CN103341214B - Silk fibroin membrane and preparation method thereof - Google Patents
Silk fibroin membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silk fibroin membrane and a preparation method of the silk fibroin membrane. The preparation method comprises the following specific steps of: dissolving natural silk taken as a main raw material in an acid inorganic salt solution, forming a membrane, desalting, and carrying out vacuum drying to prepare the silk fibroin membrane which is insoluble in water and has high mechanical property. The silk fibroin membrane has the breaking strength of greater than 50Mpa at dry state, the breaking elongation of greater than 5% at dry state, the breaking strength of greater than 10Mpa at wet state and the breaking elongation of greater than 150% at wet state. In addition, the silk fibroin membrane prepared by the method is stable and controllable in structure, has good biocompatibility and can serve as a medicinal biological material. The preparation method disclosed by the invention is simple and short in flow path, has high film formation efficiency and is suitable for industrialization large-scale production.
Description
Technical field
The present invention relates to a kind of polymeric membrane and preparation method thereof, be specifically related to a kind of fibroin protein film and preparation method thereof, the method is simply efficient, can be widely used in biology, medical domain.
Background technology
China is the major country of production of silkworm silk, and silk yield accounts for more than 70% of world wide production.In recent years, the research and apply of silkworm silk extends to high-technology field from traditional field of textiles, as photoelectron and bio-medical material, particularly achieves impressive progress as bio-medical material.Natural silk is threadiness, and bio-medical material requires that support shape has multiformity and plasticity, therefore, is the steps necessary widening its range of application to the regeneration processing of natural silk cellulose fiber.Current fibroin can be processed to rope, regeneration long filament, nano fibrous membrane, fibroin protein film, perforated membrane, hydrogel etc.; wherein, fibroin protein film can be used as artificial skin, blood vessel, ligament, esophagus, anticoagulant material, drug release material etc. and receives extensive concern and research (Chen Yanxiong; Chen Min; Zhu composes newly; Du Zongliang. textile technology is in progress. 2007(2): 13).
But the fibroin protein film of regeneration preparation is impalpable structure, and soluble in water, mechanical property is poor, special performance fragility is after treatment large, and intensity is low, is therefore difficult to the requirement meeting application.
In prior art, research worker is all improved and improved the mechanical property (Hang Yichun of fibroin protein film by blended, grafting, the method such as crosslinked; Zhang Yaopeng; Shao Huili; Hu Xuechao. functional material. 2010,1(41): 108), but inevitably, these methods or limited to the raising of material mechanical performance, or significantly can reduce the biocompatibility of silk fibroin bracket, and improve the inflammatory reaction of material, be difficult to obtain promising result.Therefore, the biocompatibility not reducing material while improving the mechanical property of fibroin material is significant as the clinical practice of medical material to fibroin material.
On the other hand, inner at natural silk, have diameter to be the line structure of tens nanometers in the sericterium before silkworms spin silk, this nanostructured plays pivotal role in the formation of silkworm silk and the mechanical property of silkworm silk excellence; But in prior art, in natural silk regenerative process, this nanostructured of dissolving step heavy damage, this becomes the one of the main reasons of the silk fibroin nano-fiber film mechanical property difference of regeneration preparation.
Therefore, find a kind of method preparing fibroin protein film newly, thus the nanostructured not destroying natural silk inside in the process of dissolving silkworm silk is necessary.
Summary of the invention
The object of this invention is to provide a kind of avirulence, good biocompatibility, there is excellent mechanical properties, fibroin protein film being applicable to tissue engineering bracket and preparation method thereof.
The present invention adopts following technical scheme to realize object of the present invention: a kind of method preparing fibroin protein film, comprises the following steps:
(1) acid and water are mixed in proportion, and then add inorganic salt and obtain silkworm silk lysate;
(2) natural silk degumming drying is placed in the silkworm silk lysate of step (1), obtains fibroin protein solution stir 0.5 ~ 6h at 10 ~ 100 DEG C after, be poured into vacuum drying film forming in polyethylene ware; In silk fibroin protein solution, the mass fraction of fibroin albumen is 10 ~ 25%;
(3) film that step (2) is obtained is placed in water or alcohol solution for soaking 1 ~ 72h, after vacuum drying, obtains described fibroin protein film.
In technique scheme, the acid in described step (1) is the blend of formic acid, phosphoric acid or formic acid and phosphoric acid, and being preferably mass ratio is the formic acid of 1: 0.25 ~ 4 and the blend of phosphoric acid; Described inorganic salt is one or more in lithium bromide, calcium chloride, zinc chloride, magnesium chloride, lithium rhodanate, sodium rhodanate, Magnesium sulfocyanate., lime nitrate, copper nitrate.
In technique scheme, in the silkworm silk lysate of described step (1), acid concentration is 10 ~ 100wt%; Inorganic salt concentration is 0.1 ~ 50wt%.
In technique scheme, described silkworm silk is one or more in mulberry silk, tussah silk, ricinus silk, wild silk yarn.
In technique scheme, the alcohol in described step (3) is methanol, ethanol or isopropyl alcohol; Described alcoholic solution concentration is 1 ~ 100wt%.
In preferred technical scheme, the fibroin protein film of preparation in step (3) is dissolved in formic acid or hexafluoroisopropanol to prepare mass fraction be 5% ~ 20% silk fibroin solution, then silk fibroin solution is poured into vacuum drying in polyethylene ware and become fibroin membrane; Again fibroin membrane is placed in water and soaks 1 ~ 72h, after vacuum drying, obtain fibroin protein film.This post-processing step reduces water or alcoholic solution in step (3) and, except the destruction of salt pair film morphosis, improves the mechanical property of fibroin protein film further.
Further in preferred technical scheme, by the silk fibroin solution in above-mentioned post-processing step and other high score material solutions are blended obtains composite filament cellulose solution, then drying and forming-film; Wherein other high score materials are collagen, gelatin, chitosan, polylactic acid, hyaluronic acid, hydroxyapatite, calcium carbonate, polyvinyl alcohol, cellulose, polycaprolactone or polyglycolic acid; The mass ratio of other macromolecular materials and fibroin albumen is 0
~1
:1.
In the present invention, vacuum drying temperature is 20-100 DEG C, and the time is 1-24h.
The invention also discloses the fibroin protein film prepared according to above-mentioned preparation method.
Fibroin protein film disclosed in this invention, the mass fraction of fibroin albumen is greater than 50%, and the structure of fibroin albumen is fibroin II type crystalline texture, has excellent stability: in the water of 37 DEG C, the dissolve-loss ratio of 24 hours fibroin albumens is less than 1% in water; And Stability Analysis of Structures is controlled, biocompatibility is good, can be used as the biomaterial for medical purpose such as artificial skin material, cerebral dura mater, sticking patch, esophagus, cardiac valve, blood vessel, ligament, tendon, nerve trachea, cornea.
Because technique scheme is used, the present invention compared with prior art has following advantages:
(1) the present invention utilizes the aqueous dissolution boiled silk of acid and salt and prepares fibroin protein film, protect the nanostructured of natural silk inside, compared with prior art, thus obtained fibroin protein film has excellent mechanical performance, its dry break strength is greater than 50MPa, elongation at break is greater than 5%, and wet break strength is greater than 10 MPa, elongation at break is greater than 150%; This fibroin protein film remains excellent biocompatibility and degradation property simultaneously;
(2) processing method disclosed by the invention is simply efficient, and the dissolving of silkworm silk is fast, concentration of ordinary dissolution is high, and without the need to dialysis, the masking time is short, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the surface scan Electronic Speculum figure of the fibroin protein film of preparation in embodiment one;
Fig. 2 is the profile scanning Electronic Speculum figure of the fibroin protein film of preparation in embodiment one;
Fig. 3 is the infrared spectrogram of the fibroin protein film of preparation in embodiment four;
Fig. 4 is the infrared spectrum of the fibroin protein film of preparation in embodiment five;
Fig. 5 is the mechanical stretch curve in embodiment five under fibroin protein film dry state;
Fig. 6 is the mechanical stretch curve in embodiment five under fibroin protein film hygrometric state;
Fig. 7 is the mechanical stretch curve in comparative example one under fibroin protein film dry state;
Fig. 8 is the mechanical stretch curve in comparative example one under fibroin protein film hygrometric state.
Detailed description of the invention
Below in conjunction with drawings and Examples, comparative example, the invention will be further described:
Embodiment one
(1) sodium carbonate liquor of natural mulberry silk 0.5wt% boils 30min, comes unstuck, and obtains degummed mulberry silk after repeating 3 times;
(2) degummed mulberry silk is placed in the 80wt% formic acid of chloride containing calcium 2wt% with the concentration of 15wt%, stirring and dissolving 2h under room temperature, then pours drying and forming-film in polyethylene board into;
(3) film in step (2) is placed in circulating water and soaks 8h removal calcium chloride, be then placed in 40 DEG C, vacuum drying oven, after 24h drying, obtain fibroin protein film.
Accompanying drawing 1, Fig. 2 are respectively surface and the profile scanning Electronic Speculum figure of above-mentioned fibroin protein film; Therefrom can find out that the smooth surface of the silk fibroin membrane that the present invention obtains is smooth, visible a large amount of nano thread structure in section.
Embodiment two
(1) sodium carbonate liquor of natural mulberry silk 0.5wt% boils 30min and comes unstuck, and obtains degummed mulberry silk after repeating 3 times;
(2) degummed mulberry silk is placed in the formic acid of the 95wt% containing lithium bromide 5wt% with the concentration of 20wt%, stirring and dissolving 6h under room temperature, then pours drying and forming-film in polyethylene board into;
(3) film in step (2) is placed in circulating water and soaks 10h removal lithium bromide, be then placed in vacuum drying oven dry;
(4) film in step (3) is dissolved in the silk fibroin solution preparing 20wt% in the formic acid of 80wt%, after pour in polyethylene board and be dried to fibroin membrane;
(5) fibroin membrane that step (4) obtains is placed in circulating water and soaks the residual formic acid of 1h removal, then 60 DEG C, 20h vacuum drying can obtain fibroin protein film.
Embodiment three:
(1) sodium carbonate liquor of natural mulberry silk 0.5wt% boils 30min and comes unstuck, and obtains degummed mulberry silk after repeating 3 times;
(2) degummed mulberry silk is placed in 50wt% mixed acid (phosphoric acid: formic acid=1:4) containing lithium rhodanate 5wt% with the concentration of 10wt%, 60 DEG C of stirring and dissolving 1h, then pour drying and forming-film in polyethylene board into;
(3) fibroin protein film in step (2) is placed in circulating water and soaks 1h removal salt and residual acid, be then placed in vacuum drying oven dry;
(4) film in step (3) is dissolved in hexafluoroisopropanol prepares 10wt% solution, chitosan is dissolved in hexafluoroisopropanol simultaneously and prepares 10wt% solution, then be 10wt% by two kinds of solution by the blended compound concentration of 1:1 volume, the blended silk fibroin solution of fibroin and polylactic acid 1:1;
(5) fibroin/chitosan blend silk fibroin solution that step (4) is prepared is poured in polyethylene board drying and forming-film, then obtained fibroin protein film is soaked in circulating water and removes residual hexafluoroisopropanol, finally be placed in 60 DEG C, vacuum drying oven, 20h is drying to obtain fibroin protein film.
Embodiment four:
(1) sodium carbonate liquor of natural mulberry silk 0.5wt% boils 30min and comes unstuck, and obtains degummed mulberry silk after repeating 3 times;
(2) degummed mulberry silk is placed in the 80wt% formic acid of Containing Zinc Chloride 10wt% with the concentration of 10wt%, stirring and dissolving 2h at 100 DEG C, then pours drying and forming-film in polyethylene board into, is untreated fibroin protein film;
(3) fibroin protein film in step (2) is placed in circulating water or ethanol to soak 4h and remove zinc chloride and residual acid, be then placed in 60 DEG C, vacuum drying oven, 20h is drying to obtain described fibroin protein film, is the fibroin protein film processed;
Accompanying drawing 3 is the infrared spectrogram of above-mentioned three kinds of fibroin protein films, and wherein a is untreated, b is soak with ethanol process, c is water soaking process; Therefrom can find out, the fibroin protein film prepared by the present invention is mainly fibroin II type crystalline texture.
Embodiment five
(1) sodium carbonate liquor of natural tussah silk mass fraction 0.5wt% boils 30min and comes unstuck, and repeats 3 times and obtains tussah silk of coming unstuck afterwards;
(2) tussah silk of coming unstuck is placed in the 30wt% phosphoric acid of chloride containing calcium 5wt% with the concentration of 10wt%, stirring and dissolving 4h at 10 DEG C, then pours drying and forming-film in polyethylene board into;
(3) fibroin protein film in step (2) is placed in circulating water and soaks 2h removal calcium chloride and phosphoric acid, be then placed in 50 DEG C, drying baker, 24h is drying to obtain fibroin protein film.
The infrared spectrum of the above-mentioned fibroin protein film of accompanying drawing 4, can find out that fibroin albumen is mainly fibroin II type crystalline texture.
Embodiment six
(1) sodium carbonate liquor of natural mulberry silk 0.1wt% boils 30min and comes unstuck, and obtains degummed mulberry silk after repeating 3 times;
(2) degummed mulberry silk is placed in the formic acid of the 95wt% containing lithium bromide 5wt% with the concentration of 10wt%, under room temperature, stirring and dissolving 6h obtains solution;
(3) add 1% hyaluronic acid in the solution in step (2), obtain fibroin albumen and hyaluronic acid blend solution, then pour solution in polyethylene board drying and forming-film;
(3) film in step (2) is placed in ethanol and soaks 10h removal lithium bromide, be then placed in 80 DEG C, vacuum drying oven, namely 15h drying obtains fibroin albumen/Hyaluronic Acid Blend Membrane.
Embodiment seven
(1) sodium carbonate liquor of natural mulberry silk 0.1wt% boils 30min and comes unstuck, and obtains degummed mulberry silk after repeating 3 times;
(2) degummed mulberry silk is placed in 50wt% mixed acid (phosphoric acid: formic acid=1:4) containing lithium rhodanate 5wt% with the concentration of 15wt%, 60 DEG C of stirring and dissolving 1h, then pour drying and forming-film in polyethylene board into;
(3) fibroin protein film in step (2) is placed in circulating water and soaks 1h removal salt and residual acid, be then placed in 50 DEG C, vacuum drying oven, 20h is drying to obtain fibroin protein film.
Accompanying drawing 5,6 is the mechanical stretch curve under above-mentioned fibroin protein film dry state and hygrometric state, can find out that the method gained fibroin protein film all has good mechanical performance under dry state and hygrometric state.
Comparative example one
(1) sodium carbonate liquor of natural mulberry silk 0.5wt% boils 30min and comes unstuck, and obtains degummed mulberry silk after repeating 3 times;
(2) boiled silk that step (1) is obtained is dissolved in the lithium bromide water solution of 9.3M, solution temperature 60
dEG C, dissolution time 6h;
(3) silk fibroin protein solution that step (2) obtained injects bag filter and is placed in flow deionized water and dialyses 3d;
(4) the pure silk fibroin protein solution that step (3) obtains is poured in polyethylene board drying and forming-film;
(5) film obtained for step (4) is soaked in 75% ethanol processes half an hour, obtain after drying based on the regenerated silk fibroin film of beta sheet structure.
Accompanying drawing 7,8 is the mechanical stretch curve under above-mentioned fibroin protein film dry state and hygrometric state, can find out and illustrate that method of the present invention has superiority in structure excellent performance regenerated silk fibroin film by the fibroin protein film that its mechanical property under dry state and hygrometric state all obviously will be worse than the inventive method and prepares.
Claims (6)
1. prepare a method for fibroin protein film, it is characterized in that, comprise the following steps:
(1) mixed acid and water, and then add inorganic salt and obtain silkworm silk lysate;
Described acid is the blend of formic acid, phosphoric acid or formic acid and phosphoric acid; Described inorganic salt is one or more in lithium bromide, calcium chloride, zinc chloride, lithium rhodanate;
(2) natural silk degumming drying is placed in the silkworm silk lysate of step (1), obtains silk fibroin protein solution stir 0.5 ~ 6h at 10 ~ 100 DEG C after, be poured into vacuum drying film forming in polyethylene ware; In described silk fibroin protein solution, the mass fraction of fibroin albumen is 0.1 ~ 50%;
(3) film that step (2) is obtained is placed in water and soaks 1 ~ 72h, after vacuum drying, obtain fibroin protein film;
(4) fibroin protein film of preparation in step (3) is dissolved in formic acid or hexafluoroisopropanol prepares the silk fibroin solution that mass fraction is 5% ~ 20%, then silk fibroin solution is poured into vacuum drying in polyethylene ware and become fibroin membrane; Again fibroin membrane is placed in water and soaks 1 ~ 72h, after vacuum drying, obtain described fibroin protein film.
2. according to the preparation method described in claim 1, it is characterized in that: in the silkworm silk lysate of described step (1), acid concentration is 10 ~ 95wt%; Inorganic salt concentration is 0.1 ~ 50wt%.
3. according to the preparation method described in claim 1, it is characterized in that: described silkworm silk is one or more in mulberry silk, tussah silk, ricinus silk, wild silk yarn.
4. according to the preparation method described in claim 1, it is characterized in that: described silk fibroin solution also comprises collagen, gelatin, chitosan, polylactic acid, hyaluronic acid, hydroxyapatite, calcium carbonate, polyvinyl alcohol, cellulose, polycaprolactone or polyglycolic acid.
5. the fibroin protein film that any one preparation method according to claims 1 to 4 prepares.
6. fibroin protein film according to claim 5, is characterized in that: in described fibroin protein film, and the mass fraction of fibroin albumen is greater than 50%.
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