CN115584036A - Method for dissolving fibroin by mixed acid - Google Patents

Method for dissolving fibroin by mixed acid Download PDF

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CN115584036A
CN115584036A CN202211165497.3A CN202211165497A CN115584036A CN 115584036 A CN115584036 A CN 115584036A CN 202211165497 A CN202211165497 A CN 202211165497A CN 115584036 A CN115584036 A CN 115584036A
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silk
acid
silk fibroin
dissolving
fibroin
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黄继伟
梁苏平
牛翔宇
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Guangxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • 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
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/095—Oxygen containing compounds
    • 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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Abstract

The invention provides a method for dissolving fibroin by mixed acid, which comprises the following steps: s1, degumming silk to obtain degummed silk; s2, mixing organic acid and inorganic acid to obtain a mixed acid solution, and then adding the degummed silk prepared in the step S1 into the mixed acid solution to obtain a silk fibroin solution. The invention provides a method for dissolving silk fibroin by using organic acid and inorganic acid, which can simply and quickly dissolve silk fibroin, has the advantages of easily controlled conditions, good solution stability, less environmental pollution and easy recovery and recycling.

Description

Method for dissolving fibroin by mixed acid
Technical Field
The invention relates to the field of natural high polymer materials, in particular to a method for dissolving fibroin by using neutral salt-mixed acid.
Background
The silk can be used as textile clothing and non-textile clothing materials, for example, silk fibroin can be obtained by some means, and the silk fibroin can be processed and modified into silk fibroin materials and applied to the field of biological medical treatment and the like. The mulberry silk is composed of silk fibroin and sericin, wherein the silk fibroin contains amino acid required by human body, can degrade the silk fibroin into low molecular silk peptide and amino acid, and can be applied to the fields of cosmetics, food, pharmaceutical industry and medical treatment.
An article of Method of creating silk products by Camile et al discloses that inorganic strong acid is used to dissolve silk fibroin, although the silk fibroin can be completely degraded, the reaction conditions are violent, the damage to amino acid is serious, the hydrolysis degree is difficult to control, the Method is harmful to human body, and the Method cannot be used in the aspect of biological medicine. First, hydrochloric acid destroys hydrogen bonds, van der waals force, and the like between polypeptide chains of mulberry silk protein, so that the structure of silk becomes loose, and thus elongation at break may increase. However, as the strength of hydrochloric acid increases, more holes and gaps are formed in the silk fibers, and the number of weak nodes increases, so that the elongation at break is reduced.
Secondly, hydrochloric acid can perform chemical reaction in water, namely the hydrochloric acid generates hydrogen ions and chloride ions to enhance the polarity of the water, the hydrochloric acid can be used as a catalyst of silk to catalyze the hydrolysis of the silk, the chloride ions in the hydrochloric acid can destroy amido bonds of connecting polypeptide chains in the protein, and amino acid sequences in large molecules of the protein can be decomposed into small-molecule free amino acids. Hydrochloric acid can be combined with free amino acid to form a chelate, for example, the group of hydrochloric acid can react with tryptophan group in the silk peptide chain, so that the color is gradually deepened when silk is dissolved.
Therefore, the regenerated silk fibroin membrane prepared by dissolving the silk fibroin solution of the mulberry silk by hydrochloric acid has poor performance and greatly changed structure. The regenerated silk fibroin film is easy to dissolve in water, low in crystallinity, low in initial modulus, poor in mechanical property and easy to crack after being dried. The strong degradation of hydrochloric acid to silk destroys hydrogen bonds and van der Waals force between silks, and decomposes protein macromolecules in mulberry silk into micromolecule amino acids, so that the formed regenerated silk fibroin film lacks macromolecules or intermolecular force connection, the regenerated silk fibroin film is easy to dissolve in water, and the film is easy to crack.
Fibroin does not change obviously in formic acid, but the fibroin is degraded slowly with the lapse of time, and the regenerated fibroin material is easy to dissolve in formic acid, which shows that formic acid not only plays a role of a dispersing agent but also can play a role of dissolving the regenerated fibroin in the fibroin dissolving process; while Ca 2+ 、Li + The surface layer of the silk fibroin is destroyed by the cation with equal strong polarity under the acidic condition, but compared with the traditional method, the method has the defects ofThe support of little high temperature energy, which cannot break van der waals forces and hydrogen bonds of the fibroin molecules, enables to obtain nanofibrillar fibers. Therefore, the formic acid can slowly dissolve the fibroin to a certain extent, the strong polar cations are needed for fast dissolution, the solution contains the strong polar cations under the condition that the further utilization is limited, the strong acid can thoroughly destroy Van der Waals force and hydrogen bonds of fibroin molecules, and the mechanical property of the regenerated material is ensured.
Disclosure of Invention
The technical problem to be solved is as follows: the invention aims to provide a method for dissolving silk fibroin by using organic acid and inorganic acid, which can achieve and give consideration to high solubility, mild dissolving conditions and low solvent consumption as much as possible.
The technical scheme is as follows: a method for dissolving fibroin by mixed acid, comprising the steps of:
s1, degumming silk to obtain degummed silk;
and S2, mixing organic acid and inorganic acid to obtain a mixed acid solution, and adding the degummed silk prepared in the step S1 into the mixed acid solution to obtain the silk fibroin solution.
Preferably, the silk is one or a combination of two or more of mulberry silk, tussah silk and castor-oil plant silk.
Preferably, the organic acid is formic acid and the inorganic acid is phosphoric acid or hydrochloric acid.
Preferably, the concentration of the organic acid is 80-100wt.%, the concentration of the inorganic acid is 0.01-5wt.%, and the volume ratio of the organic acid to the inorganic acid is 1.
Preferably, the concentration of the silk fibroin solution is 0.1-50wt.%.
The regenerated silk fibroin solution is prepared by any method of dissolving silk fibroin by using mixed acid.
The regenerated silk fibroin solution is applied to preparing regenerated silk fibroin materials.
Preferably, the regenerated silk fibroin material comprises a film, a filament, a nanofiber, a porous scaffold, and a hydrogel.
Has the advantages that: the method for dissolving the fibroin by the mixed acid has the following advantages:
1. under the general condition, namely under the condition of normal temperature, fibroin can be dissolved by mixing a small amount of inorganic acid and organic acid without strong polar cations, the method can simply and quickly dissolve the fibroin, the condition is easy to control, the solution stability is good, the environmental pollution is less, and the recovery and the cyclic utilization are easy;
2. the invention overcomes the problems that the regenerated silk fibroin film prepared by dissolving fibroin solution of fibroin by hydrochloric acid in the traditional mode is easy to dissolve in water, has low crystallinity, low initial modulus and poor mechanical property, and is easy to crack after the film is dried.
Drawings
FIG. 1 is a line graph showing the MSF dissolution amount of different hydrochloric acids and the MSF dissolution amount of hydrochloric acid-assisted formic acid;
fig. 2 is an appearance of a regenerated silk membrane after being dried for a period of time, wherein a is a silk membrane in which 2wt.% calcium chloride and 98wt.% formic acid dissolve MSF; b is a fibroin film with 1wt.% hydrochloric acid-98 wt.% formic acid to dissolve MSF; c is a fibroin membrane with 2wt.% hydrochloric acid-98 wt.% formic acid to dissolve MSF; d is a fibroin membrane with MSF dissolved by 3wt.% hydrochloric acid-98 wt.% formic acid; e is a fibroin membrane with 4wt.% hydrochloric acid-98 wt.% formic acid to dissolve MSF; f is 5wt.% hydrochloric acid-98 wt.% formic acid to dissolve the silk fibroin film of MSF;
fig. 3 is a FTIR plot of silk fibroin for different dissolution systems, where a is 2wt.% calcium chloride-98 wt.% formic acid dissolved 0.8g MSF; b is 1wt.% hydrochloric acid to 98wt.% formic acid dissolved in 0.8g MSF; c 5wt.% hydrochloric acid to 98wt.% formic acid to dissolve 0.8g MSF; d is 10wt.% hydrochloric acid to 98wt.% formic acid dissolved in 0.8g MSF; e is 20wt.% hydrochloric acid to 98wt.% formic acid dissolved in 0.8g MSF; f is 30wt.% hydrochloric acid to 98wt.% formic acid dissolved in 0.8g MSF;
figure 4 is the XRD pattern of silk fibroin for different dissolution systems, wherein a is 2wt.% calcium chloride-98 wt.% formic acid dissolving 8g MSF; b is 1wt.% hydrochloric acid to 98wt.% formic acid dissolved in 0.8g MSF; c 5wt.% hydrochloric acid to 98wt.% formic acid to dissolve 0.8g MSF; d is 10wt.% hydrochloric acid-98 wt.% formic acid dissolved 0.8g MSF; e is 20wt.% hydrochloric acid to 98wt.% formic acid dissolved in 0.8g MSF; f is 30wt.% hydrochloric acid to 98wt.% formic acid dissolved in 0.8g MSF;
fig. 5 is an electrophoretic picture of silk fibroin used for dissolving MSF in different dissolving systems, wherein a is 2wt.% calcium chloride-98 wt.% formic acid dissolving 8g MSF; b is 1wt.% hydrochloric acid to 98wt.% formic acid dissolved in 0.8g MSF; c 5wt.% hydrochloric acid to 98wt.% formic acid to dissolve 0.8g MSF; d is 10wt.% hydrochloric acid to 98wt.% formic acid dissolved in 0.8g MSF; e is 20wt.% hydrochloric acid-98 wt.% formic acid dissolved 0.8g MSF; f is 30wt.% hydrochloric acid-98 wt.% formic acid dissolved 0.8g MSF.
Detailed Description
The present invention will be further described with reference to the following embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Verification experiment:
hydrochloric acid to degummed mulberry silk dissolution rate
S1, boiling natural mulberry silk with 0.1wt% of sodium carbonate solution for 30min to be degummed, and repeating for 3 times to obtain degummed Mulberry Silk (MSF);
s2, preparing hydrochloric acid with the concentration of 1-6 mol/L, dissolving 0.8g of MSF in 10mL of hydrochloric acid with different concentrations, and hydrolyzing the MSF in a water bath for 4h at the temperature of 40 ℃ and the bath ratio of 1. And cleaning the hydrolyzed product by using deionized water, and drying to obtain the dissolution rate.
Hydrochloric acid assisted formic acid dissolution degumming mulberry silk dissolution rate
S1, boiling natural mulberry silk with 0.1wt% of sodium carbonate solution for 30min to degum, and repeating for 3 times to obtain degummed mulberry silk;
and S2, preparing different quality dissolving systems (1 wt.% hydrochloric acid and 98wt.% formic acid, 2wt.% hydrochloric acid and 98wt.% formic acid, 3wt.% hydrochloric acid and 98wt.% formic acid, 4wt.% hydrochloric acid and 98wt.% formic acid, 5wt.% hydrochloric acid and 98wt.% formic acid), taking 1wt.% MSF as a dissolving step, adding in series until the dissolving saturation is reached, and stopping adding to obtain the MSF dissolving amount.
As can be seen from fig. 1, formic acid has the effect of swelling MSF and hydrochloric acid has the effect of catalyzing the hydrolysis of MSF. In a hydrochloric acid-formic acid dissolving system, the hydrochloric acid and the formic acid are combined, the hydrochloric acid can generate chemical reaction in water to generate ions, and the polarity of the water is enhanced after the ions are dissolved in the water, so that the silk fibroin is more easily swelled and dissolved in the water, the MSF is completely dissolved, and the dissolving amount of the MSF is increased. The dissolution curves of the different hydrochloric acid concentrations versus MSF in fig. 1 a increase relatively slowly, whereas the dissolution curves of the hydrochloric acid assisted formic acid versus MSF in fig. 1 b increase relatively rapidly. It was therefore concluded that hydrochloric acid assisted formic acid is better able to dissolve MSF.
Example 1
A method for dissolving fibroin by mixed acid comprises the following steps:
s1, boiling natural mulberry silk with 0.1wt% of sodium carbonate solution for 30min to degum, and repeating for 3 times to obtain degummed mulberry silk;
and S2, mixing 98wt.% organic acid and 1wt.% inorganic acid according to a volume ratio of 1.
Example 2
A method for dissolving fibroin by mixed acid comprises the following steps:
s1, boiling natural mulberry silk with 0.1wt% of sodium carbonate solution for 30min to degum, and repeating for 3 times to obtain degummed mulberry silk;
and S2, mixing 98wt.% organic acid and 2wt.% inorganic acid according to a volume ratio of 1.
Example 3
A method for dissolving fibroin by mixed acid comprises the following steps:
s1, boiling natural mulberry silk with 0.1wt% of sodium carbonate solution for 30min to degum, and repeating for 3 times to obtain degummed mulberry silk;
and S2, mixing 98wt.% organic acid and 3wt.% inorganic acid according to a volume ratio of 1.
Example 4
A method for dissolving fibroin by mixed acid comprises the following steps:
s1, boiling natural mulberry silk with 0.1wt% of sodium carbonate solution for 30min to degum, and repeating for 3 times to obtain degummed mulberry silk;
and S2, mixing 98wt.% organic acid and 4wt.% inorganic acid according to a volume ratio of 1.
Example 5
A method for dissolving fibroin by mixed acid, comprising the steps of:
s1, boiling natural mulberry silk with 0.1wt% of sodium carbonate solution for 30min to degum, and repeating for 3 times to obtain degummed mulberry silk;
and S2, mixing 98wt.% organic acid and 5wt.% inorganic acid according to a volume ratio of 1.
Comparative example 1
Formic acid-CaCl 2 A method of lysing silk fibroin comprising the steps of:
s1, boiling natural mulberry silk with 0.1wt% of sodium carbonate solution for 30min to degum, and repeating for 3 times to obtain degummed mulberry silk;
s2, adding CaCl 2 Adding to 98wt.% formic acid solution, and adding into the mixed acid solutionAdding the degummed mulberry silk prepared in the step S1 and CaCl 2 And the mass ratio of the degummed silk to the degummed silk is 2.
Comparative example 2
A method for dissolving fibroin by mixed acid comprises the following steps:
s1, boiling natural mulberry silk with 0.1wt% of sodium carbonate solution for 30min to degum, and repeating for 3 times to obtain degummed mulberry silk;
and S2, mixing 98wt.% organic acid and 10wt.% organic acid according to a volume ratio of 1.
The silk fibroin solutions prepared in examples 1-5 and comparative example 1 were respectively spread on petri dishes with flat surfaces, and placed in a dry and cool vent until the membranes were dried. And (3) soaking the membrane containing calcium chloride in the comparative example 1 in deionized water for desalting for 2 days, wherein the deionized water needs to be replaced, and airing the desalted membrane.
After the films of examples 1 to 5 and comparative example 1 were dried for a while, the surfaces were compared, and it can be seen from FIG. 2 that a is a regenerated silk fibroin film in which MSF is dissolved by calcium chloride-formic acid, and has small brittleness, high toughness, and high crystallinity. The silk fibroin consists of a crystalline region and an amorphous region, and strong hydrogen bonds and intermolecular forces are formed between peptide chains in the crystalline region, so that the combination is tight, the arrangement is neat, and the tensile resistance is strong; the intermolecular binding force of peptide chains in the amorphous region is weak, unstable and the arrangement is very irregular, so the peptide chains are easily dissolved in acid, enzyme and salt. The effect of calcium chloride on MSF is thus to disrupt the amorphous regions of the regenerated silk fibroin membrane. b. c, d, e and f are regenerated silk fibroin films (respectively corresponding to the embodiments 1 to 5) formed by dissolving MSF by hydrochloric acid-formic acid, and the brittleness is gradually increased. Hydrochloric acid is a strong acid, can violently hydrolyze MSF, destroy intermolecular force and hydrogen bonds of peptide chain segments and peptide bonds in polypeptide, and decompose silk fibroin macromolecules into micromolecular amino acids, so that the regenerated silk fibroin film is easy to crack and is easy to dissolve in water.
To verify the dissolution of the mixed acid and formic acid-CaCl 2 Dissolving and degumming silkThe regenerated silk fibroin membrane is subjected to infrared test and XRD test, and the infrared test shows that the silk fibroin dissolved by hydrochloric acid-formic acid generates an obvious absorption peak, and the peak type of the absorption peak is sharp; the absorption peak generated by the silk fibroin solution dissolved by calcium chloride-formic acid is widened, and the sharpness is not obvious. The difference between chloride ions and calcium ions in a hydrochloric acid-formic acid and calcium chloride-formic acid dissolving system is that the ions of the hydrochloric acid-formic acid and the calcium chloride-formic acid act on groups or hydrogen bonds in the protein to change the groups in the protein, so that the structure of the protein is changed; as can be seen from XRD test, alpha-helix structure of silk I structure and beta-sheet structure of silk II structure exist in a and b in the figure, but the beta-sheet structure is taken as main structure; curve c shows a silk i structure, and curves d, e, and f all show random coil structures. Therefore, the hydrochloric acid can change the structure in the silk fibroin, and as the mass fraction of the hydrochloric acid is increased, the diffraction peak related to a beta-fold structure gradually disappears, the diffraction peak related to a random coil structure appears, and the peak type is more and more obvious. It is hypothesized herein that the increased amount of hydrochloric acid is responsible for the more random coil structures that appear in silk fibroin.
FIG. 5 is an electrophoresis diagram of a SDS-PAGE gel electrophoresis detection method after MSF is dissolved under different dissolution conditions to obtain silk fibroin solutions with different molecular weights. From left to right, panel M is a standard protein Marker (17-180 kDa). The SDS-PAGE results of silk fibroin solutions with different solubilization systems for dissolving MSF are obviously different, and the mulberry silk fibroin is generally considered to be composed of heavy chain (H chain), light chain (L chain) and P25 protein, the relative molecules of the heavy chain (H chain) and the light chain (L chain) are 390kDa, respectively, and the L chain (L chain) and the P25 protein 25kDa, respectively, and the heavy chain (H chain) and the light chain (L chain) are connected together in a disulfide bond mode, while the P25 protein is connected with the heavy chain (H chain) and the light chain (L chain) in a non-covalent bond mode. The molecular weight distribution in the graph a is the most extensive, and the molecular weight distribution is in the range of 17 to 180kDa, which is caused by the degradation of the heavy chain in the silk fibroin due to the influence of calcium chloride on the macromolecules of the silk fibroin.
Along with the increase of the mass fraction of the hydrochloric acid, the colors of b, c, d, f and g (g corresponds to a comparative example 2) in the strip intervals of 35 to 180kDa gradually become lighter, wherein the molecular weights of b, c, d, f and g are respectively as follows: the molecular weight of the band b is 35kDa, the molecular weights of c, d and f are all 28kDa, and the band g is below 17 kDa. This shows that the hydrochloric acid can reduce the molecular weight of silk fibroin, the mass fraction of the hydrochloric acid increases, and the degree of reduction of the molecular weight of silk fibroin is greater, so that it can be confirmed that the hydrochloric acid seriously damages the silk fibroin macromolecules, and the degree of damage of the silk fibroin molecules is greater as the mass fraction of the hydrochloric acid increases. Compared with the graph a, the molecular weight of the bands b, c, d, f and g is reduced to the greatest extent. Therefore, the molecular weight and the distribution of the silk fibroin are related to the mass fractions of the hydrochloric acid and the hydrochloric acid, the hydrochloric acid has a large influence on the molecular weight of the silk fibroin, and the molecular weight of the silk fibroin is gradually reduced along with the increase of the mass fraction of the hydrochloric acid.
The invention discovers that the MSF is hydrolyzed more violently by hydrochloric acid, the intermolecular force, hydrogen bonds and peptide bonds for connecting polypeptides of the protein are destroyed, the macromolecular protein is decomposed into micromolecular amino acids, and the dissolving amount of the MSF is gradually increased along with the increase of the concentration of the hydrochloric acid; the hydrochloric acid assists the formic acid to dissolve the MSF, the formic acid has the function of swelling the MSF, and the hydrochloric acid plays the role of catalyzing the MSF hydrolysis. When the two are combined in a hydrochloric acid-formic acid dissolving system, the hydrochloric acid can generate chemical reaction in water to generate ions, and the polarity of the water is enhanced after the ions are dissolved in the water, so that the silk fibroin is easier to swell and dissolve in the water, the MSF is completely dissolved, and the dissolving amount of the MSF is increased. And along with the increase of the concentration of the hydrochloric acid, the MSF dissolution amount is larger than that of hydrochloric acid with different concentrations, so that the solubility of the hydrochloric acid auxiliary formic acid to the MSF is better than that of the hydrochloric acid with different concentrations. Calcium chloride and hydrochloric acid both degrade MSF, both reduce the molecular weight of MSF, but the degradation degree of both are different. The calcium chloride-formic acid and the hydrochloric acid-formic acid dissolve the regenerated silk fibroin membrane of the MSF, the calcium chloride has a small degree of reducing the molecular weight of the MSF, the hydrochloric acid has a large degree of reducing the molecular weight of the MSF, the molecular weight distribution is below 35kDa, and the molecular weight is reduced less along with the increase of the mass fraction of the hydrochloric acid. Therefore, the molecular weight of the silk fibroin needing regeneration for silk fibroin dissolution is lower than 35kDa, and the silk fibroin can be prepared by adopting the method.
In order to verify that the silk fibroin solution prepared by the dissolving method has spinnability, mixing 98wt.% organic acid and 0.5wt.% inorganic acid according to a volume ratio of 1; the regenerated silk fibroin fiber filament prepared by wet spinning is measured for mechanical property, the breaking strength is 117.2 +/-25.3 MPa, the breaking productivity is 12.3 +/-3.9%, the breaking strength of the regenerated silk fibroin fiber prepared by wet spinning with the silk fibroin solution in a comparative example is 376.6 +/-44.5 MPa, and the breaking elongation is 19.2 +/-4.5%; from the above results, it can be seen that although the mechanical properties of the regenerated silk fibroin filament prepared by the present invention are inferior to those of the comparative examples, the data show that the silk fibroin solution prepared by the dissolution method of the present invention has spinnability, and the regenerated silk fibroin filament with a certain mechanical property can be prepared. The regenerated silk fibroin solution can be applied to preparing regenerated silk fibroin materials.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (8)

1. The method for dissolving the silk fibroin by the mixed acid is characterized by comprising the following steps:
s1, degumming silk to obtain degummed silk;
and S2, mixing organic acid and inorganic acid to obtain a mixed acid solution, and adding the degummed silk prepared in the step S1 into the mixed acid solution to obtain the silk fibroin solution.
2. The method of dissolving silk elements with mixed acids according to claim 1, wherein: the silk is one or a combination of two or more of mulberry silk, tussah silk or castor-oil plant silk.
3. The method of dissolving silk elements with mixed acids according to claim 1, wherein: the organic acid is formic acid, and the inorganic acid is phosphoric acid or hydrochloric acid.
4. The method of mixed acid dissolving silk fibroin according to claim 3, wherein: the concentration of the organic acid is 80-100wt.%, the concentration of the inorganic acid is 0.01-5wt.%, and the volume ratio of the organic acid to the inorganic acid is 1.
5. The method of mixed acid dissolving silk element of claim 1, wherein: the concentration of the silk fibroin solution is 0.1-50wt.%.
6. The regenerated silk fibroin solution prepared by the method for dissolving silk fibroin with mixed acid as claimed in any one of claims 1-6.
7. Use of the regenerated silk fibroin solution of claim 6 in the preparation of regenerated silk fibroin material.
8. The use of claim 7, wherein the regenerated silk fibroin material comprises a film, a filament, a nanofiber, a porous scaffold, and a hydrogel.
CN202211165497.3A 2022-09-23 2022-09-23 Method for dissolving fibroin by mixed acid Pending CN115584036A (en)

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