CN109867811A - Porous-entity composite silk material of one kind and preparation method thereof - Google Patents
Porous-entity composite silk material of one kind and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of porous-entity composite silk material preparation methods, comprising: (1) fibroin albumen is dissolved in hexafluoroisopropanol, obtains silk fibroin protein solution；(2) silk fibroin protein solution is injected into porous mold, stood；Wherein, the porous mold includes peripheral wall and protective shell, and the peripheral wall has multiple apertures；(3) silk fibroin protein solution in Xiang Suoshu porous mold fills water soluble salt particle, obtains water soluble salt particle-silk fibroin protein solution mixture；(4) impregnating in methyl alcohol after the protective shell containing water soluble salt particle-silk fibroin protein solution mixture porous mold will be removed, the fibroin albumen solid containing water soluble salt particle is made；(5) methanol and water soluble salt particle in the fibroin albumen solid containing water soluble salt particle are removed, the compound fibroin material of porous-entity is obtained.
Description
Technical field
The present invention relates to organic high molecular polymer field of material technology, are specifically designed a kind of porous-entity composite silk
Material and preparation method thereof.
Background technique
It has excellent performance, is environmental-friendly, is numerous in variety, the bio-based materials that added value is high, widely used are always China's war
Slightly one of the key areas of property new industry and Biomass Industry development.The life of biological macromolecule material, especially natural product
Object macromolecular material has the advantages that many uniquenesses, such as good bio-compatibility, degradable spy in polymer material field
Property and property from a wealth of sources.
Fibroin material is the natural egg of the earliest exploitation of the mankind as a kind of biomaterial that applicating history is long
One of white matter material.Wherein, fibroin albumen is the main composition material (account for about silk quality 70%) of silk, is to have the modern times
A kind of novel green bio-based materials of scientific and technological feature.Compared to other oroteins material and organic polymer material, fibroin egg
White have unique and excellent biology, optically and mechanically a performance, including high transparency, without human body rejection, human body it is absorbable,
Dissolution and degradation rate is controllable, high strength, from a wealth of sources etc., thus play in many new Disciplinary Frontiers important
Role.
Currently, fibroin albumen bulk form is mainly porous support, without the compound fibroin material of porous-entity, thus
Limiting it has extensive use in fields such as biologic medical, novel microelectronics.Therefore, porous-entity composite filament how is prepared
Fibroin material is the project for being worth research.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of porous-entity composite silks
Material and preparation method thereof, to prepare adjustable a kind of porosity and aperture diameter, porous structure and entity structure are firmly combined,
Biodegrade and the regulatable porous-entity composite silk material of mechanical property can be widely applied to biological implantable medical neck
Domain.
First method of the present invention provides a kind of porous-entity composite silk material preparation method, and the porous-entity is multiple
Silk material preparation method is closed the following steps are included: the fibroin albumen is dissolved in hexafluoroisopropanol by (1), acquisition fibroin albumen is molten
Liquid；(2) silk fibroin protein solution is injected into porous mold, stood；Wherein, the porous mold includes peripheral wall and protective shell,
The peripheral wall has multiple apertures；(3) silk fibroin protein solution in Xiang Suoshu porous mold fills water soluble salt particle, obtains water
Dissolubility salt particle-silk fibroin protein solution mixture；(4) it will remove after the protective shell and contain water soluble salt particle-fibroin egg
The porous mold of white solution mixture impregnates in methyl alcohol, and the fibroin albumen solid containing water soluble salt particle is made；(5) it removes
Methanol and water soluble salt particle in the fibroin albumen solid containing water soluble salt particle obtain porous-entity composite filament
Fibroin material.
In one embodiment of the present of invention, in step (1), the fibroin albumen is anhydrous fibroin albumen.
In one embodiment of the present of invention, the fibroin albumen prepares fibroin before being dissolved in hexafluoroisopropanol
Protein solution, freeze-drying become anhydrous fibroin albumen dried powder；The anhydrous fibroin albumen dried powder is dissolved in six
Fluorine isopropanol obtains the silk fibroin protein solution.
In one embodiment of the present of invention, the step (1) includes: that silk cocoon is placed in sodium carbonate liquor, heating, shape
At silk；First is dry；LiBr LiSCN solution is added, and keeps the temperature preset time, obtains mixed solution；It dialyses described mixed
Solution, and the solution after spin dialysis are closed, supernatant is taken, obtains silk fibroin water solution；The second freeze-drying fibroin egg
White solution obtains the fibroin albumen.
Preferably, the silk cocoon is the silkworm cocoon for removing silkworm chrysalis；Further, the silk cocoon is integral finish silk cocoon or cuts
Broken silk cocoon, wherein the shape for shredding silk cocoon is bar shaped or rectangular, 1~1000mm of area2。
Preferably, the concentration of the sodium carbonate liquor is 0~100g/L, the cocoon quality and sodium carbonate liquor volume ratio
For 10:(1~100) g/L.
Preferably, heating method is that electric furnace heats or pressure cooker heating, heating temperature are 50~121 DEG C, and heating pressure is
0.1~2MPa, heating time are 1s~1000h.
Preferably, the average molecular weight of fibroin albumen is adjusted by control heating time, fibroin albumen average molecular weight is
100KDa~350KDa.
Preferably, the silk of formation is placed in ultrapure water and is washed, and be repeated several times；Further, the mode of washing is
Agitator treating is standing and soaking, wherein the agitating mode of agitator treating is mechanical stirring or magnetic agitation, and magnetic stirring speed is
1r/min~2000r/min；During single wash, silk and water quality ratio are 1:10~1:1000, and the time is 1s~200h,
Silk is taken out each time after washing and is extracted, and washing number of repetition is 1~50 time.
Preferably, first it is dry be natural air drying or heating aeration-drying, wherein the heating temperature for heating aeration-drying is
40~100 DEG C, drying time is 0.1~100h.
Preferably, LiBr LiSCN solution concentration is 0.01~2g/mL, silk quality and LiBr after the first drying
Or LiSCN liquor capacity ratio is (1~100): 100g/mL.
Preferably, the temperature of the heat preservation is 20~100 DEG C, and the preset time is 0.1~100h.
Preferably, the bag filter specification of the dialysis is 10~10000000Da, and the mode of the dialysis is to stand dialysis
Or magnetic agitation dialysis, wherein 1~2000r/min of mixing speed of magnetic agitation dialysis, between the time for changing water in dialysis procedure
It is divided into 0.1~100h, the volume of changed ultrapure water is 1mL~1000L every time.
Preferably, the revolving speed of the centrifugation is 1~40000r/min, time 1s~10h, and temperature when centrifugation is -3~10
℃。
Preferably, second freeze-drying is included at a temperature of -80~0 DEG C, freezes the silk fibroin protein solution；Vacuum
The silk fibroin protein solution after freezing processing freezing；Wherein, the time be 1~500 hour, vacuum pressure be 0.001~
1mBar, temperature are -80~0 DEG C.Further, the vacuum refrigeration processing is carried out using freeze drier.
In one embodiment of the present of invention, the average molecular weight of the fibroin albumen is 100KDa~350KDa.
In one embodiment of the present of invention, the step (1) includes: that the fibroin albumen of 1 parts by weight is dissolved in 1
The hexafluoroisopropanol of~20 parts by weight；Wherein, the temperature of the fibroin albumen and/or hexafluoroisopropanol is 5~80 DEG C, when dissolution
Between be 0.1~100 hour.
In one embodiment of the present of invention, the opening diameter is 0.05~2 millimeter, and the distribution on the peripheral wall is close
Degree is 1~50/square centimeter.
In one embodiment of the present of invention, the protective shell is the hard protective shell of plastics or thin polymer film protective shell.
In one embodiment of the present of invention, the time of the standing is 1~100 hour.
In one embodiment of the present of invention, the diameter of the water soluble salt particle is 0.05~2 millimeter.
In one embodiment of the present of invention, the water soluble salt particle is sodium chloride particle and/or potassium chloride particle.
In one embodiment of the present of invention, the volume of the water soluble salt particle and the water soluble salt particle-fibroin
The volume ratio of protein solution mixture is 1%~99%.
In one embodiment of the present of invention, the step (4) includes: to change liquid every the methanol of replacement in 1~50 hour
Number is 1~50 time.
In one embodiment of the present of invention, the step (4) includes: the water soluble salt particle-silk fibroin protein solution
After fibroin albumen solid state in mixture, the porous mold is removed.
In one embodiment of the present of invention, the step (5) includes: to be soaked using the methanol aqueous solution that concentration gradient is successively decreased
Steep the fibroin albumen solid containing water soluble salt particle；Wherein, methanol concentration range is 100%~0 in methanol aqueous solution,
It is 1~50 hour that methanol aqueous solution, which replaces interval time range, and changing liquid number is 1~50 time.
In one embodiment of the present of invention, the porous-entity composite silk material preparation method preparation further include:
The compound fibroin material of porous-entity is dried under ventilated environment；Wherein, the ventilated environment temperature be 10~
80 DEG C, being dried the time is 1~200 day.
In one embodiment of the present of invention, the porous-entity composite silk material preparation method preparation further include:
Cut the compound fibroin material of porous-entity；Wherein, the cutting includes vehicle and/or milling.
It is described porous-real by controlling the fibroin albumen average molecular weight regulation in one embodiment of the present of invention
The mechanical property of bluk recombination silk material.
Second aspect of the present invention additionally provides a kind of porous-entity composite silk material, using more described in first aspect
Hole-entity composite silk material preparation method is prepared.
The third aspect of the present invention provides previous porous-entity composite silk material and is preparing biological implanted medical device
In purposes.
The fourth aspect of the present invention provides previous porous-use of the entity composite silk material in novel microelectronic field
On the way.
Compared with prior art, the invention has the following beneficial effects:
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention is simple, is suitable for work
Industry；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous structure and entity structure knot
Secured, biodegrade and the regulatable porous-entity composite silk material of mechanical property are closed, can be widely applied to biological implantation
Medical field.
Detailed description of the invention
Fig. 1 is the flow diagram of porous-entity composite silk material preparation method provided in an embodiment of the present invention.
Fig. 2 is silk fibroin protein solution schematic diagram provided in an embodiment of the present invention.
Fig. 3 is water soluble salt particle provided in an embodiment of the present invention-silk fibroin protein solution mixture schematic diagram.
Fig. 4 is that the fibroin albumen solid provided in an embodiment of the present invention containing water soluble salt particle prepares schematic diagram.
Fig. 5 is the fibroin albumen solid schematic diagram provided in an embodiment of the present invention containing water soluble salt particle.
Fig. 6 is the compound fibroin material schematic diagram of porous-entity provided in an embodiment of the present invention.
Fig. 7 is the compound fibroin material schematic diagram of porous-entity of cutting forming provided in an embodiment of the present invention.
Fig. 8 is the compound fibroin material schematic diagram of porous-entity of cutting forming provided in an embodiment of the present invention.
Specific embodiment
Before further describing the specific embodiments of the present invention, it should be appreciated that protection scope of the present invention is not limited to down
State specific specific embodiment；It is also understood that term used in the embodiment of the present invention is specific specific in order to describe
Embodiment, rather than limiting the scope of protection of the present invention；In description of the invention and claims, unless in text
In addition explicitly point out, singular "one", " one " and " this " include plural form.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, the present invention used in all technologies and
Scientific term is identical as the normally understood meaning of those skilled in the art of the present technique.Except specific method, equipment used in embodiment,
Outside material, grasp and record of the invention according to those skilled in the art to the prior art can also be used and this
Any method, equipment and the material of the similar or equivalent prior art of method described in inventive embodiments, equipment, material come real
The existing present invention.
Embodiment 1
The embodiment of the present invention 1 provides a kind of porous-entity composite silk material preparation method, as shown in Figure 1, described more
Hole-entity composite silk material preparation method includes the following steps.
S1, the fibroin albumen is dissolved in hexafluoroisopropanol, obtains silk fibroin protein solution 1 (1 in Fig. 2 as shown in Figure 2
Represent silk fibroin protein solution).
Specifically, every part of 10g silk cocoon, which shreds, is placed in the sodium carbonate liquor that 4L concentration is 2g/L, and electricity consumption stove heating is boiled simultaneously
Magnetic agitation, revolving speed 200r/min, heating time are 60 minutes.Then, the silk that every part was boiled is placed in 2L ultrapure water
Agitator treating is pinched dry, is repeated 6 times, then be dried, mixing speed 200r/min, mixing time 20min is changed ultrapure every time
The volume of water is 2L, and drying mode is 25 DEG C, dries under normal pressure (0.1MPa).Then, dry silk is immersed in concentration is
In the lithium-bromide solution of 0.98g/mL, the relationship of silk is 4mL:1g after the volume and drying of lithium-bromide solution, is kept the temperature at 60 DEG C
4h obtains the mixed solution of fibroin and lithium bromide.Then, the mixed solution of fibroin and lithium bromide is packed into retention point
Son amount is to be placed in 4L ultrapure water and dialyse in 3500Da bag filter, and interval 0.5h changes a ultrapure water, changes water volume 4L every time,
Dialyse 48h in total.Finally, the fibroin solutions dialysed are centrifugated at 4 DEG C, revolving speed 12000r/min, when centrifugation
Between 30min, collect supernatant liquor, finally obtain required fibroin aqueous solution.
Then, the fibroin aqueous solution obtained above is dried.Specifically, using -80 DEG C of refrigerator freezings, or
Use liquid nitrogen frozen.Freezing-vacuum condition uses vacuum drier, and vacuum refrigeration is handled 100 hours in freeze drier, described
The vacuum pressure of freeze drier is 0.02mBar, and temperature is -10 DEG C.Obtain powdered fibroin albumen.
The powdered fibroin albumen and hexafluoroisopropanol mass ratio are 1:4, and dissolution ambient temperature range is 25 DEG C of (rooms
Warm environment), dissolution time range is 24 hours, is dissolved.It needs sealing container to prevent hexafluoroisopropanol from volatilizing when dissolution, makes
With sealed glass jars with a lid, sealing injection device, beaker of thin polymer film sealing etc..
S2, the silk fibroin protein solution is injected to porous mold 2 as shown in Figure 3 (2 in Fig. 3 represent porous mold),
It stands；Wherein, the porous mold 2 includes peripheral wall and protective shell 3 as shown in Figure 3 (3 in Fig. 3 represent protective shell), described
Peripheral wall has multiple apertures.
Specifically, silk fibroin protein solution 1 is injected in porous mold 2.The porous mold 2 includes protective shell 3, is prevented
Silk fibroin protein solution 1 flows out.The form of protective shell can be the hard protective shell of plastics, or thin polymer film protective shell, but
It is without being limited thereto.The peripheral wall of the porous mold 2 has multiple apertures, and opening diameter range is 0.05~2 millimeter, aperture density
1~50/square centimeter of range.The silk fibroin protein solution 1 injects after the porous mold 2 time of repose 24 hours, until
Bubble release in solution is complete.
Silk fibroin protein solution in S3, Xiang Suoshu porous mold 2 fills water soluble salt particle 4 as shown in Figure 3 (in Fig. 3
4 represent water soluble salt particle), obtain water soluble salt particle-silk fibroin protein solution mixture；Wherein, the water soluble salt
Grain does not dissolve in hexafluoroisopropanol.
Standing a period of time precipitates water soluble salt particle 4 sufficiently, and controls the packing volume ratio of water soluble salt particle 4
Example.Specifically, it is filled into the hexafluoroisopropanol solution of fibroin albumen using sodium chloride particle 4 (0.5 millimeter of average diameter), it is quiet
Setting 12 hours precipitates sodium chloride sufficiently, and controlling the volume ratio of sodium chloride in the solution is 50%.
S4, by remove after the protective shell 3 containing water soluble salt particle-silk fibroin protein solution mixture porous mold
3 are immersed in methanol 5 (5 in Fig. 4 represent methanol) as shown in Figure 4, and the silk containing water soluble salt particle as shown in Figure 5 is made
Fibroin solid 6 (6 in Fig. 5 represent the fibroin albumen solid for having water soluble salt particle).
In S4, hexafluoroisopropanol is replaced using methanol 5, while making fibroin albumen crystallisation solidification, it can be under ventilated environment
It dries and obtains the fibroin albumen solid 6 comprising water soluble salt particle 4.
Specifically, after the bubble of silk fibroin protein solution 1 discharges completely, the protection of 2 surface of the porous mold covering is removed
Shell 3, and the porous mold 2 containing silk fibroin protein solution 1 and sodium chloride salt particle 4 is soaked in 5 environment of methanol.It is small every 12
Methanol solution of Shi Genghuan changes liquid number 10 times.Fibroin albumen removes porous mold 2 after being solidified completely by methyl alcohol process, so
Making the moisture evaporation in fibroin albumen under ventilated environment afterwards and air-dries, ventilated environment temperature is 25 DEG C, and the processing time is 20 days,
Obtain the fibroin albumen solid 6 comprising water soluble salt particle 4.
The methanol and water soluble salt particle 4 in fibroin albumen solid 6 described in S5, removal containing water soluble salt particle, is obtained
Obtain the compound fibroin material of porous-entity.
Methanol and water soluble salt particle 4 are removed by displacement method.Specifically, by the fibroin egg comprising water soluble salt particle 4
White solid 6 is soaked in the methanol aqueous solution as shown in FIG. 67 (7 in Fig. 6 represent methanol aqueous solution) that concentration gradient is successively decreased；
Wherein, methanol concentration is successively decremented to 0% from 100% in methanol aqueous solution 7, and methanol aqueous solution 7 is primary every replacement in 12 hours；
Changing liquid number is 10 times.By displacement method by remaining methanol replacement Cheng Shui, while water soluble salt particle 4 being made to be completely dissolved in water
In.
The compound fibroin material of porous-entity that S5 is obtained is dry under ventilated environment, cuts repairing type into required shape
Shape, shape can be the shape as representated by Fig. 78,9,10.
In one example, it is specifically in venting ring that the compound fibroin material of porous-entity is dry under ventilated environment
Make the moisture evaporation in fibroin albumen solid under border and air-dry, ventilated environment temperature is 25 DEG C, and the processing time is 15 days.It is described to cut
Cut repairing type technique include vehicle, milling the methods of, but not limited to this；The compound fibroin albumen material shape packet of porous-entity of cutting
Cuboid, square, cylindrical body, triangle are included, but not limited to this；The compound fibroin albumen material shape of porous-entity of cutting
Size range be 0.1~1000 cubic centimetre.Fig. 8 shows the compound fibroin albumen circle of a kind of porous-entity to have cut
Cylindrical material.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention is simple, is suitable for work
Industry；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous structure and entity structure knot
Secured, biodegrade and the regulatable porous-entity composite silk material of mechanical property are closed, can be widely applied to biological implantation
Medical field.
The embodiment of the invention also provides a kind of using the more of above-mentioned porous-entity composite silk material preparation method preparation
Hole-entity composite silk material.
Porous-entity composite silk material porosity and aperture diameter provided in an embodiment of the present invention be adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property, can be extensive
Medical field is implanted into applied to biology.
Embodiment 2
In example 2, the lithium-bromide solution in S1 replaces with lithium rhodanate solution, other operations are same as Example 1.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 3
In embodiment 3, powdered fibroin albumen and hexafluoroisopropanol mass ratio are 1:1, other operations and embodiment 1
It is identical.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 4
In the present embodiment, powdered fibroin albumen and hexafluoroisopropanol mass ratio are 1:10, other operations and implementation
Example 1 is identical.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 5
In the present embodiment, powdered fibroin albumen and hexafluoroisopropanol mass ratio are 1:20, other operations and implementation
Example 1 is identical.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 6
In the present embodiment, it be temperature is 5 DEG C that powdered fibroin albumen, which is dissolved in the environment of hexafluoroisopropanol, dissolution time
It is 50 hours, other operations are same as Example 1.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 7
In the present embodiment, it be temperature is 40 DEG C that powdered fibroin albumen, which is dissolved in the environment of hexafluoroisopropanol, when dissolution
Between be 0.1 hour, other operations are same as Example 1.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 8
In the present embodiment, it be temperature is 80 DEG C that powdered fibroin albumen, which is dissolved in the environment of hexafluoroisopropanol, when dissolution
Between be 100 hours, other operations are same as Example 1.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 9
In the present embodiment, silk fibroin protein solution injection porous mold after, quiescent time be 100 hours, other operation with
Embodiment 1 is identical.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 10
In the present embodiment, after silk fibroin protein solution injection porous mold, quiescent time is 50 hours, other operations with it is real
It is identical to apply example 1.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 11
In the present embodiment, after silk fibroin protein solution injection porous mold, quiescent time is 1 hour, other operations with it is real
It is identical to apply example 1.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 12
In the present embodiment, water soluble salt particle is potassium chloride, other operations are same as Example 1.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 13
In the present embodiment, water soluble salt particle is potassium chloride, other operations are same as Example 1.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 14
In the present embodiment, the volume ratio of control sodium chloride in the solution is 99%, other operations are same as Example 1.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 15
In the present embodiment, the volume ratio of control sodium chloride in the solution is 1%, other operations are same as Example 1.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 16
In the present embodiment, in S4, a more preferable methanol every 1 hour, changing liquid number is 25 times, other operations and implementation
Example 1 is identical.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 17
In the present embodiment, in S4, a more preferable methanol every 25 hours, changing liquid number is 1 time, other operations and implementation
Example 1 is identical.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 18
In the present embodiment S4, every the methanol of replacement in 50 hours, changing liquid number is 25 times, other operations and embodiment
1 is identical.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 19
In the present embodiment S5, every the methanol of replacement in 50 hours, changing liquid number is 25 times, other operations and embodiment
1 is identical.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 20
In the present embodiment S4, a more preferable methanol every 25 hours, changing liquid number is 50 times, other operations and embodiment
1 is identical.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 21
In the present embodiment S4, a more preferable methanol every 1 hour, changing liquid number is 10 times, other operations and embodiment 1
It is identical.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 22
The compound fibroin material of porous-entity that S5 is obtained is 100 days dry in the case where temperature is 80 DEG C of ventilated environments,
He operates same as Example 1.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 23
The compound fibroin material of porous-entity that S5 is obtained is 50 days dry in the case where temperature is 40 DEG C of ventilated environments,
He operates same as Example 1.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
Embodiment 24
The compound fibroin material of porous-entity that S5 is obtained is 200 days dry in the case where temperature is 10 DEG C of ventilated environments,
He operates same as Example 1.
Porous-entity composite silk material preparation method technological operation provided in an embodiment of the present invention provided in this embodiment
Simply, it is suitable for industrialization；Its porous-entity composite silk material porosity prepared and aperture diameter is adjustable, porous knot
Structure and entity structure be firmly combined, biodegrade and the regulatable porous-entity composite silk material of mechanical property.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (20)
1. a kind of porous-entity composite silk material preparation method, which is characterized in that the porous-entity composite silk material
Preparation method the following steps are included:
(1) fibroin albumen is dissolved in hexafluoroisopropanol, obtains silk fibroin protein solution；
(2) silk fibroin protein solution is injected into porous mold, stood；Wherein, the porous mold includes peripheral wall and protective shell,
The peripheral wall has multiple apertures；
(3) silk fibroin protein solution in Xiang Suoshu porous mold fills water soluble salt particle, obtains water soluble salt particle-fibroin egg
White solution mixture；
(4) impregnating after the protective shell containing water soluble salt particle-silk fibroin protein solution mixture porous mold will be removed
In methyl alcohol, the fibroin albumen solid containing water soluble salt particle is made；
(5) methanol and water soluble salt particle in the fibroin albumen solid containing water soluble salt particle are removed, obtain it is porous-
The compound fibroin material of entity.
2. porous-entity composite silk material preparation method according to claim 1, which is characterized in that in step (1),
The fibroin albumen is anhydrous fibroin albumen.
3. porous-entity composite silk material preparation method according to claim 1, which is characterized in that the fibroin egg
It is white before being dissolved in hexafluoroisopropanol, for the anhydrous fibroin albumen xeraphium that is obtained from aqueous solution state directly freezed seasoning
End；
The anhydrous fibroin albumen dried powder is dissolved in hexafluoroisopropanol, obtains the silk fibroin protein solution.
4. porous-entity composite silk material preparation method according to claim 1, which is characterized in that the step (1)
Include:
Silk cocoon is placed in sodium carbonate liquor, is heated, silk is formed；First is dry；LiBr LiSCN solution is added, and protects
Warm preset time obtains mixed solution；
It dialyses the mixed solution, and the solution after spin dialysis, takes supernatant, obtain silk fibroin water solution；Second freezing
The dry silk fibroin water solution, obtains the fibroin albumen.
5. porous-entity composite silk material preparation method according to claim 4, which is characterized in that described second is cold
It is lyophilized dry are as follows:
At a temperature of -80~0 DEG C, the silk fibroin water solution is freezed；
The silk fibroin protein solution after vacuum refrigeration processing freezing；Wherein, the time is 1~500 hour, and vacuum pressure is
0.001~1mBar, temperature are -80~0 DEG C.
6. porous-entity composite silk material preparation method according to claim 1, which is characterized in that the fibroin egg
White average molecular weight is 100KDa~350KDa.
7. porous-entity composite silk material preparation method according to claim 1, which is characterized in that the step (1)
Include:
The fibroin albumen of 1 parts by weight is dissolved in the hexafluoroisopropanol of 1~20 parts by weight；Wherein, the fibroin albumen and/
Or the temperature of hexafluoroisopropanol is 5~80 DEG C, dissolution time is 0.1~100 hour.
8. porous-entity composite silk material preparation method according to claim 1, which is characterized in that the aperture is straight
Diameter is 0.05~2 millimeter, and the distribution density on the peripheral wall is 1~50/square centimeter.
9. porous-entity composite silk material preparation method according to claim 1, which is characterized in that the protective shell
For the hard protective shell of plastics or thin polymer film protective shell.
10. porous-entity composite silk material preparation method according to claim 1, which is characterized in that the standing
Time is 1~100 hour.
11. porous-entity composite silk material preparation method according to claim 1, which is characterized in that the water solubility
The diameter of salt particle is 0.05~2 millimeter.
12. porous-entity composite silk material preparation method according to claim 1, which is characterized in that the water solubility
Salt particle is sodium chloride particle and/or potassium chloride particle.
13. porous-entity composite silk material preparation method according to claim 1, which is characterized in that the water solubility
The volume of salt particle and the volume ratio of the water soluble salt particle-silk fibroin protein solution mixture are 1%~99%.
14. porous-entity composite silk material preparation method according to claim 1, which is characterized in that the step
(4) include:
Every the methanol of replacement in 1~50 hour, changing liquid number is 1~50 time.
15. porous-entity composite silk material preparation method according to claim 1, which is characterized in that the step
It (4) include: to remove described porous after fibroin albumen solid state in the water soluble salt particle-silk fibroin protein solution mixture
Mold.
16. porous-entity composite silk material preparation method according to claim 1, which is characterized in that the step
(5) include:
The methanol aqueous solution to be successively decreased using concentration gradient impregnates the fibroin albumen solid containing water soluble salt particle；Wherein,
Methanol concentration range is 100%~0 in methanol aqueous solution, and it is 1~50 hour that methanol aqueous solution, which replaces interval time range, changes liquid
Number is 1~50 time.
17. porous-entity composite silk material preparation method according to claim 1, which is characterized in that further include:
The compound fibroin material of porous-entity is dried under ventilated environment；Wherein, the ventilated environment temperature is
10~80 DEG C, being dried the time is 1~200 day.
18. porous-entity composite silk material preparation method according to claim 1, which is characterized in that further include:
Cut the compound fibroin material of porous-entity；Wherein, the cutting includes vehicle and/or milling.
19. a kind of porous-entity composite silk material, which is characterized in that described in any item more using claim 1~18
Hole-entity composite silk material preparation method is prepared.
20. porous-entity composite silk material as claimed in claim 19 is in the biological implanted medical device of preparation or novel
Purposes in microelectronic field.
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| CN113332498A (en) * | 2021-05-20 | 2021-09-03 | 湖北赛罗生物材料有限公司 | Silk fibroin/hydroxyapatite composite material and preparation method and application thereof |
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