CN109232919A - A kind of preparation method of the recessed native composite aerogel of fibroin- - Google Patents
A kind of preparation method of the recessed native composite aerogel of fibroin- Download PDFInfo
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- CN109232919A CN109232919A CN201811054047.0A CN201811054047A CN109232919A CN 109232919 A CN109232919 A CN 109232919A CN 201811054047 A CN201811054047 A CN 201811054047A CN 109232919 A CN109232919 A CN 109232919A
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- China
- Prior art keywords
- fibroin
- recessed
- preparation
- composite aerogel
- solution
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
Abstract
The invention discloses a kind of preparation methods of the recessed native composite aerogel of fibroin-, its main preparation process are as follows: under alkaline condition, recessed soil paste material and silk fibroin solution are carried out effective processing to be blended, it handles to obtain the recessed native composite hydrogel of fibroin-by being physical crosslinking and being chemically crosslinked collaboration, which can be widely applied to the pharmaceutical field such as medicine sustained and controlled release and dressing for skin；Further frozen dried had both obtained the recessed native composite aerogel of fibroin-, can be used for the directions such as air humidity adjusting and air cleaning.Compared with traditional silk extract gel, the introducing of recessed soil assigns the faster gelation rate of plural gel and higher mechanical property, and while keeping former silk extract gel good biocompatibility, Effective Regulation gel pore structure simultaneously significantly reduces gel preparation cost.The raw materials used present invention is natural green materials, have good biocompatibility, safety and environmental protection and simple process.
Description
Technical field
The invention belongs to clay field of deep, are related to the preparation method of clay-based gel, and in particular to a kind of fibroin-is recessed
The preparation method of native composite aerogel.
Background technique
Fibroin albumen is natural macromolecular material, has excellent biocompatibility and biodegradability, in consolidating for enzyme
The biomedicine fields such as the slow controlled release of fixedization and drug have a extensive future.Fibroin albumen usually all with gel form application, but
Fibroin albumen at least needs 8 days from solution to the gel conversion time, and the mechanical property of gained gel is insufficient.Min of Zhejiang University
Think good (CN1379055) and disclose a kind of method that chemical crosslinking prepares silk extract gel, is handed over by ethylene glycol diglycidylether
Connection is so that silk extract gel is greatly improved in mechanical property；The Yan Shuqin etc. of Wuhan Textile University
(CN106866996A) silk fibroin solution is placed under weak electric field and is electrolysed, accelerate fibroin protein gel preparation speed.
The research of silk extract gel at present focuses primarily upon the preparation of single silk extract gel, few about fibroin and other objects
Matter is compound, prepares the report of plural gel.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation methods of the recessed native composite aerogel of fibroin-.
The present invention is achieved by the following technical solutions:
A kind of preparation method of the recessed native composite aerogel of fibroin-, comprising the following steps:
A, silk cocoon peeled off, go pupa, degumming process, drying, obtain fibroin fiber；
B, fibroin fiber is dissolved with lithium bromide or calcium chloride solution, centrifugation removes dialysis and drying and dewatering after precipitated impurities, obtains fibroin
Protein solids；
C, sodium hydroxide solution is dispersed by recessed soil, obtains recessed soil paste material；
D, fibroin albumen solid particle obtained by step b is dissolved in sodium hydroxide solution, obtains silk fibroin solution；
E, the silk fibroin solution of recessed soil paste material and step d made from step c are mixed, is immersed in deionized water at least 20h gel
Change；
F, by the material after gelation obtained by step e, it is soaked in 8~10h of glutaraldehyde solution, obtains the high-intensitive recessed soil of fibroin-
Composite hydrogel；
G, the recessed native composite aerogel of fibroin-will be obtained after the drying of composite hydrogel cryogenic quick freezing obtained by step f.
Further improvement of the present invention scheme are as follows:
Lithium bromide described in step b or calcium chloride solution concentration are 35wt%~45wt%.
Concentration of sodium hydroxide solution described in step c be 3~7%, recessed soil paste material concave soil concentration obtained be 2wt%~
5wt%。
Concentration of sodium hydroxide solution described in step d is 3~7%, in silk fibroin solution obtained fibroin concentration be 1wt%~
4wt%。
The mass ratio of recessed soil paste material and silk fibroin solution described in step e is 4:1~1:4.
The dry temperature of cryogenic quick freezing described in step g is -80~-200 DEG C
The invention has the benefit that
Recessed soil is natural monodimension nanometer material, belongs to rich magnesium aluminosilicate clays mineral, and fiber has preferable toughness and physics
Crosslinking advantage is the ideal composition for preparing macromolecule plural gel.
Recessed soil content can arbitrarily regulate and control between 20-80% mass ratio, significantly reduce gel preparation cost.Simple process peace
Entirely, process is easily controllable, is suitable for industrialized production.
For the present invention compared with simple Silk fibroin gel, porosity can be up to 99%, and aperture is down to 10 μm, hygroscopic capacity
Reach 60% or more of own wt, have better filling effect, moisture absorption, performance of keeping humidity have to be promoted significantly, in damping material
Material field has biggish application potential.
Specific embodiment
Embodiment 1
A, silk cocoon peeled off, remove pupa, be placed in degumming process in 0.5wt% sodium carbonate liquor, drying obtains fibroin fiber at 80 DEG C；
B, fibroin fiber is dissolved with 9.3M lithium-bromide solution, centrifugation removes dialysis and drying and dewatering after precipitated impurities, obtains fibroin albumen
Solid particle；
C, 5% sodium hydroxide solution is dispersed by recessed soil, is configured to the recessed soil paste material of 5wt%；
D, fibroin albumen solid particle obtained by step b is dissolved in 5% sodium hydroxide solution, the fibroin for being configured to clear 1wt% is molten
Liquid；
E, the 4:1 ratio in mass ratio of the silk fibroin solution of recessed soil paste material and step d made from step c is mixed, is immersed in deionization
It is for 24 hours afterwards gelation in water；
F, hydrogel obtained by step e is immersed in glutaraldehyde solution 12h, obtains the recessed native composite hydrogel of high-intensitive fibroin-, draws
Intensity is stretched up to 2g/mm2；
G, composite hydrogel obtained by step f is placed in after -196 DEG C of fast freezings dryings and obtains the recessed native composite aerogel of fibroin -.
Through detecting, the density of composite aerogel is about 0.095g/cm3, aperture 12nm, porosity 98%, BET compares table
Face is 78m2·g-1, maximum hygroscopicity reaches the 75% of own wt, reaches the primary condition as humidity adjusting material.
Embodiment 2:
A, silk cocoon peeled off, remove pupa, be placed in degumming process in 0.5wt% sodium carbonate liquor, drying obtains fibroin fiber at 80 DEG C；
B, fibroin fiber is dissolved with 9.3M lithium-bromide solution, centrifugation removes dialysis and drying and dewatering after precipitated impurities, obtains fibroin albumen
Solid particle；
C, 5% sodium hydroxide solution is dispersed by recessed soil, is configured to the recessed soil paste material of 3wt%；
D, fibroin albumen solid particle obtained by step b is dissolved in 5% sodium hydroxide solution, the fibroin for being configured to clear 2wt% is molten
Liquid；
E, the 1:1 ratio in mass ratio of the silk fibroin solution of recessed soil paste material and step d made from step c is mixed, is immersed in deionization
It is for 24 hours afterwards gelation in water；
F, hydrogel obtained by step e is immersed in glutaraldehyde solution 12h, obtains the recessed native composite hydrogel of high-intensitive fibroin-, draws
Intensity is stretched up to 5g/mm2；
G, composite hydrogel obtained by step f is placed in after -80 DEG C of fast freezings dryings and obtains the recessed native composite aerogel of fibroin -.
Through detecting, the density of composite aerogel is 0.056g/cm3。
Embodiment 3:
A, silk cocoon peeled off, remove pupa, be placed in degumming process in 0.5wt% sodium carbonate liquor, drying obtains fibroin fiber at 80 DEG C；
B, fibroin fiber is dissolved with 9.3M lithium-bromide solution, centrifugation removes dialysis and drying and dewatering after precipitated impurities, obtains fibroin albumen
Solid particle；
C, 5% sodium hydroxide solution is dispersed by recessed soil, is configured to the recessed soil paste material of 2wt%；
D, fibroin albumen solid particle obtained by step b is dissolved in 5% sodium hydroxide solution, the fibroin for being configured to clear 4wt% is molten
Liquid；
E, the 1:4 ratio in mass ratio of the silk fibroin solution of recessed soil paste material and step d made from step c is mixed, is immersed in deionization
It is for 24 hours afterwards gelation in water；
F, hydrogel obtained by step e is immersed in glutaraldehyde solution 12h, obtains the recessed native composite hydrogel of high-intensitive fibroin-, it is compound
The tensile strength of hydrogel reaches 9g/mm2；
G, composite hydrogel obtained by step f is placed in after -200 DEG C of fast freezings dryings and obtains the recessed native composite aerogel of fibroin -.
Through detecting, the density of composite aerogel is 0.042g/cm3.It is applied to energy storage material, paraffin adsorbance reaches
3000%, latent heat of phase change 164J/g reach the primary condition as energy storage material.
Claims (6)
1. a kind of preparation method of the recessed native composite aerogel of fibroin-, which comprises the following steps:
A, silk cocoon peeled off, go pupa, degumming process, drying, obtain fibroin fiber；
B, fibroin fiber is dissolved with lithium bromide or calcium chloride solution, centrifugation removes dialysis and drying and dewatering after precipitating, obtains fibroin albumen
Solid particle；
C, aqueous slkali is dispersed by recessed soil, obtains recessed soil paste material；
D, fibroin albumen solid particle obtained by step b is dissolved in aqueous slkali, obtains silk fibroin solution；
E, the silk fibroin solution of recessed soil paste material and step d made from step c are mixed, is immersed at least 20h gelation in water；
F, by the material after gelation obtained by step e, it is soaked in 8~10h of glutaraldehyde solution, obtains the high-intensitive recessed soil of fibroin-
Composite hydrogel；
G, the recessed native composite aerogel of fibroin-will be obtained after composite hydrogel frozen drying obtained by step f.
2. a kind of preparation method of the recessed native composite aerogel of fibroin-according to claim 1, it is characterised in that: step b institute
It states lithium bromide or calcium chloride solution concentration is 35wt%~45wt%.
3. a kind of preparation method of the recessed native composite aerogel of fibroin-according to claim 1, it is characterised in that: step c institute
The aqueous slkali stated is sodium hydroxide solution, and concentration is 3~7%, and recessed soil paste material concave soil concentration obtained is 2wt%~5wt%.
4. a kind of preparation method of the recessed native composite aerogel of fibroin-according to claim 1, it is characterised in that: step d institute
The aqueous slkali stated is sodium hydroxide solution, and concentration is 3~7%, and fibroin concentration is 1wt%~4wt% in silk fibroin solution obtained.
5. a kind of preparation method of the recessed native composite aerogel of fibroin-according to claim 1, it is characterised in that: the step
The mass ratio of rapid e concave soil paste material and silk fibroin solution is 4:1~1:4.
6. a kind of preparation method of the recessed native composite aerogel of fibroin-according to claim 1, it is characterised in that: the step
The temperature of frozen drying is -80~-200 DEG C in rapid g.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811054047.0A CN109232919A (en) | 2018-09-11 | 2018-09-11 | A kind of preparation method of the recessed native composite aerogel of fibroin- |
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| CN201811054047.0A CN109232919A (en) | 2018-09-11 | 2018-09-11 | A kind of preparation method of the recessed native composite aerogel of fibroin- |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110669247A (en) * | 2019-09-24 | 2020-01-10 | 淮阴工学院 | Preparation method and application of attapulgite-based silk sodium alginate composite aerogel |
| CN113769669A (en) * | 2021-09-30 | 2021-12-10 | 大连理工大学 | Ionic crosslinked clay aerogel material, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379055A (en) * | 2001-04-06 | 2002-11-13 | 浙江大学 | Process for preparing Chemically cross-linked silk extract gel or spongy silk extract gel |
| CN105017555A (en) * | 2014-04-29 | 2015-11-04 | 中国科学院化学研究所 | Cellulose aerogel and preparation method for hybrid aerogel thereof |
| CN105837861A (en) * | 2016-04-03 | 2016-08-10 | 苏鑫 | Composite natural polymer gel material |
| CN106178131A (en) * | 2016-07-04 | 2016-12-07 | 南通纺织丝绸产业技术研究院 | A kind of preparation method of fibroin albumen aeroge |
-
2018
- 2018-09-11 CN CN201811054047.0A patent/CN109232919A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379055A (en) * | 2001-04-06 | 2002-11-13 | 浙江大学 | Process for preparing Chemically cross-linked silk extract gel or spongy silk extract gel |
| CN105017555A (en) * | 2014-04-29 | 2015-11-04 | 中国科学院化学研究所 | Cellulose aerogel and preparation method for hybrid aerogel thereof |
| CN105837861A (en) * | 2016-04-03 | 2016-08-10 | 苏鑫 | Composite natural polymer gel material |
| CN106178131A (en) * | 2016-07-04 | 2016-12-07 | 南通纺织丝绸产业技术研究院 | A kind of preparation method of fibroin albumen aeroge |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110669247A (en) * | 2019-09-24 | 2020-01-10 | 淮阴工学院 | Preparation method and application of attapulgite-based silk sodium alginate composite aerogel |
| CN113769669A (en) * | 2021-09-30 | 2021-12-10 | 大连理工大学 | Ionic crosslinked clay aerogel material, preparation method and application thereof |
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Application publication date: 20190118 |