CN107298766A - Regenerate tussah silk fibroin solution and preparation method thereof - Google Patents
Regenerate tussah silk fibroin solution and preparation method thereof Download PDFInfo
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- CN107298766A CN107298766A CN201710502045.2A CN201710502045A CN107298766A CN 107298766 A CN107298766 A CN 107298766A CN 201710502045 A CN201710502045 A CN 201710502045A CN 107298766 A CN107298766 A CN 107298766A
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- Prior art keywords
- tussah silk
- silk fibroin
- preparation
- regeneration
- tussah
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- 108010022355 Fibroins Proteins 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000008929 regeneration Effects 0.000 claims abstract description 40
- 238000011069 regeneration method Methods 0.000 claims abstract description 40
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000502 dialysis Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 45
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 40
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 23
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 17
- 235000019253 formic acid Nutrition 0.000 claims description 17
- 230000001172 regenerating effect Effects 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 238000002203 pretreatment Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 5
- 238000002525 ultrasonication Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 18
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 230000029087 digestion Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000011664 nicotinic acid Substances 0.000 abstract 1
- 210000001519 tissue Anatomy 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000002121 nanofiber Substances 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 108090000623 proteins and genes Proteins 0.000 description 5
- 102000004169 proteins and genes Human genes 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- 108090000765 processed proteins & peptides Proteins 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000255789 Bombyx mori Species 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 2
- 235000008708 Morus alba Nutrition 0.000 description 2
- 240000000249 Morus alba Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003295 alanine group Chemical group N[C@@H](C)C(=O)* 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000003519 biomedical and dental material Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 241000255978 Antheraea pernyi Species 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010037362 Extracellular Matrix Proteins Proteins 0.000 description 1
- 102000010834 Extracellular Matrix Proteins Human genes 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 210000002744 extracellular matrix Anatomy 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012460 protein solution Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08J3/098—Other compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/227—Other specific proteins or polypeptides not covered by A61L27/222, A61L27/225 or A61L27/24
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/52—Hydrogels or hydrocolloids
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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
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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
- C08J3/09—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
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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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Abstract
The present invention relates to one kind regeneration tussah silk fibroin solution and preparation method thereof, the solution constitutes for pure tussah silk fibroin, and fibroin albumen is mainly nanofibrous structures, and its diameter is in below 50nm, and length is between 100~500nm.The solution manufacturing method dissolves directly using natural tussah silk as raw material, by organic solvent, obtain after deionized water dialysis treatment.Preparation method of the present invention is directly dissolved with organic solvent, it is to avoid the strong degradation problem of high concentration neutral salt high-temperature digestion, and technique is simple, and thus obtained solution is remained without reagent, simultaneously containing nano bionic structure, with excellent biological safety.
Description
Technical field
The present invention relates to a kind of natural polymer solution and preparation method thereof, and in particular to one kind regeneration tussah silk fibroin
Solution and preparation method thereof.
Background technology
Bio-medical material is one of current life science and the common forward position study hotspot of material science.Open at present
The degradable high polymer material that hair is applied to the biomedical sectors such as organizational project is a lot, but the original Journal of Sex Research work of these materials
Make to belong to external mostly and applied for multinomial patent in China.Therefore suitable raw material is actively found, developing has China autonomous
The biomaterial of intellectual property, for reducing the biomaterials such as China's tissue engineering bracket to external dependence, is cultivated newly
New high-tech industry and the sustainable development for realizing national economy are significant.Tussah silk（Tussah silk；
Antheraea pernyi）It is the natural silk fiber using tussah cocoon as raw material reel silk from cocoons system, is the precious resources of China.China
Produce tussah cocoon 3~40,000 ton per year, account for 90 more than % of world's tussah cocoon total output, this is the distinctive valuable money of rare China of the world
Source, but tussah silk is mainly used as common textile raw material at present, and the economic value embodied is extremely limited.Except making low value spinning
Knit beyond raw material, the demand that tussah silk is used as into biomedical material is more and more stronger, trained such as enzyme immobilization carrier, cell
Support matrix, wound dressing, artificial skin, tissue engineering bracket etc..
From the sixties so far, amino acid composition, molecular structure, physical property of the domestic and foreign scholars to tussah silk fibroin
Etc. having carried out more research.Compared with domestic silkworm silk, tussah silk has stronger hygroscopicity, heat resistance, resistance to acids and bases, its amino
Acid composition is also different：Tussah silk fibroin primary amino acid content sequence is alanine（Ala）＞ glycine（Gly）＞
Propylhomoserin（Ser）＞ tyrosine（Tyr）, and contain abundant aspartic acid（Asp）And arginine（Arg）, therefore containing arginine-
Gly-Asp (RGD) tripeptide sequence.RGD sequences are combined as the plain acceptor of cell integral membrane with extracellular ligand
Recognition site, the interaction between mediated cell and extracellular matrix and cell can promote cell to stick support.
These excellent characteristics imparting tussah silk fibroins are in the advantageous advantage of the technical field of biological material such as tissue engineering bracket and extensively
General application prospect.
Natural tussah silk is because form is single（Threadiness）With the higher difficult degradation of crystallinity and limit its application.It is known to have
Many salting liquids can dissolve natural mulberry silk, such as calcium chloride（CaCl2）, magnesium chloride (MgCl2), lithium bromide (LiBr) etc. so that
Bombyx mori silk fibroin can be made easily（B fibroin albumens）Solution.Yet with extremely strong intermolecular interaction, tussah silk compares silkworm
Silk is more difficult to dissolving, and the system of general dissolving mulberry silk is difficult dissolving tussah silk.Strong acid and highly basic can all send out tussah silk fibroin
Raw acutely hydrolysis, molecular weight is substantially reduced, and such as the molecular weight after persalt, phosphoric acid and sulfuric acid dissolution is about in 200-5000
D, so being generally only that silk peptide and fibroin powder are produced with strong acid and highly basic, greatly limits its application.
Molecular weight is between 2000-3000D made from the microwave hydrolysis method occurred in recent years, the tussah silk peptide of the molecular weight
Albumen can not still meet the requirement of medical material, it is therefore desirable to explore other dissolving methods to obtain the tussah of larger molecular weight
Fibroin albumen, so as to meet the requirement to tussah silk fibroin solution processing and forming and finished product physical and mechanical properties again.
Being currently available the method for tussah silk fibroin solution mainly has two kinds：First method is directly from ripe tussah rear portion silk
Liquid tussah silk fibroin is extracted in gland, this method operating procedure is simple, but be only applicable to prepare tussah silk fibroin in a small amount molten
Liquid and progress correlative study, it is impossible to industrialize；Another method is that the method dissolved with neutral salt obtains regeneration tussah silk peptide
Protein solution, the neutral salt that tussah silk can be dissolved at present is mainly calcium nitrate and lithium rhodanate（LiSCN）, although this method can
To improve the amount to obtain of tussah silk fibroin solution, but dissolved efficiency is low, complex process, it is often more important that can heavy damage tussah
The original multilevel hierarchy of silk so that regeneration tussah silk fibroin material property is poor, it is difficult to meet application requirement.
The content of the invention
In view of the shortcomings of the prior art, present invention solves the technical problem that being to provide a kind of regeneration tussah silk fibroin solution
And preparation method thereof, the tussah silk fibroin obtained by this method retains the original multistage fibrillar structure of itself.
In order to solve the above technical problems, the technical proposal of the invention is realized in this way：
A kind of preparation method for regenerating tussah silk fibroin solution, comprises the following steps：
（1）Removal of impurities, degumming, ultrasonication are carried out to tussah silk, pre-treatment tussah silk is obtained；
（2）Pre-treatment tussah silk is placed in the trifluoroacetic acid aqueous solution containing formic acid, stirring and dissolving under mixed liquor, normal temperature is prepared,
Obtain regenerating tussah silk fibroin organic solution；
（3）Regeneration tussah silk fibroin organic solution is placed in deionized water and dialysed, obtains regenerating tussah silk fibroin solution.
In above-mentioned technical proposal, the power of the excusing from death ripple processing is 1~10kW, and the time is 30~50 minutes；It is preferred that,
The power of the excusing from death ripple processing is 3~6kW, and the time is 35~40 minutes.
In above-mentioned technical proposal, the mass concentration of the trifluoroacetic acid aqueous solution is 80~90%；It is preferred that, the trifluoro
The mass concentration of acetic acid aqueous solution is 85~88%.
In above-mentioned technical proposal, in the mixed liquor, the quality of formic acid is the 3~5% of trifluoroacetic acid.
In above-mentioned technical proposal, in the mixed liquor, the concentration of pre-treatment tussah silk（Silk concentration of ordinary dissolution）For 5wt%~
10wt%；It is preferred that silk concentration of ordinary dissolution be 7~8wt%.
In above-mentioned technical proposal, the time of the stirring and dissolving is 5~20 minutes.
In above-mentioned technical proposal, the temperature of the dialysis is 4~10 DEG C, and the time of dialysis is 3~5 days.
The invention also discloses one kind regeneration tussah silk fibroin material and preparation method thereof, comprise the following steps：
（1）Removal of impurities, degumming, ultrasonication are carried out to tussah silk, pre-treatment tussah silk is obtained；
（2）Pre-treatment tussah silk is placed in the trifluoroacetic acid aqueous solution containing formic acid, stirring and dissolving under mixed liquor, normal temperature is prepared,
Obtain regenerating tussah silk fibroin organic solution；
（3）Regeneration tussah silk fibroin organic solution is placed in deionized water and dialysed, regeneration tussah silk fibroin is obtained water-soluble
Liquid；
（4）The regeneration tussah silk fibroin aqueous solution is prepared into regeneration tussah silk fibroin material.
In above-mentioned technical proposal, the regeneration tussah silk fibroin material includes regeneration tussah silk fibroin film, regeneration toothed oak
Fibroin protein gel.
The present invention is substantially to use trifluoroacetic acid for solvent, adds a small amount of formic acid, at normal temperatures directly quick dissolving toothed oak
Silk, then removes organic solvent through dialysis, obtains regenerating the tussah silk fibroin aqueous solution, using nanofiber as primary structure；
Regenerated silk material is prepared into, with good mechanical property.
Compared with the prior art compared with advantages of the present invention is as follows：
Preparation method disclosed by the invention uses the tight structure inside ultrasonic wave pre-treating technology, loose silk, is conducive to
Solvent penetration accelerates the dissolving of silk, and is conducive to adjusting solvent to the dissolution degree of silk-fibroin.
Regeneration tussah silk fibroin solution disclosed by the invention and preparation method thereof, only with organic solvent, it is to avoid highly concentrated
The serious degraded of neutral salt under the high temperature conditions to silk is spent, and regulation and control silk egg is realized by the mixing match of organic solvent
The purpose of white dissolution degree.
Regeneration tussah silk fibroin solution disclosed by the invention is noteworthy characterized by compared with conventional tussah silk fibroin solution
Using tussah silk fibroin nanometer fibril as formant, this nanometer of fibril is that natural tussah silk has in itself, and non-regenerative process
In by being self-assembly of, be natural tussah silk fibroin nanometer fibril.
Regeneration tussah silk fibroin solution disclosed by the invention is first only using organic solvent as lysate, stirring at normal temperature
Realize prepared by product, the preparation method technique is simple, obtained solution is salt-free, organic solvent residual, is pure tussah silk fibroin
Solution.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of fibroin albumen form in the obtained solution of the embodiment of the present invention one；
Fig. 2 is the infrared spectrum of regenerated silk fibroin film before and after the processing made from the embodiment of the present invention one；
Fig. 3 is the scanning electron microscope (SEM) photograph of fibroin albumen form in the obtained solution of the embodiment of the present invention two.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, people in the art
Member obtains every other embodiment under the premise of creative work is not made, and belongs to the scope of protection of the invention.
Embodiment one
Natural tussah silk mass fraction 0.5wt% sodium bicarbonate solution boils 60min, deionized water is fully washed dry after
Obtain boiled silk.Boiled silk is placed in beaker, deionized water is added, then carries out ultrasonically treated, ultrasonic power
5kW, ultrasonic treatment time 40 minutes.At room temperature, boiled silk is placed in containing 3% formic acid（Trifluoroacetic acid quality is radix）
86wt% trifluoroacetic acid aqueous solutions in, silk quality fraction 7% obtains regenerated silk fibroin trifluoro second after magnetic agitation 10min
Acid solution.Then solution is injected in bag filter, is placed in flow deionized water the 3d that dialyses, 10 DEG C of temperature of dialysing is purified
The regeneration tussah silk fibroin nanofiber aqueous solution.Fibroin albumen is nanometer fibrous in the solution, and fibre length is 0.1-
15 μm, 0.01-1 μm of diameter（As shown in Figure 1）, 150~300kDa of silk fibroin molecular amount distribution.Regenerated silk fibroin is molten
In liquid injection polyethylene ware, spontaneously dry and obtain regenerating tussah silk fibroin film, protein structure is impalpable structure, through second
Beta sheet crystalline texture is converted into after alcohol solution processing（As shown in Figure 2）, the film dynamic performance is excellent, fracture strength 98MPa,
Elongation at break 6.5%；Handled by gelation, can obtain the regeneration tussah silk fibroin gel of biocompatibility well；Hygrometric state
Modulus of compressibility is 96MPa；It can be applicable to and prepare in tissue engineering bracket.
Comparative example one：
Referring to the technique of embodiment one, wherein without formic acid, 50~70kDa of silk fibroin molecular amount distribution；Regenerate tussah
The fracture strength 46MPa of fibroin protein film, elongation at break 3.5%；Regeneration tussah silk fibroin gel hygrometric state modulus of compressibility be
36MPa。
Embodiment two：
Natural tussah silk mass fraction 0.05wt% sodium bicarbonate solution boils 60min, and then deionized water is fully washed,
Boiled silk is obtained after drying in triplicate.Boiled silk is placed in beaker, deionized water is added, then carried out at ultrasound
Reason, ultrasonic power 3kW, ultrasonic treatment time 35 minutes.At room temperature, boiled silk is placed in containing 5% formic acid（Trifluoro second
Sour quality is radix）85wt% trifluoroacetic acid aqueous solutions in, silk quality fraction 8% obtains regenerated silk after magnetic agitation 5min
Fibroin organic solution.Then solution is injected in bag filter, is placed in flow deionized water the 5d that dialyses, 4 DEG C of temperature of dialysing is obtained
To the regeneration tussah silk fibroin nanofiber aqueous solution of purifying.Fibroin albumen is nanometer fibrous in the solution, such as Fig. 3 institutes
Show, 140~200kDa of silk fibroin molecular amount distribution；Spontaneously dry and obtain regenerating tussah silk fibroin film, fracture is strong
Spend 95MPa, elongation at break 6.1%；Handled by gelation, can obtain the regeneration tussah silk fibroin of biocompatibility well
Gel；Hygrometric state modulus of compressibility is 94MPa；It can be applicable to and prepare in tissue engineering bracket.
Comparative example two：
Referring to the technique of embodiment two, wherein without formic acid, 40~65kDa of silk fibroin molecular amount distribution；Regenerate tussah
The fracture strength 40MPa of fibroin protein film, elongation at break 3.2%；Regeneration tussah silk fibroin gel hygrometric state modulus of compressibility be
38MPa。
Embodiment three：
Natural tussah silk mass fraction 0.25wt% sodium bicarbonate solution boils 60min, and then deionized water is fully washed,
Boiled silk is obtained after drying in triplicate.Boiled silk is placed in beaker, deionized water is added, then carried out at ultrasound
Reason, ultrasonic power 6kW, ultrasonic treatment time 35 minutes.At room temperature, boiled silk is placed in containing 4% formic acid（Trifluoro second
Sour quality is radix）88wt% trifluoroacetic acid aqueous solutions in, silk quality fraction 7% obtains regenerated silk after magnetic agitation 20min
Fibroin organic solution.Then solution is injected in bag filter, is placed in flow deionized water the 3d that dialyses, 4 DEG C of temperature of dialysing is obtained
To the regeneration tussah silk fibroin nanofiber aqueous solution of purifying, 110~180kDa of silk fibroin molecular amount distribution；It is natural
Drying to obtain regenerates tussah silk fibroin film, and protein structure is impalpable structure, is converted into after being handled through ethanol water
Beta sheet crystalline texture, fracture strength 89MPa, elongation at break 6.1%；Handled by gelation, can obtain biocompatibility good
Good regeneration tussah silk fibroin gel；Hygrometric state modulus of compressibility is 95MPa；It can be applicable to and prepare in tissue engineering bracket.
Comparative example three：
Referring to the technique of embodiment three, wherein ultrasonication is not used, 90~120kDa of silk fibroin molecular amount distribution；
Regenerate the fracture strength 68MPa of tussah silk fibroin film, elongation at break 5.5%；Regenerate the hygrometric state pressure of tussah silk fibroin gel
Contracting modulus is 82MPa.
Example IV：
Natural tussah silk mass fraction 0.5wt% sodium bicarbonate solution boils 60min, and then deionized water is fully washed, weight
Boiled silk is obtained after drying for multiple three times.Boiled silk is placed in beaker, add deionized water, then carry out it is ultrasonically treated,
Ultrasonic power 1kW, ultrasonic treatment time 50 minutes.At room temperature, boiled silk is placed in containing 4% formic acid（Trifluoroacetic acid matter
Measure as radix）80wt% trifluoroacetic acid aqueous solutions in, silk quality fraction 5% obtains regenerated silk egg after magnetic agitation 15min
White organic solution.Then solution is injected in bag filter, is placed in flow deionized water the 5d that dialyses, 10 DEG C of temperature of dialysing is obtained
The regeneration tussah silk fibroin nanofiber aqueous solution of purifying, 160~320kDa of silk fibroin molecular amount distribution；Naturally do
It is dry i.e. obtain regenerate tussah silk fibroin film, protein structure is impalpable structure, be converted into after being handled through ethanol water β-
Fold crystalline texture, fracture strength 78MPa, elongation at break 5.5%；Handled by gelation, can obtain biocompatibility good
Regeneration tussah silk fibroin gel；Hygrometric state modulus of compressibility is 82MPa；It can be applicable to and prepare in tissue engineering bracket.
Comparative example four：
Referring to the technique of example IV, wherein formic acid consumption is 8%, 8~10kDa of silk fibroin molecular amount distribution；Regenerate toothed oak
The fracture strength 40MPa of silk fibroin membrane, elongation at break 2.9%；Regenerate the hygrometric state modulus of compressibility of tussah silk fibroin gel
For 31MPa.
Embodiment five：
Natural tussah silk mass fraction 0.25wt% sodium carbonate liquor boils 60min, and then deionized water is fully washed, weight
Boiled silk is obtained after drying twice again.Boiled silk is placed in beaker, add deionized water, then carry out it is ultrasonically treated,
Ultrasonic power 10kW, ultrasonic treatment time 30 minutes.At room temperature, boiled silk is placed in containing 4% formic acid（Trifluoroacetic acid
Quality is radix）90wt% trifluoroacetic acid aqueous solutions in, silk quality fraction 5% obtains regenerated silk after magnetic agitation 10min
Albumen organic solution.Then solution is injected in bag filter, is placed in flow deionized water the 3d that dialyses, 4 DEG C of temperature of dialysing is obtained
The purifying regeneration tussah silk fibroin nanofiber aqueous solution, 130~200kDa of silk fibroin molecular amount distribution；Spontaneously dry
Obtain regenerating tussah silk fibroin film, protein structure is impalpable structure, and β-folding is converted into after handling through ethanol water
Folded crystalline texture, fracture strength 75MPa, elongation at break 5.6%；Handled by gelation, can obtain biocompatibility good
Regenerate tussah silk fibroin gel；Hygrometric state modulus of compressibility is 83MPa；It can be applicable to and prepare in tissue engineering bracket.
Comparative example five：
Referring to the technique of embodiment five, wherein ultrasonic power 20kW, 30~80kDa of silk fibroin molecular amount distribution；Again
The fracture strength 58MPa of raw tussah silk fibroin film, elongation at break 4.5%；Regenerate the hygrometric state compression of tussah silk fibroin gel
Modulus is 49MPa.
Embodiment six：
Natural tussah silk mass fraction 0.5wt% sodium carbonate liquor boils 60min, deionized water is fully washed dry after obtain
Obtain boiled silk.Boiled silk is placed in beaker, deionized water is added, then carries out ultrasonically treated, ultrasonic power 6kW,
Ultrasonic treatment time 50 minutes.At room temperature, boiled silk is placed in containing 4% formic acid（Trifluoroacetic acid quality is radix）'s
In 85wt% trifluoroacetic acid aqueous solutions, silk quality fraction 10% obtains regenerated silk fibroin after magnetic agitation 10min organic molten
Liquid.Then solution is injected in bag filter, is placed in flow deionized water the 3d that dialyses, dialyse 4 DEG C of temperature, the regeneration purified
The tussah silk fibroin nanofiber aqueous solution, 160~300kDa of silk fibroin molecular amount distribution；Spontaneously dry and obtain again
Raw tussah silk fibroin film, protein structure is impalpable structure, and beta sheet crystallization knot is converted into after being handled through ethanol water
Structure, fracture strength 72MPa, elongation at break 5.5%；Handled by gelation, can obtain the regeneration tussah of biocompatibility well
Silk fibroin gel；Hygrometric state modulus of compressibility is 81MPa；It can be applicable to and prepare in tissue engineering bracket.
Comparative example six：
Referring to the technique of embodiment six, wherein being dissolved using 90% formic acid, trifluoroacetic acid, silk fibroin molecular amount point are not used
6~8kDa of cloth scope；Regenerate the fracture strength 28MPa of tussah silk fibroin film, elongation at break 2.5%；Regenerate tussah silk peptide egg
The hygrometric state modulus of compressibility of white gel is 29MPa.
Claims (10)
1. a kind of preparation method for regenerating tussah silk fibroin solution, it is characterised in that comprise the following steps：
（1）Removal of impurities, degumming, ultrasonication are carried out to tussah silk, pre-treatment tussah silk is obtained；
（2）Pre-treatment tussah silk is placed in the trifluoroacetic acid aqueous solution containing formic acid, stirring and dissolving under mixed liquor, normal temperature is prepared,
Obtain regenerating tussah silk fibroin organic solution；
（3）Regeneration tussah silk fibroin organic solution is placed in deionized water and dialysed, obtains regenerating tussah silk fibroin solution.
2. a kind of preparation method for regenerating tussah silk fibroin material, it is characterised in that comprise the following steps：
（1）Removal of impurities, degumming, ultrasonication are carried out to tussah silk, pre-treatment tussah silk is obtained；
（2）Pre-treatment tussah silk is placed in the trifluoroacetic acid aqueous solution containing formic acid, stirring and dissolving under mixed liquor, normal temperature is prepared,
Obtain regenerating tussah silk fibroin organic solution；
（3）Regeneration tussah silk fibroin organic solution is placed in deionized water and dialysed, regeneration tussah silk fibroin is obtained water-soluble
Liquid；
（4）The regeneration tussah silk fibroin aqueous solution is prepared into regeneration tussah silk fibroin material.
3. the preparation method according to claims 1 or 2, it is characterised in that the power of the excusing from death ripple processing for 1~
10kW, the time is 30~50 minutes.
4. preparation method according to claim 3, it is characterised in that the power of the excusing from death ripple processing is 3~6kW, when
Between be 35~40 minutes.
5. the preparation method according to claims 1 or 2, it is characterised in that the quality of the trifluoroacetic acid aqueous solution is dense
Spend for 80~90%；In the mixed liquor, the concentration of pre-treatment tussah silk is 5~10wt%.
6. preparation method according to claim 5, it is characterised in that the mass concentration of the trifluoroacetic acid aqueous solution is 85
~88%；In the mixed liquor, the concentration of pre-treatment tussah silk is 7~8wt%.
7. the preparation method according to claims 1 or 2, it is characterised in that in the mixed liquor, the quality of formic acid is three
The 3~5% of fluoroacetic acid；The time of the stirring and dissolving is 5~20 minutes；The temperature of the dialysis be 4~10 DEG C, dialysis when
Between be 3~5 days.
8. preparation method according to claim 2, it is characterised in that the regeneration tussah silk fibroin material includes regeneration
Tussah silk fibroin film, regeneration tussah silk fibroin gel.
9. regeneration tussah silk fibroin solution prepared by preparation method according to claim 1.
10. regeneration tussah silk fibroin material prepared by preparation method according to claim 2.
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