin/gelatin hydrogels made under these conditions
The following is a description of the mechanism of formation of the fibroin-based hydrogel:
in the presence of a cross-linking agent, the residue of the silk fibroin reacts with the cross-linking agent to promote the combination of the fibrin and the cross-linking agent in a chemical bond manner; then, adding gelatin solution into the chemically cross-linked silk fibroin solution, standing at low temperature, converting the silk fibroin from a random structure to a beta-folded structure at low temperature, and simultaneously mutually inserting the silk fibroin solution and the gelatin solution to form a macromolecular structure, so that gelation can be quickly realized under the two effects, and the silk fibroin/gelatin hydrogel is prepared; when soaking the silk fibroin/gelatin hydrogel in (NH)4)2SO4When in solution, due to (NH)4)2SO4Chain entanglement, hydrophobic interactions, and microphase separated regions in the hydrogel network can be induced within the hydrogel, thereby promoting enhanced mechanical properties of the hydrogel.
As will be appreciated by those skilled in the art, (NH)4)2SO4The mass fraction of (b) may also be 10% or 20%, and the mass fraction is not limited to this, and only needs to be set according to actual needs.
In conclusion, the preparation method of the rapid-gelling silk fibroin-based strong hydrogel provided by the invention takes gelatin and silk fibroin as raw materials, and prepares the double-crosslinking high-strength hydrogel with a three-dimensional crosslinking network structure through 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 as to realize the controllable preparation of the gel, and the requirements on hydrogels with different mechanical strengths in actual needs are met; the influence of the salt solution on the structures of the fibroin and the gelatin is fully utilized, 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, the integration of high performance and controllability is effectively realized. Compared with the scheme for preparing the hydrogel in the prior art, the method can realize rapid gelation, the formation of the hydrogel only needs 3min, and meanwhile, the method provided by the invention also has the advantages of wide raw material source, mild, green and rapid preparation conditions and simple preparation process, and has important significance in the controllable preparation of the high-strength functional hydrogel.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A preparation method of a rapid-gelling silk fibroin-based strong hydrogel is characterized by comprising the following steps:
s1, preparation of the fibroin solution: cleaning the degummed silk with deionized water, and drying to obtain dry silk; dissolving the dry silk and dialyzing to prepare a silk fibroin solution I;
s2, preparation of silk fibroin-based hydrogel: adding a cross-linking agent into the silk fibroin solution I obtained in the step S1 for chemical cross-linking to obtain a chemically cross-linked silk fibroin solution II, 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.
2. The method for preparing the silk fibroin-based strong hydrogel for rapid gelation according to claim 1, further comprising the steps of:
s3, sequentially soaking the silk fibroin/gelatin hydrogel obtained in the step S2 in (NH)4)2SO4And (3) obtaining the silk fibroin-based hydrogel in the solution and deionized water.
3. The method of claim 2, wherein the (NH) is selected from the group consisting of4)2SO4The mass fraction of the solution is 10-20%.
4. The method for preparing rapid-gelling silk fibroin-based strong hydrogel according to claim 2, wherein said silk fibroin/gelatin hydrogel is soaked in (NH)4)2SO4The time in the solution is 10-12 h.
5. The preparation method of the rapid-gelling silk fibroin-based strong hydrogel according to claim 1, wherein the mass fraction of the silk fibroin solution I is 5-10%, and the mass fraction of the gelatin solution is 5-20%.
6. The method for preparing the rapid-gelling silk fibroin-based strong hydrogel according to claim 5, wherein the volume of the mixture of the silk fibroin solution II and the gelatin solution is (1-2): (0.5-2).
7. The preparation method of the rapid-gelling silk fibroin-based strong hydrogel according to claim 1, wherein the dialysis treatment temperature is 0-4 ℃ and the dialysis treatment time is 24-72 hours.
8. The method for preparing the silk fibroin-based strong hydrogel capable of rapidly gelling according to claim 1, wherein in step S2, the low temperature condition is 0-4 ℃, and the standing time under the low temperature condition is 3-10 min.
9. The method for preparing the silk fibroin-based strong hydrogel for rapid gelation according to claim 1, wherein the cross-linking agent is one or more of MES, NHS and EDC.
10. The method for preparing the silk fibroin-based strong hydrogel for rapid gelation according to claim 2, wherein in step S3, the soaking time of the silk fibroin/gelatin hydrogel in deionized water is 24-96 h.
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