CN106620844A - Calcium carbonate enhanced fibroin fiber scaffold and preparation method thereof - Google Patents
Calcium carbonate enhanced fibroin fiber scaffold and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a calcium carbonate enhanced fibroin fiber scaffold and a preparation method thereof. The preparation method comprises the following steps: conducting degumming treatment on silks so as to obtain fibroin fibers; dispersing the fibroin fibers in calcium salt/formic acid mixed liquid, so that fibroin fiber dispersion liquid is obtained; dropping the fibroin fiber dispersion liquid into a carbonate solution, so that reaction liquid is obtained; then, filtering the reaction liquid, and washing and drying a filter cake so as to obtain a calcium carbonate nanowire; adding sodium chloride to the fibroin fiber dispersion liquid, uniformly stirring the liquid and then adding the calcium carbonate nanowire; and stirring obtained liquid, removing formic acid through volatilization, conducting treatment in flowing water and implementing freezing treatment so as to obtain a frozen body, and freeze-drying the frozen body, so as to obtain the calcium carbonate enhanced fibroin fiber scaffold. The internal structure of the calcium carbonate enhanced fibroin fiber scaffold prepared by the preparation method provided by the invention mainly contains fibers; and the calcium carbonate enhanced fibroin fiber scaffold, as an ideal tissue engineering scaffold, is high in porosity, high in holing ratio and excellent in mechanical performance.
Description
Technical field
The present invention relates to enhanced fibroin fiber support of a kind of Calcium Carbonate and preparation method thereof, can be used for soft tissue, hard group
Knit the regenerative medicine fields such as reparation and medicament slow release.
Background technology
Fibroin is derived from the natural polymer biomaterial of nature, with excellent mechanical property, controllable
Biological degradability, workability and become the raw material of preferable regenerative medicine support.With modern medicine and surgical operation skill
The development of art, has been widely accepted by tissue or organ transplantation come repair function loss, but is but faced with huge confession
Body breach.The reparation for forming tissue or organ in vivo or in vitro to be damaged function by regenerative medicine means body provides new
Therapeutic scheme.Wherein, the selection of tissue engineering bracket material and it is configured to one of key of the Therapeutic Method.
At present, preparing the method for silk fibroin porous scaffold has a lot, including lyophilization, salting out method, gas foaming method,
3 D-printing etc., but all still there are some deficiencies for being difficult to overcome in these methods.For example, freeze-drying easily forms lamella
Structure, is unfavorable for cell and tissue growth, although prior art reports one kind and film dissolving control fibroin albumen is repeated certainly
Assembling forms nanofibrous structures, and then forms porous support, but efficiency is low, poor repeatability, and the presence of hole wall structure is straight
Connect and limit the migration of cell and interact, tissue growth is also therefore limited.
For this purpose, overcoming the problems referred to above of existing process technology and fibroin supporting structure, a kind of preparation method, and structure are developed
Build out and be conducive to cell to cure in the application of biomedical materials field and regeneration to fibroin albumen with the fibroin support of tissue growth
Clinical practice all has and has very great significance.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the enhanced fibroin fiber support of Calcium Carbonate, and by party's legal system
The enhanced fibroin fiber support of standby Calcium Carbonate, the large aperture high voidage advantage with porous support, while having threadiness
Inner structural features, strengthen especially by calcium carbonate nano wire, being greatly facilitated cell growth, such as cell propagation with
It is highly beneficial to tissue engineering technique clinical practice with good mechanical property while migration and tissue growth.
To reach above-mentioned purpose, the present invention provides a kind of preparation method of the enhanced fibroin fiber support of Calcium Carbonate, including
Following steps,
（1）Degumming process is carried out to silkworm silk, fibroin fiber is obtained；
（2）Fibroin fiber is scattered in calcium salt/formic acid mixed liquor, fibroin fiber dispersion liquid is obtained；
（3）By step（2）Fibroin fiber dispersant liquid drop add carbonate solution in, obtain reactant liquor；Then filtering reacting liquid,
Filter cake obtains calcium carbonate nano wire through washing, after being dried；
（4）Sodium Chloride is added into step（2）Fibroin fiber dispersion liquid in, stir, be subsequently adding step（3）Calcium Carbonate
Nano wire；Volatilization after stirring removes formic acid and obtains fibroin fiber-Sodium Chloride-calcium carbonate solid；
（5）Fibroin fiber-Sodium Chloride-calcium carbonate solid is placed in the water of flowing and is processed, obtain hygrometric state fibroin fiber support；
（6）Hygrometric state fibroin fiber support is carried out into freezing processing and obtains Frozen Body, then lyophilization is carried out to Frozen Body and obtained final product
To the enhanced fibroin fiber support of Calcium Carbonate.
In above-mentioned technical proposal, the silkworm silk be mulberry silk, tussah silk, ricinus silk or wild silk yarn, preferred mulberry silk.
In above-mentioned technical proposal, the mass concentration of the formic acid is 50-99%, preferred 80-98%；Calcium salt/the formic acid is mixed
In closing liquid, the mass concentration of calcium salt is 1.1-1.8%, and calcium salt is calcium chloride etc..The present invention is fine with salt/formic acid dispersion fibroin albumen
Dimension, and does not dissolve, the natural fibroin fiber internal stent structure of preparation based on fiber, with high porosity, high insertion rate, excellent
Good mechanical property.
In above-mentioned technical proposal, in the fibroin fiber dispersion liquid, the mass concentration of fibroin fiber is 2-30%, preferred 5-
10%。
In above-mentioned technical proposal, the particle diameter of the Sodium Chloride is 1-20 μm, preferred 10-15 μm.Thus obtained porous knot
Structure is more beneficial for sticking and growth for cell, and tissue grows into, while good mechanical properties.
In above-mentioned technical proposal, the fibroin fiber is 1 with the mass ratio of Sodium Chloride:（80-100）, preferably 1:（88-
92）.Thus obtained support has loose structure, the suitable porosity being more uniformly distributed, and is more suitable for cell and tissue growth.
In above-mentioned technical proposal, the fibroin fiber is 1 with the mass ratio of carbonate:（0.1-0.8）；The carbonate is
Sodium carbonate or sodium bicarbonate.Carbonate is instilled in fibroin fiber dispersion liquid, calcium carbonate nano wire can be formed, with good
Biocompatibility, the mechanical property that can not only improve porous support compound with fibroin fiber increases machinability, and can be with
Keep support to be used as organizational structure and make the biological nature for needing；The calcium carbonate nano wire that especially prepared by the inventive method has
High draw ratio, can form good interfacial effect, it is to avoid boundary defect caused by existing inorganic material with fibroin fiber.
The present invention is swelling first to prepare fibroin fiber dispersion liquid, based on this, for calcium carbonate nano wire and fibroin
The preparation of fiber multihole support, according to limit mass ratio and be actually needed, select required for fibroin fiber dispersion liquid；Institute
It is 1 that fibroin fiber is stated with the mass ratio of calcium carbonate nano wire:（0.01-0.05）.
In above-mentioned technical proposal, the temperature of freezing processing is -10～-196 DEG C, and cryodesiccated temperature is -10～-80
DEG C, the time of freezing processing is less than the cryodesiccated time；The advantage for so processing takes into account energy conservation and loose structure
It is stable to obtain.
The invention also discloses the enhanced fibroin fiber support of Calcium Carbonate prepared according to above-mentioned preparation method, it is internal main
To be made up of fibroin fiber, fibre diameter is 50nm-50 μm, while also there is calcium carbonate nano wire between fiber；Brace aperture
Rate is more than 50%, and pore diameter range is 80-180 μm, and modulus of compressibility is 5kPa-100MPa.
The invention also discloses application of the enhanced fibroin fiber support of above-mentioned Calcium Carbonate in tissue engineering bracket is prepared.
Compared with prior art, the present invention directly builds textile porous materials with natural fibroin fiber, the preparation method profit
The slightly soluble effect existed to the good dispersion and a small amount of salt of silkworm silk with acid, with reference to handling process, prepared Calcium Carbonate increases
Strong fibroin fiber internal stent structure is based on fiber, while there is calcium carbonate nano wire, with high porosity, high insertion
Rate, excellent mechanical property, are very beneficial for conveying, the migration of cell, the growth of tissue of nutrient substance, are preferably to organize
Engineering rack.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of calcium carbonate nano wire prepared by embodiment one.
Specific embodiment
With reference to embodiment, the invention will be further described：
Embodiment one
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；
（2）Fibroin fiber is dissolved in the formic acid solution of 1.1% calcium chloride -98%, fibroin fiber dispersion liquid concentration 5%；
（3）Fibroin fiber dispersion liquid is slowly dropped into into sodium carbonate liquor carries out mineralising reaction, time for adding 0.5h；Fibroin fiber with
The mass ratio of sodium carbonate is 1: 0.1；Reacted solution is filtered, is washed, is dried to obtain the Calcium Carbonate of appearance white, powder
Nano wire；Accompanying drawing 1 is the scanning electron microscopic picture of above-mentioned calcium carbonate nano wire；As seen from the figure Calcium Carbonate linear diameter is in 80-160nm,
Length about 650nm, with high draw ratio；
（4）The sodium chloride particle of 10-15 μm of diameter is obtained by sub-sieve, in being subsequently adding fibroin fiber dispersion liquid, and stirs equal
It is even, calcium carbonate nano wire is added, to remove and remove Sodium Chloride in immersion circulating water after formic acid, obtain hygrometric state fibroin fiber support；It is wet
State fibroin fiber support obtains the enhanced fibroin fiber support of Calcium Carbonate in -20 DEG C of freezings, then -20 DEG C of lyophilizations, compresses
Modulus about 29kPa, internal stent fibre diameter is 880nm-50 μm, also there is calcium carbonate nano wire, brace aperture between fiber
Rate is more than 50%, and pore diameter range is 90-100 μm, and fibroin fiber is 1: 100 with the mass ratio of Sodium Chloride, calcium carbonate nano wire:
0.01。
Embodiment two
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；
（2）Fibroin fiber is dissolved in the formic acid solution of 1.6% calcium chloride -90%, fibroin fiber dispersion liquid concentration 5%；
（3）Fibroin fiber dispersion liquid is slowly dropped into into sodium carbonate liquor carries out mineralising reaction, time for adding 0.5h；Fibroin fiber with
The mass ratio of sodium carbonate is 1: 0.1；Reacted solution is filtered, is washed, is dried to obtain the Calcium Carbonate of appearance white, powder
Nano wire；Calcium Carbonate linear diameter in 90-150nm, length about 630nm, with high draw ratio；
（4）The sodium chloride particle of 10-15 μm of diameter is obtained by sub-sieve, in being subsequently adding fibroin fiber dispersion liquid, and stirs equal
It is even, calcium carbonate nano wire is added, to remove and remove Sodium Chloride in immersion circulating water after formic acid, obtain hygrometric state fibroin fiber support；It is wet
State fibroin fiber support obtains the enhanced fibroin fiber support of Calcium Carbonate in -10 DEG C of freezings, then -20 DEG C of lyophilizations, compresses
Modulus about 82kPa, internal stent fibre diameter is 500nm-25 μm, also there is calcium carbonate nano wire, brace aperture between fiber
Rate is more than 50%, and pore diameter range is 110-180 μm, and fibroin fiber is 1: 100 with the mass ratio of Sodium Chloride, calcium carbonate nano wire:
0.02。
Embodiment three
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；
（2）Fibroin fiber is dissolved in the formic acid solution of 1.5% calcium chloride -98%, fibroin fiber dispersion liquid concentration 10%；
（3）Fibroin fiber dispersion liquid is slowly dropped into into sodium carbonate liquor carries out mineralising reaction, time for adding 0.5h；Fibroin fiber with
The mass ratio of sodium carbonate is 1: 0.5；Reacted solution is filtered, is washed, is dried to obtain the Calcium Carbonate of appearance white, powder
Nano wire；Calcium Carbonate linear diameter in 100-160nm, length about 670nm, with high draw ratio；
（4）The sodium chloride particle of 1-15 μm of diameter is obtained by sub-sieve, in being subsequently adding fibroin fiber dispersion liquid, and stirs equal
It is even, calcium carbonate nano wire is added, to remove and remove Sodium Chloride in immersion circulating water after formic acid, obtain hygrometric state fibroin fiber support；It is wet
State fibroin fiber support obtains the enhanced fibroin fiber support of Calcium Carbonate in -196 DEG C of freezings, then -30 DEG C of lyophilizations, presses
Contracting modulus about 122kPa, internal stent fibre diameter is 500nm-25 μm, also there are calcium carbonate nano wire, bracket holes between fiber
Gap rate is more than 50%, and pore diameter range is 80-90 μm, and fibroin fiber is 1: 100 with the mass ratio of Sodium Chloride, calcium carbonate nano wire:
0.03。
Example IV
（1）Wild silk yarn boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；
（2）Fibroin fiber is dissolved in the formic acid solution of 1.6% calcium chloride -980%, fibroin fiber dispersion liquid concentration 5%；
（3）Fibroin fiber dispersion liquid is slowly dropped into into sodium carbonate liquor carries out mineralising reaction, time for adding 0.5h；Fibroin fiber with
The mass ratio of sodium carbonate is 1: 0.1；Reacted solution is filtered, is washed, is dried to obtain the Calcium Carbonate of appearance white, powder
Nano wire；Calcium Carbonate linear diameter in 90-150nm, length about 600nm, with high draw ratio；
（4）The sodium chloride particle of 10-15 μm of diameter is obtained by sub-sieve, in being subsequently adding fibroin fiber dispersion liquid, and stirs equal
It is even, calcium carbonate nano wire is added, to remove and remove Sodium Chloride in immersion circulating water after formic acid, obtain hygrometric state fibroin fiber support；It is wet
State fibroin fiber support obtains the enhanced fibroin fiber support of Calcium Carbonate in -90 DEG C of freezings, then -20 DEG C of lyophilizations, compresses
Modulus about 10MPa, internal stent fibre diameter is 500nm-15 μm, also there is calcium carbonate nano wire, brace aperture between fiber
Rate is more than 50%, and pore diameter range is 120-180 μm, and fibroin fiber is 1: 90 with the mass ratio of Sodium Chloride, calcium carbonate nano wire:
0.02。
Embodiment five
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；
（2）Fibroin fiber is dissolved in the formic acid solution of 1.8% calcium chloride -50%, fibroin fiber dispersion liquid concentration 5%；
（3）Fibroin fiber dispersion liquid is slowly dropped into into sodium carbonate liquor carries out mineralising reaction, time for adding 0.5h；Fibroin fiber with
The mass ratio of sodium carbonate is 1: 0.8；Reacted solution is filtered, is washed, is dried to obtain the Calcium Carbonate of appearance white, powder
Nano wire；Calcium Carbonate linear diameter in 90-110nm, length about 600nm, with high draw ratio；
（4）The sodium chloride particle of 10-20 μm of diameter is obtained by sub-sieve, in being subsequently adding fibroin fiber dispersion liquid, and stirs equal
It is even, calcium carbonate nano wire is added, to remove and remove Sodium Chloride in immersion circulating water after formic acid, obtain hygrometric state fibroin fiber support；It is wet
State fibroin fiber support obtains the enhanced fibroin fiber support of Calcium Carbonate in -150 DEG C of freezings, then -80 DEG C of lyophilizations, presses
Contracting modulus about 982kPa, internal stent fibre diameter is 50nm-5 μm, also there is calcium carbonate nano wire, brace aperture between fiber
Rate is more than 50%, and pore diameter range is 80-110 μm, and fibroin fiber is 1: 100 with the mass ratio of Sodium Chloride, calcium carbonate nano wire:
0.04。
Embodiment six
（1）Ricinus silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；
（2）Fibroin fiber is dissolved in the formic acid solution of 1.6% calcium chloride -90%, fibroin fiber dispersion liquid concentration 30%；
（3）Fibroin fiber dispersion liquid is slowly dropped into into sodium carbonate liquor carries out mineralising reaction, time for adding 0.5h；Fibroin fiber with
The mass ratio of sodium carbonate is 1: 0.1；Reacted solution is filtered, is washed, is dried to obtain the Calcium Carbonate of appearance white, powder
Nano wire；Calcium Carbonate linear diameter in 140-160nm, length about 680nm, with high draw ratio；
（4）The sodium chloride particle of 10-15 μm of diameter is obtained by sub-sieve, in being subsequently adding fibroin fiber dispersion liquid, and stirs equal
It is even, calcium carbonate nano wire is added, to remove and remove Sodium Chloride in immersion circulating water after formic acid, obtain hygrometric state fibroin fiber support；It is wet
State fibroin fiber support obtains the enhanced fibroin fiber support of Calcium Carbonate in -10 DEG C of freezings, then -20 DEG C of lyophilizations, compresses
Modulus about 812kPa, internal stent fibre diameter is 500nm-0.8 μm, also there are calcium carbonate nano wire, bracket holes between fiber
Gap rate is more than 50%, and pore diameter range is 80-140 μm, and fibroin fiber is 1: 100 with the mass ratio of Sodium Chloride, calcium carbonate nano wire:
0.01。
Embodiment seven
（1）Tussah silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；
（2）Fibroin fiber is dissolved in the formic acid solution of 1.2% calcium chloride -98%, fibroin fiber dispersion liquid concentration 24%；
（3）Fibroin fiber dispersion liquid is slowly dropped into into sodium carbonate liquor carries out mineralising reaction, time for adding 0.5h；Fibroin fiber with
The mass ratio of sodium carbonate is 1: 0.6；Reacted solution is filtered, is washed, is dried to obtain the Calcium Carbonate of appearance white, powder
Nano wire；Calcium Carbonate linear diameter in 90-100nm, length about 620nm, with high draw ratio；
（4）The sodium chloride particle of 10-15 μm of diameter is obtained by sub-sieve, in being subsequently adding fibroin fiber dispersion liquid, and stirs equal
It is even, calcium carbonate nano wire is added, to remove and remove Sodium Chloride in immersion circulating water after formic acid, obtain hygrometric state fibroin fiber support；It is wet
State fibroin fiber support obtains the enhanced fibroin fiber support of Calcium Carbonate in -10 DEG C of freezings, then -20 DEG C of lyophilizations, compresses
Modulus about 98MPa, internal stent fibre diameter is 500nm-5 μm, also there is calcium carbonate nano wire, brace aperture rate between fiber
More than 50%, pore diameter range is 80-100 μm, and fibroin fiber is 1: 100: 0.05 with the mass ratio of Sodium Chloride, calcium carbonate nano wire.
Embodiment eight
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；
（2）Fibroin fiber is dissolved in the formic acid solution of 1.5% calcium chloride -98%, fibroin fiber dispersion liquid concentration 10%；
（3）Fibroin fiber dispersion liquid is slowly dropped into into sodium carbonate liquor carries out mineralising reaction, time for adding 0.5h；Fibroin fiber with
The mass ratio of sodium carbonate is 1: 0.3；Reacted solution is filtered, is washed, is dried to obtain the Calcium Carbonate of appearance white, powder
Nano wire；Calcium Carbonate linear diameter in 90-130nm, length about 640nm, with high draw ratio；
（4）The sodium chloride particle of 10-15 μm of diameter is obtained by sub-sieve, in being subsequently adding fibroin fiber dispersion liquid, and stirs equal
It is even, calcium carbonate nano wire is added, to remove and remove Sodium Chloride in immersion circulating water after formic acid, obtain hygrometric state fibroin fiber support；It is wet
State fibroin fiber support obtains the enhanced fibroin fiber support of Calcium Carbonate in -10 DEG C of freezings, then -60 DEG C of lyophilizations, compresses
Modulus about 192kPa, internal stent fibre diameter is 800nm-12 μm, also there is calcium carbonate nano wire, brace aperture between fiber
Rate is more than 50%, and pore diameter range is 90-110 μm, and fibroin fiber is 1: 100 with the mass ratio of Sodium Chloride, calcium carbonate nano wire:
0.02。
Embodiment nine
（1）Mulberry silk boils 30min degummings with 0.5% sodium bicarbonate solution, and fibroin fiber is obtained after being repeated 3 times；
（2）Fibroin fiber is dissolved in the formic acid solution of 1.1% calcium chloride -90%, fibroin fiber dispersion liquid concentration 8%；
（3）Fibroin fiber dispersion liquid is slowly dropped into into sodium carbonate liquor carries out mineralising reaction, time for adding 0.5h；Fibroin fiber with
The mass ratio of sodium carbonate is 1: 0.12；Reacted solution is filtered, is washed, is dried to obtain the carbonic acid of appearance white, powder
Calcium nano wire；Calcium Carbonate linear diameter in 90-140nm, length about 630nm, with high draw ratio；
（4）The sodium chloride particle of 10-15 μm of diameter is obtained by sub-sieve, in being subsequently adding fibroin fiber dispersion liquid, and stirs equal
It is even, calcium carbonate nano wire is added, to remove and remove Sodium Chloride in immersion circulating water after formic acid, obtain hygrometric state fibroin fiber support；It is wet
State fibroin fiber support obtains the enhanced fibroin fiber support of Calcium Carbonate in -90 DEG C of freezings, then -20 DEG C of lyophilizations, compresses
Modulus about 782kPa, internal stent fibre diameter is 780nm-2 μm, also there is calcium carbonate nano wire, brace aperture between fiber
Rate is more than 50%, and pore diameter range is 80-90 μm, and fibroin fiber is 1: 100 with the mass ratio of Sodium Chloride, calcium carbonate nano wire:
0.02。
Embodiment ten
（1）Mulberry silk, wild silk yarn boil 30min degummings with 0.5% sodium bicarbonate solution respectively, and respective silk is obtained after being repeated 3 times
Fibroin fiber；
（2）Fibroin fiber is dissolved in the formic acid solution of 1.6% calcium chloride -98%, giant silkworm fibroin fiber dispersion liquid concentration 10%；Bombyxmori Linnaeuss
Fibroin fiber dispersion liquid concentration 10%；
（3）Mulberry fibroin fiber dispersion liquid is slowly dropped into into sodium carbonate liquor carries out mineralising reaction, time for adding 0.5h；Fibroin fiber
It is 1: 0.1 with the mass ratio of sodium carbonate；Reacted solution is filtered, is washed, is dried to obtain the carbonic acid of appearance white, powder
Calcium nano wire；Calcium Carbonate linear diameter in 110-150nm, length about 650nm, with high draw ratio；
（4）The sodium chloride particle of 10-15 μm of diameter is obtained by sub-sieve, in being subsequently adding giant silkworm fibroin fiber dispersion liquid, and is stirred
Mix uniform, add calcium carbonate nano wire, to remove and remove Sodium Chloride in immersion circulating water after formic acid, obtain hygrometric state fibroin fiber
Frame；Hygrometric state fibroin fiber support obtains the enhanced fibroin fiber of Calcium Carbonate in -40 DEG C of freezings, then -50 DEG C of lyophilizations
Frame, modulus of compressibility about 88MPa, internal stent fibre diameter is 500nm-25 μm, also there is calcium carbonate nano wire between fiber,
Frame porosity is more than 50%, and pore diameter range is 80-180 μm, and fibroin fiber is 1 with the mass ratio of Sodium Chloride, calcium carbonate nano wire:
100∶0.02。
Claims (10)
1. the preparation method of the enhanced fibroin fiber support of a kind of Calcium Carbonate, it is characterised in that comprise the steps,
（1）Degumming process is carried out to silkworm silk, fibroin fiber is obtained；
（2）Fibroin fiber is scattered in calcium salt/formic acid mixed liquor, fibroin fiber dispersion liquid is obtained；
（3）By step（2）Fibroin fiber dispersant liquid drop add carbonate solution in, obtain reactant liquor；Then filtering reacting liquid,
Filter cake obtains calcium carbonate nano wire through washing, after being dried；
（4）Sodium Chloride is added into step（2）Fibroin fiber dispersion liquid in, stir, be subsequently adding step（3）Calcium Carbonate
Nano wire；Volatilization after stirring removes formic acid and obtains fibroin fiber-Sodium Chloride-calcium carbonate solid；
（5）Fibroin fiber-Sodium Chloride-calcium carbonate solid is placed in the water of flowing and is processed, obtain hygrometric state fibroin fiber support；
（6）Hygrometric state fibroin fiber support is carried out into freezing processing and obtains Frozen Body, then lyophilization is carried out to Frozen Body and obtained final product
To the enhanced fibroin fiber support of Calcium Carbonate.
2. preparation method according to claim 1, it is characterised in that step（1）In, the silkworm silk is mulberry silk, Antherea pernyi Guerin-Meneville
Silk, ricinus silk or wild silk yarn.
3. preparation method according to claim 1, it is characterised in that step（2）In, the mass concentration of the formic acid is
50-99%；In the calcium salt/formic acid mixed liquor, the mass concentration of calcium salt is 1.1-1.8%.
4. preparation method according to claim 1, it is characterised in that step（2）In, in the fibroin fiber dispersion liquid,
The mass concentration of fibroin fiber is 2-30%.
5. preparation method according to claim 1, it is characterised in that step（4）In, the particle diameter of the Sodium Chloride is 1-20
μm。
6. preparation method according to claim 1, it is characterised in that step（4）In, the fibroin fiber and Sodium Chloride
Mass ratio is 1:（80-100）.
7. preparation method according to claim 1, it is characterised in that step（3）In, the fibroin fiber and carbonate
Mass ratio is 1:（0.1-0.8）；The carbonate is sodium carbonate or sodium bicarbonate.
8. preparation method according to claim 1, it is characterised in that step（6）In, the temperature of the freezing processing for-
10～-196 DEG C, cryodesiccated temperature is -10～-80 DEG C.
9. the enhanced fibroin fiber support of Calcium Carbonate that prepared by any one preparation method according to claim 1-8, it is special
Levy and be, the porosity of the enhanced fibroin fiber support of the Calcium Carbonate is more than 50%, and aperture is 80-180 μm.
10. application of the enhanced fibroin fiber support of Calcium Carbonate described in claim 9 in tissue engineering bracket is prepared.
Priority Applications (1)
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