CN103319731A - Regenerated silk fibroin solution and preparation method thereof - Google Patents
Regenerated silk fibroin solution and preparation method thereof Download PDFInfo
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- CN103319731A CN103319731A CN2013102842279A CN201310284227A CN103319731A CN 103319731 A CN103319731 A CN 103319731A CN 2013102842279 A CN2013102842279 A CN 2013102842279A CN 201310284227 A CN201310284227 A CN 201310284227A CN 103319731 A CN103319731 A CN 103319731A
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Abstract
The invention discloses regenerated silk fibroin solution and a preparation method thereof. The specific preparation method comprises the following steps of: taking phosphoric acid, formic acid and water as a main solvent (having an acid solution concentration of 50-100%), and adding inorganic salt having a concentration of 0.1-50% as a cosolvent, and preparing dissolution solution; and placing degummed silk in the dissolution solution, wherein the concentration of degummed silk is 0.1-50%; and dissolving the degummed silk for 0.5-5 hours at 10-80 DEG C, so as to obtain the regenerated silk fibroin solution. The preparation method disclosed by the invention is simple and short in flow; and the main component in the regenerated silk fibroin solution obtained by the preparation method is silk fibroin fibril, and the regenerated silk fibroin material prepared from the solution has excellent mechanical performance and is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to the natural macromolecular material field, be specifically related to a kind of regenerated silk protein solution and preparation method thereof, the method is simply efficient, can be widely used in biology, medical science aspect.
Background technology
Natural silk is fibrous, and bio-medical material requires the support shape to have diversity and plasticity-, and therefore, it is the steps necessary of widening its range of application that the regeneration of natural silk cellulose fiber is processed.Can be processed to rope, regeneration long filament, nano fibrous membrane, fibroin membrane, porous-film, hydrogel etc. after fibroin comes unstuck and dissolves at present, wherein the dissolving of boiled silk is a very crucial step, it affects the performance of follow-up fibroin material, mechanical property particularly, thus be related to the application performance of fibroin material.
Although the high density strong acid and strong base can dissolve silk, can significantly reduce the Silk Protein Molecules amount, even can not again process, thereby not be widely adopted.The neutral salt solution of high density can dissolve boiled silk, and can not cause the remarkable reduction of silk fibroin molecular amount, thereby the optimum solvent that is used as silk fiber has been subject to extensive and deep research, as the lithium bromide water solution that calcium chloride, second alcohol and water ternary solvent, 9.3mol are arranged commonly used etc. (referring to Wu Zhangwei etc. silkworm industry science. 2010,36 (4): 707～712).But after adopting the neutral salt solution dissolving silk of high density, also need the silk fibroin salts solution is placed dialysis tubing dialyse for a long time (general more than 3 days), and then acquisition regenerated silk fibroin water solution, and drying and forming-film or be lyophilized into porous support, this process is comparatively complicated, the cycle long, silk to make rate low, and the mechanical property of the silk fibroin support of regeneration preparation is relatively poor, show that especially the material fragility after the processing is large, intensity is low, has therefore limited greatly suitability for industrialized production and the widespread use thereof of fibroin regeneration preparation.
On the other hand, inner at natural silk, in the sericterium before silkworms spin silk diameter being arranged is the line structure of tens nanometers, and this nanostructure is brought into play keying action in the mechanical property of the formation of silk and silk excellence; Yet in the prior art, in the natural silk regenerative process, the dissolving step havoc this nanostructure, this becomes the one of the main reasons that the regenerated silk protein support is difficult to obtain the excellent mechanical property of natural silk.
Therefore, seek a kind of new method for preparing regenerated silk protein solution, necessary thereby simple and fast ground dissolving boiled silk does not destroy the nanostructure of natural silk inside.
Summary of the invention
The purpose of this invention is to provide a kind of simple and easy, prepare the method for regenerated silk protein solution fast, it does not destroy the nanostructure of natural silk inside in the process of dissolving boiled silk.
The present invention adopts following technical scheme to realize purpose of the present invention: a kind of method for preparing regenerated silk protein solution may further comprise the steps:
(1) natural silk comes unstuck through yellow soda ash, sodium bicarbonate or neutral soap and obtains the boiled silk fiber;
(2) mixing acid and water, and then the adding inorganic salt make the silk lysate;
(3) the boiled silk fiber that step (1) is prepared is put into the silk lysate of step (2), obtains described regenerated silk protein solution behind 10～100 ℃ of lower 0.5～6h of stirring.
In the technique scheme, the silk in the described step (1) is one or more in mulberry silk, tussah silk, the ricinus silk.
In the technique scheme, the acid in the described step (2) is the blend of formic acid, phosphoric acid or formic acid and phosphoric acid; Be preferably mass ratio and be 1: 0.25～4 formic acid and the blend of phosphoric acid.
In the technique scheme, described inorganic salt are one or more in lithiumbromide, calcium chloride, zinc chloride, magnesium chloride, lithium thiocyanate, Sodium Thiocyanate 99, Magnesium sulfocyanate, nitrocalcite, cupric nitrate, calcium carbonate, the calcium phosphate.
In the technique scheme, acid concentration is 10～100wt% in the silk lysate of described step (2); Salt concn is 0.1～50wt%.
The invention also discloses the regenerated silk protein solution for preparing according to above-mentioned preparation method.
In the above-mentioned regenerated silk protein solution, the massfraction of regenerated silk protein is 0.1%～50%.
Because technique scheme is used, the present invention compared with prior art has following advantages:
(1) the present invention utilizes the aqueous solution dissolving boiled silk of acid and salt and makes regenerated silk protein solution, be mainly unbroken natural fibrillar structure in the solution, compared with prior art, thus obtained regenerated silk protein material has excellent mechanical property, dry state breaking tenacity such as fibroin protein film reaches 80MPa, and the hygrometric state breaking tenacity reaches 20MPa;
(2) working method disclosed by the invention is simply efficient, and the dissolving of silk is fast, and need not dialysis, is fit to industrial applications.
Description of drawings
Fig. 1 is that the regenerated silk protein solution of preparation among embodiment one and the embodiment two drops in dried infrared spectrum on the pressing potassium bromide troche;
Fig. 2 is the scanning electron microscope (SEM) photograph of the regenerated silk protein solution of preparation among the embodiment one, two, three and four;
Fig. 3 is the stress strain curve figure of the regenerated silk fibroin film that makes of embodiment five and Comparative Examples one.
Embodiment
The invention will be further described below in conjunction with drawings and Examples, Comparative Examples:
Embodiment one:
(1) natural mulberry silk boils 30min with the sodium carbonate solution of 0.1wt% and comes unstuck, and repeats 3 times and obtains to come unstuck afterwards mulberry silk;
(2) preparing natural boiled silk lysate: 98% formic acid is diluted with water to 80%, then adds lithiumbromide and be made into 80% formic acid solution that contains 2% lithiumbromide, be the silk lysate;
(3) boiled silk of step (1) is dissolved in the lysate of step (2) with 5% concentration, solvent temperature is 60 ℃, and stirring at low speed 2h obtains regenerated silk protein solution.
Embodiment two:
(1) natural mulberry silk boils 30min with the sodium hydrogen carbonate solution of 0.05wt% and comes unstuck, and repeats 3 times and obtains to come unstuck afterwards mulberry silk;
(2) preparing natural boiled silk lysate: in 98% formic acid, add 5% calcium chloride, be the silk lysate;
(3) boiled silk of step (1) is dissolved in the lysate of step (2) with 20% concentration, solvent temperature is 30 ℃, and stirring at low speed 4h obtains regenerated silk protein solution;
Accompanying drawing 1 drops in dried infrared spectrum on the pressing potassium bromide troche for embodiment one with the regenerated silk protein solution that embodiment two prepares, referring to Fig. 1, in the regenerated silk protein solution that makes by technical scheme provided by the present invention, the silk fibroin structure is take amorphous as main.
Embodiment three:
(1) natural mulberry silk boils 30min with the sodium carbonate solution of 0.5wt% and comes unstuck, and repeats 3 times and obtains to come unstuck afterwards mulberry silk;
(2) preparing natural boiled silk lysate: 85% phosphoric acid is diluted with water to 30%, then adds lithiumbromide and be made into 30% phosphoric acid solution that contains 5% lithiumbromide, be the silk lysate;
(3) boiled silk of step (1) is dissolved in the lysate of step (2) with 15% concentration, solvent temperature is 60 ℃, and stirring at low speed 6h obtains regenerated silk protein solution.
Embodiment four:
(1) natural mulberry silk boils 30min with the neutral soap solution of 5wt% and comes unstuck, and repeats 3 times and obtains to come unstuck afterwards mulberry silk;
(2) preparing natural boiled silk lysate: with 85% phosphoric acid, 80% formic acid and water blend, be made into and contain sour 50%(phosphoric acid: the solution of formic acid=1:4), then in this solution, add 5% lithium thiocyanate, be the silk lysate;
(3) boiled silk of step (1) is dissolved in the lysate of step (2) with 25% concentration, solvent temperature is 80 ℃, and stirring at low speed 2h obtains regenerated silk protein solution.
Accompanying drawing 2 is the scanning electron microscope picture of the silk fibroin protein solution of embodiment one, two, three and four preparations, referring to Fig. 2, be mainly unbroken fibrillar structure in the regenerated silk protein solution by technical scheme preparation provided by the present invention, illustrate that preparation method provided by the present invention mainly is a minute fibre to the solubility behavior of silk.
Embodiment five:
(1) pours the regenerated silk protein solution of embodiment one preparation in polyethylene board drying and forming-film;
(2) film in the step (1) is placed flowing water soak 3h and remove lithiumbromide, then place 40 ℃ of dry 20h of vacuum drying oven;
(3) film that step (2) is made is soaked in 75% ethanol processes half an hour, obtains after the drying that (sample a) take the beta sheet structure as main regenerated silk fibroin film.
Comparative Examples one:
(1) natural mulberry silk boils 30min with the sodium carbonate solution of 0.1wt% and comes unstuck, and repeats 3 times and obtains to come unstuck afterwards mulberry silk;
(2) boiled silk that step (1) is made is dissolved in the lithium bromide water solution of 9.3M, solvent temperature 60
℃, dissolution time 6h;
(3) silk fibroin protein solution that step (2) is obtained injects dialysis tubing and places the flow deionized water 3d that dialyses;
(4) the pure silk fibroin solution that step (3) is obtained is poured drying and forming-film in the polyethylene board into;
(5) film that step (4) is made is soaked in 75% ethanol processes half an hour, obtains after the drying take the beta sheet structure as main regenerated silk fibroin film (sample b).
The stress strain curve figure of two kinds of regenerated silk fibroin films that accompanying drawing 3 makes for embodiment five and Comparative Examples one, wherein a is that the present invention prepares fibroin membrane (sample a), b is for one of existing typical technology preparation fibroin membrane (sample b), finds out that therefrom the regenerated silk protein solution that the present invention makes can make up the more excellent regenerated silk fibroin film of mechanical property.
Claims (9)
1. a method for preparing regenerated silk protein solution is characterized in that, may further comprise the steps:
(1) natural silk comes unstuck through yellow soda ash, sodium bicarbonate or neutral soap and obtains the boiled silk fiber;
(2) mixing acid and water, and then the adding inorganic salt make the silk lysate;
(3) the boiled silk fiber that step (1) is prepared is put into the silk lysate of step (2), obtains described regenerated silk protein solution behind 10～100 ℃ of lower 0.5～6h of stirring.
2. preparation method according to claim 1, it is characterized in that: the silk in the described step (1) is one or more in mulberry silk, tussah silk, the ricinus silk.
3. preparation method according to claim 1, it is characterized in that: the inorganic salt in the described step (2) are one or more in lithiumbromide, calcium chloride, zinc chloride, magnesium chloride, lithium thiocyanate, Sodium Thiocyanate 99, Magnesium sulfocyanate, nitrocalcite, cupric nitrate, calcium carbonate, the calcium phosphate.
4. preparation method according to claim 1, it is characterized in that: the acid in the described step (2) is the blend of formic acid, phosphoric acid or formic acid and phosphoric acid.
5. preparation method according to claim 4, it is characterized in that: in the blend of described formic acid and phosphoric acid, the mass ratio of formic acid and phosphoric acid is 1: 0.25～4.
6. preparation method according to claim 1, it is characterized in that: acid concentration is 10～100wt% in the silk lysate of described step (2).
7. preparation method according to claim 1, it is characterized in that: inorganic salt concentration is 0.1～50wt% in the silk lysate of described step (2).
8. preparation method according to claim 1, it is characterized in that: in the regenerated silk protein solution of described step (3), the massfraction of regenerated silk protein is 0.1%～50%.
9. the regenerated silk protein solution for preparing of described any one preparation method according to claim 1～8.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885070A (en) * | 2016-05-04 | 2016-08-24 | 南京师范大学 | Preparation method of regenerated silk fibroin membrane |
| CN105968384A (en) * | 2016-05-19 | 2016-09-28 | 苏州大学 | Amorphous silk fibroin nanofiber solution and preparation method thereof |
| CN106422522A (en) * | 2015-08-11 | 2017-02-22 | 清华大学 | Silk nano-fiber-based air filtering device |
| CN106589091A (en) * | 2016-12-09 | 2017-04-26 | 宁波芸生纺织品科技有限公司 | Method for dissolving fiber of natural silk |
| CN107083674A (en) * | 2017-05-25 | 2017-08-22 | 南京林业大学 | A kind of preparation method of silk nanofiber dispersion liquid |
| CN107298766A (en) * | 2017-06-27 | 2017-10-27 | 广西科技大学 | Regenerate tussah silk fibroin solution and preparation method thereof |
| CN108114315A (en) * | 2018-02-22 | 2018-06-05 | 南通大学 | A kind of mariages fibroin nerve graft |
| CN108329385A (en) * | 2018-03-06 | 2018-07-27 | 苏州先蚕丝绸有限公司 | A kind of preparation method of regenerated silk fibroin solution |
| CN109187960A (en) * | 2018-09-10 | 2019-01-11 | 浙江理工大学 | A method of the detection Ancient Silk Textile based on immunochromatography technique |
| CN112048778A (en) * | 2020-09-10 | 2020-12-08 | 贵州大学 | Preparation method of silk solution |
| CN113980109A (en) * | 2021-09-13 | 2022-01-28 | 苏州大学 | Preparation method of regenerated silk fibroin material |
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| CN101724920A (en) * | 2009-11-13 | 2010-06-09 | 东华大学 | Method for preparing regenerated silk fiber by means of dry spinning |
| CN103184570A (en) * | 2013-04-09 | 2013-07-03 | 苏州维赛生物医药有限公司 | Silk-fibroin-based antibacterial nanofiber and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101724920A (en) * | 2009-11-13 | 2010-06-09 | 东华大学 | Method for preparing regenerated silk fiber by means of dry spinning |
| CN103184570A (en) * | 2013-04-09 | 2013-07-03 | 苏州维赛生物医药有限公司 | Silk-fibroin-based antibacterial nanofiber and preparation method thereof |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106422522A (en) * | 2015-08-11 | 2017-02-22 | 清华大学 | Silk nano-fiber-based air filtering device |
| CN105885070A (en) * | 2016-05-04 | 2016-08-24 | 南京师范大学 | Preparation method of regenerated silk fibroin membrane |
| CN105885070B (en) * | 2016-05-04 | 2019-02-22 | 南京师范大学 | A kind of preparation method of regenerated silk fibroin membrane |
| CN105968384B (en) * | 2016-05-19 | 2018-03-27 | 苏州大学 | A kind of amorphous silk fibroin nano-fiber solution and preparation method thereof |
| CN105968384A (en) * | 2016-05-19 | 2016-09-28 | 苏州大学 | Amorphous silk fibroin nanofiber solution and preparation method thereof |
| CN106589091A (en) * | 2016-12-09 | 2017-04-26 | 宁波芸生纺织品科技有限公司 | Method for dissolving fiber of natural silk |
| CN107083674A (en) * | 2017-05-25 | 2017-08-22 | 南京林业大学 | A kind of preparation method of silk nanofiber dispersion liquid |
| CN107298766A (en) * | 2017-06-27 | 2017-10-27 | 广西科技大学 | Regenerate tussah silk fibroin solution and preparation method thereof |
| CN107298766B (en) * | 2017-06-27 | 2020-10-27 | 广西科技大学 | Regenerated tussah silk fibroin solution and preparation method thereof |
| CN108114315A (en) * | 2018-02-22 | 2018-06-05 | 南通大学 | A kind of mariages fibroin nerve graft |
| CN108329385A (en) * | 2018-03-06 | 2018-07-27 | 苏州先蚕丝绸有限公司 | A kind of preparation method of regenerated silk fibroin solution |
| CN109187960A (en) * | 2018-09-10 | 2019-01-11 | 浙江理工大学 | A method of the detection Ancient Silk Textile based on immunochromatography technique |
| CN112048778A (en) * | 2020-09-10 | 2020-12-08 | 贵州大学 | Preparation method of silk solution |
| CN112048778B (en) * | 2020-09-10 | 2023-03-10 | 贵州大学 | Preparation method of silk solution |
| CN113980109A (en) * | 2021-09-13 | 2022-01-28 | 苏州大学 | Preparation method of regenerated silk fibroin material |
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Application publication date: 20130925 Assignee: Nine silk limited company of a specified duration Assignor: Soochow University Contract record no.: 2015320010041 Denomination of invention: Regenerated silk fibroin solution and preparation method thereof License type: Exclusive License Record date: 20150416 |
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