CN105524472A - Keratin/silk fibroin blended membrane and preparation method thereof - Google Patents
Keratin/silk fibroin blended membrane and preparation method thereof Download PDFInfo
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
The invention discloses a medical keratin/silk fibroin blended membrane and a preparation method thereof. With keratin and silk fibroin as main raw materials, a porous membrane or a bilayer membrane having a dense porous structure is obtained, wherein a mixed solution of keratin and silk fibroin performs flow-casting in a mould having a certain specification to form a dense membrane, the dense membrane is covered with composite gel of keratin and silk fibroin, and the porous membrane is obtained through low temperature freezing and vacuum drying method. The bilayer membrane is soft, has a certain toughness, can be arbitrarily clipped or bent into various shapes, and has good biocompatibility and clinical operability; the porous membrane has the thickness of 10 [mu]m-5 mm, pores inside the porous membrane mutually communicate, the average pore diameter is 5-400 [mu]m, the porosity ratio is 10-90%, and the membrane can be applied in the fields of artificial skin, dental implant restoration, organ restoration and the like.
Description
Technical field
The present invention relates to a kind of Keratin sulfate/silk fibroin duplicature and preparation method thereof, in particular to one with Keratin sulfate, silk fibroin for main raw material, preparation has method that is fine and close and the double-deck composite protein film of porous concurrently, and prepared material can be applicable to the aspects such as tissue engineering material, artificial skin, oral implant rehabilitation or medicament slow release.
Background technology
Three-dimensional porous cell scaffold material is an important directions of biomedical engineering, can with tissue biopsy Cell binding and implantable bioartificial body, and the timbering material possessing certain function all has important academic significance and practical value in scientific research and clinical application.In the research of existing tissue engineering bracket material, be the three dimensional scaffold structure for artificial organs such as bone, blood vessel, nerves mostly, then also few to meeting mould material research required in clinical application.
During China applies for a patent " a kind of bio-medical material and its production and use " (CN1544097A), adopt collagen protein or gelatin, konjac glucomanna, chondroitin sulfate or chitosan, after the technical process such as stirring, deaeration, modification, lyophilize, make the spongy porous-film of 1-3mm.
During China applies for a patent " one carries bFGF collagen based composites and its preparation method and application " (CN104758983A), Isin glue collagen and chitosan is adopted to be prepared into composite membrane through lyophilize, again after chondroitin sulfate is crosslinked, introduce and carry the PLGA microballoon of bFGF, repeatedly lyophilize obtain after sterilizing aseptic carrying bFGF collagen base porous compound material.
As can be seen here, in the prior art, the natural materials that the preparation of porous film material adopts has collagen protein, gelatin, Mierocrystalline cellulose etc., but there is defect more or less in these materials, as bad in biocompatibility, and extraction process is complicated, high cost etc.Therefore more research is devoted to adopt desirable natural materials to substitute.
Keratin sulfate is as a kind of natural protein, there is good biocompatibility, RGD (arginine-glycine-aspartic acid) tripeptide sequence promoting that osteocyte adheres to all is there is in the keratic aminoacid sequence existed in the filoplume such as human hair, wool, good affinity and adsorptivity is had to cell, can also optimize the growth of osseous tissue, therefore Keratin sulfate is as having very large advantage in bio-medical material.
Silk fibroin is the macromolecular fibre albumen extracted from natural silk, and its content accounts for 70 ~ 80% of silk.A part in its amino acid composition is essential amino acid, human non-toxic is had no side effect, there is excellent mechanical property, therefore the domestic and international applied research to silk fibroin is also widened from field of textiles to multiple field already, especially increasingly extensive in the research of field of biomedical materials.
As follows for the correlative study adopting these two kinds of native proteins to obtain porous-film both at home and abroad:
During China applies for a patent " a kind of technique of preparing keratin porous membrane by refrigerating " (CN102585277B), adopt freeze drying process directly to carry out freeze-drying to wool keratin solution and obtain Keratin sulfate porous-film.This Keratin sulfate porous-film thickness is even, hole good dispersity, but the Keratin sulfate porous-film mechanical property of one-component is poor.
During China applies for a patent " a kind of porous fibroin membrane and preparation method thereof " (CN1260363A), take silk as main raw material, lyophilize is carried out to the mixing solutions of concentrated silk fibroin and additive, linking agent, makes porous fibroin membrane.This fibroin membrane has stronger mechanical property and good biocompatibility, but the feel of whole film is partially hard, have impact on the operability of clinical application.
Therefore existing certain snappiness, has again the albumen porous-film of good biocompatibility and cytoactive and preparation method thereof to be the urgently problems that solve of people.
Summary of the invention
The object of the invention is to the deficiency for existing porous film material, provide one to have some strength and snappiness, can bend arbitrarily, biocompatibility is good, biodegradablely have densification and porous double-deck Keratin sulfate/silk fibroin blend film and preparation method thereof concurrently.
For achieving the above object, the present invention is by the following technical solutions:
Blend film of the present invention adopts Keratin sulfate and silk fibroin to be main raw material(s), is undertaken mixing and being prepared into gel from silk fibroin with certain density Keratin sulfate by different volume percent, then is obtained by cryogenic freezing, vacuum drying method.Blend film after shaping is the porous-film in vesicular structure, and it is soft and tough, and thickness is even, and thickness can be controlled between 10 μm ~ 5mm, is interconnected between the Kong Yukong of film inside, and mean pore size is 30 ~ 400 μm, and porosity is 10 ~ 90%.
The preparation method of blend film of the present invention, step is as follows:
(1) use the concentration of reductive agent for 0.01M ~ 0.1M the segment animal filoplume being cut into 0.5 ~ 1cm is dissolved after through filtering, dialysis, concentration technology obtains keratin solution; Natural silk come unstuck, dissolves, dialyse, filter, concentrate, obtain silk fibroin water solution;
(2) get keratin solution and silk fibroin protein solution, by certain volume ratio configuration mixing solutions, after standing and defoaming, inject the mould with specified shape and size, under fixed temperature and humidity condition, form Keratin sulfate/silk fibroin plural gel;
(3) the albumen plural gel pre-freeze under the low temperature of-20 ~-80 DEG C step (2) obtained, the pre-freeze time is 4 ~ 24 hours, and then vacuum-drying forms cavernous Keratin sulfate/silk fibroin blend film under cryogenic.
Preferably, the concentration of step (1) keratin solution and silk fibroin protein solution of preparing gained is 1 ~ 20%.
Preferably, in the mixing solutions described in step (2), the volume ratio of silk fibroin is 5 ~ 95%, and the fixed temperature and humidity condition forming cavernous Keratin sulfate/silk fibroin blend film is as follows: temperature is 20 ~ 70 DEG C, and humidity is 30 ~ 70%.
Preferably, for accelerating the transformation of solution-gel state in step (2), can add a certain amount of additive, this additive is mainly alcohols, and as ethanol, propyl alcohol etc., concentration is 1 ~ 20%.
Preferably, described in step (3), the lyophilisation condition of plural gel is as follows: temperature-90 ~-105 DEG C, and equipment internal gas pressure is 1 ~ 10bar, and freeze-drying time is 24 ~ 48 hours.
As a modification of the present invention, described blend film can also be the bilayer structure having porous-film and dense film concurrently, namely one deck can also be had on described porous-film to adopt casting method obtained transparent, aporate dense film: the vesicular structure that described porous-film inside is communicated with promotes growing into of cell, for the growth of various cell provides support, accelerate the reparation of tissue and organ; Barrier film barrier action is played in the process that described dense film grows at guide tissue regeneration, ensure the space required for the regeneration of disease defective tissue, this duplicature can be applicable to the biomaterial aspect such as tissue engineering material, artificial aggregate, artificial skin, oral implant rehabilitation, the reparation of organ inwall.
The preparation method having the double-deck blend film of porous-film and dense film concurrently of the present invention is as follows:
(1) the segment animal filoplume being cut into 0.5 ~ 1cm dissolved, filter, dialyse, concentrate, obtain the Keratin sulfate aqueous solution, wherein dissolve through appropriate reductive agent and obtain Keratin sulfate I solution, dissolve through excessive reductive agent and obtain Keratin sulfate II solution; Natural silk come unstuck, dissolves, dialyse, filter, concentrate, obtain silk fibroin water solution;
(2) get Keratin sulfate I solution and silk fibroin protein solution, by certain volume ratio configuration mixing solutions, after standing and defoaming, inject the mould with specified shape and size, adopt casting method to form tight zone film under fixed temperature and humidity condition;
(3) Keratin sulfate II solution and silk fibroin protein solution is got, by certain volume ratio configuration mixing solutions, add a certain amount of additive and accelerate albumen plastic, slowly be laid on the tight zone film described in step (2), under fixed temperature and humidity condition, form Keratin sulfate/silk fibroin plural gel;
(4) the plural gel pre-freeze under the low temperature of-20 ~-80 DEG C step (3) obtained, the pre-freeze time is 4 ~ 24 hours, and then under cryogenic vacuum condition, freeze-drying forms Keratin sulfate/silk fibroin duplicature.
In the preparation method of two schemes of the present invention:
Preferably, described animal filoplume is preferably human hair, wool, cashmere, camel hair or the rabbit hair, and described silk is one or more in mulberry silk, tussah silk, wild silk yarn.
Preferably, prepare tight zone Keratin sulfate used I use the concentration of reductive agent for 0.01M ~ 0.1M, prepare porous layer Keratin sulfate used II use the concentration of reductive agent for 0.2M ~ 2M, the concentration of the keratin solution and silk fibroin protein solution of preparing gained is 1 ~ 20%.
Preferably, in described mixing solutions, the volume ratio of described silk fibroin is 5 ~ 95%, and the fixed temperature and humidity condition forming dense film and gel is as follows: temperature is 20 ~ 70 DEG C, and humidity is 30 ~ 70%.
Preferably, for accelerating the transformation of solution-gel state, can add a certain amount of additive, this additive is mainly alcohols, and as ethanol, glycerol, polyoxyethylene glycol etc., concentration is 1 ~ 20%.
Preferably, the lyophilisation condition of blend film is as follows: temperature-90 ~-105 DEG C, and equipment internal gas pressure is 1 ~ 10bar, and freeze-drying time is 24 ~ 48 hours.
After adopting technique scheme, the present invention has following advantage and effect compared with background technology:
(1) the present invention adopts natural silk fibroin and Keratin sulfate as raw material, and the composite membrane of gained has both the advantage of two kinds of native proteins, has more excellent mechanical property and biocompatibility than the wherein independent film forming of any one albumen;
(2) in the present invention, keratic adding improves pure silk fibroin film forming and retrodeviates hard feel, improves the operability of products obtained therefrom in clinical application;
(3) the present invention utilizes the mechanism of silk fibroin plastic to form the intermediate of Keratin sulfate/silk fibroin plural gel, again through freeze-drying film forming, effectively can control thickness and the shape of gained porous-film, avoid the spray bottle phenomenon that easily occurs in solution tiling freeze-drying process or the uneven defect of film forming;
(4) the present invention adopts solution-gel-low temperature pre-freeze-vacuum drying preparation technology, can control various structural parameter and the physicochemical property of gained porous-film, simply effectively, be easy to industrialization;
(5) duplicature of the present invention has both tight zone and porous layer, and clinical application plays more effective effect.
Accompanying drawing explanation
Fig. 1 is the field emission scanning electron microscope picture of Keratin sulfate in embodiment one/silk fibroin composite porous film;
Fig. 2 is the inner pore size distribution curve of Keratin sulfate in embodiment one/silk fibroin composite porous film;
Fig. 3 is the field emission scanning electron microscope picture of Keratin sulfate in embodiment two/silk fibroin duplicature;
Fig. 4 is the tensile stress strain curve of Keratin sulfate in embodiment two/silk fibroin duplicature.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment one
1. take 10g after silk cocoon being cut into fragment and put into the sodium hydrogen carbonate solution that 2L concentration is 0.5%, boil 30min, repeat twice, to slough the silk gum of silk, then dry with after washed with de-ionized water 5 times, obtain clean degumed silk.Degumed silk after drying is taken 1g and puts into the lithium-bromide solution that 6ml concentration is 9.3mol/L, dissolve under 50 DEG C of conditions and take out for 4 hours later, lysate being loaded molecular weight is dialyse in the dialysis tubing of 3500D, can obtain the pure silk fibroin protein solution that mass concentration is 5wt%.
2. take the scoured wool that 5g shreds, being placed in 100ml contains in the mixing solutions of urea (7M), sodium lauryl sulphate (0.2M), sodium sulphite (0.2M), stir 8h under 50 DEG C of conditions after, lysate being injected molecular weight cut-off is that the dialysis tubing of 8 ~ 14KD is dialysed, and can obtain wool keratin II solution that mass concentration is 5wt% after concentrated.
3. get above-mentioned two kinds of solution respectively, according to Keratin sulfate: silk fibroin is after the volume ratio of 20:80 mixes, mixing solutions is injected the mould of 3cm*3cm, being placed in temperature is 25 DEG C, and relative humidity is form Keratin sulfate/silk fibroin plural gel in the climatic chamber of 50%.
4. the plural gel described in step 3 to be put under the cold condition of-20 DEG C after pre-freeze 12h, in freeze drier, low-temperature vacuum drying (condition of low-temperature vacuum drying: temperature-90 ° ~-105 °, drying machine internal gas pressure 1 ~ 10bar), takes out and obtains Keratin sulfate/silk fibroin composite porous film after 48h.
5. characterize the surface of the composite porous film described in step 4 and cross-sectional morphology with field emission scanning electron microscope, result is see accompanying drawing 1, and wherein A is the surface topography of composite porous film, and B is the cross section picture of composite porous film.Blend film after shaping is soft and tough, and thickness is even, and can be controlled between 10 μm ~ 5mm, be interconnected between the Kong Yukong of film inside, porosity is 0 ~ 90%.
6. the porous-film inner porosity described in pair step 4 carries out quantitative analysis, and gained aperture is between 20 ~ 60 μm, and pore size distribution curve is see accompanying drawing 2.
Embodiment two
1. take the scoured wool that 5g shreds, being placed in 100ml contains in the mixing solutions of urea (7M), sodium lauryl sulphate (0.2M), 2 mercapto ethanol (0.08M), stir 8h under 50 DEG C of conditions after, lysate being injected molecular weight cut-off is that the dialysis tubing of 8 ~ 14KD is dialysed, and can obtain wool keratin I solution that mass concentration is 5wt% after concentrated.
2. the method as described in embodiment one prepares Keratin sulfate II and silk fibroin protein solution respectively, through concentrated or dilution, all controls the mass concentration of two kinds of albumen at 5wt%.
3. get the Keratin sulfate I described in step 1 and silk fibroin protein solution, according to Keratin sulfate: silk fibroin is the volume ratio mixing of 40:60, be laid in the separate-type paper of 3cm*3cm, in climatic chamber, (temperature 25 DEG C, humidity 50%) curtain coating forms dense film.
4. get the Keratin sulfate II described in step 2 and silk fibroin protein solution, according to Keratin sulfate: silk fibroin is add the glycerol that mass concentration is 5wt% again after the volume ratio of 40:60 mixes, the mass ratio of glycerol and conjugated protein solution is 1%-10%, by the dense membrane surface that the liquid after mixing slowly tiles described in step 2, climatic chamber (temperature 25 DEG C, humidity 50%) interior standing 1 hour, forming bottom surface is the plural gel of dense film.
5. the plural gel described in step 4 is put into pre-freeze 12h under the cold condition of-20 DEG C, in freeze drier, carrying out low-temperature vacuum drying again, (condition of low-temperature vacuum drying: temperature-90 ° ~-105 °, drying machine internal gas pressure (1 ~ 10bar), takes out and obtains Keratin sulfate/silk fibroin duplicature after 48h.
6. characterize respectively the tight zone of this duplicature and the surface topography of porous layer with field emission scanning electron microscope, see accompanying drawing 3, wherein A face is dense film one side, and B face is porous-film one side.The vesicular structure that described porous-film inside is communicated with promotes growing into of cell, for the growth of various cell provides support, accelerates the reparation of tissue and organ; Barrier film barrier action is played in the process that described dense film grows at guide tissue regeneration, ensure the space required for the regeneration of disease defective tissue, this duplicature can be applicable to the biomaterial aspect such as tissue engineering material, artificial aggregate, artificial skin, oral implant rehabilitation, the reparation of organ inwall.
7. by the duplicature described in step 5 according to GB/T1040-2006 standard system into strips, use Instronmicrotester5948 to carry out tension test.Testing circumstance is: temperature 25 DEG C, and humidity is 50%, often organizes sample and repeats 6 times, average, and can the tensile break strength of this porous-film be 1.54 ± 0.12MPa, tension fracture elongation rate be 65.1 ± 11.4%, and its tensile stress-strain curve is see accompanying drawing 4.
The above; be only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (11)
1. Keratin sulfate/silk fibroin blend film, it is characterized in that: described blend film with Keratin sulfate and silk fibroin two kinds of natural proteins for main raw material, blend film after combined shaping is have the solid apertured porous-film of nature, described porous-film thickness is 10 μm ~ 5mm, mutual Natural communication between the Kong Yukong of porous-film inside, the mean pore size in described hole is 30 ~ 400 μm.
2. Keratin sulfate according to claim 1/silk fibroin blend film, it is characterized in that: described blend film is duplicature, namely on the described unitary film with vesicular structure, also has the dense film that one deck is different from described porous membrane structure, described dense film is the transparence non-porous film adopting casting method obtained, thickness is 10 ~ 50 μm, in the process of guide tissue regeneration growth, play barrier film barrier action, ensure the space required for another side tissue regeneration; The vesicular structure that described porous-film inside is communicated with promotes growing into of cell, for the growth of various cell provides support, accelerates the growth of tissue and organ.
3. a preparation method for Keratin sulfate as claimed in claim 1/silk fibroin blend film, is characterized in that, comprise the following steps:
(1) working concentration be after the reductive agent of 0.01M ~ 0.1M dissolves the segment animal filoplume being cut into 0.5 ~ 1cm through filtering, dialysis, concentration technology obtain keratin solution; Natural silk come unstuck, dissolves, dialyse, filter, concentrate, obtain silk fibroin water solution;
(2) get keratin solution and silk fibroin protein solution, by the volume ratio configuration mixing solutions of 5%-95%, after standing and defoaming, inject the mould with specified shape and size, under fixed temperature and humidity condition, form Keratin sulfate/silk fibroin plural gel;
(3) the albumen plural gel pre-freeze under the low temperature of-20 ~-80 DEG C step (2) obtained, the pre-freeze time is 4 ~ 24 hours, and then vacuum-drying forms cavernous Keratin sulfate/silk fibroin blend film under cryogenic.
4. the preparation method of a kind of Keratin sulfate/silk fibroin blend film according to claim 3, is characterized in that: the concentration of the keratin solution and silk fibroin protein solution of preparing gained in described step (1) is 1 ~ 20%.
5. the preparation method of a kind of Keratin sulfate/silk fibroin blend film according to claim 3, it is characterized in that: the fixed temperature and humidity condition forming cavernous Keratin sulfate/silk fibroin blend film is as follows: temperature is 20 ~ 70 DEG C, humidity is 30 ~ 70%.
6. the preparation method of a kind of Keratin sulfate/silk fibroin blend film according to claim 3, it is characterized in that: the lyophilisation condition of described plural gel is as follows: temperature-90 ~-105 DEG C, equipment internal gas pressure is 1 ~ 10bar, and freeze-drying time is 24 ~ 48 hours.
7. a preparation method for Keratin sulfate as claimed in claim 2/silk fibroin blend film, is characterized in that, comprise the following steps:
(1) the segment animal filoplume being cut into 0.5 ~ 1cm dissolved, filter, dialyse, concentrate, difference according to the amount of the reductive agent added when dissolving obtains Keratin sulfate I solution and Keratin sulfate II solution respectively, wherein, prepare Keratin sulfate I solution use the concentration of reductive agent for 0.01M ~ 0.1M, prepare Keratin sulfate II use the concentration of reductive agent for 0.2M ~ 2M; Natural silk come unstuck, dissolves, dialyse, filter, concentrate, obtain silk fibroin water solution;
(2) get Keratin sulfate I solution and silk fibroin protein solution, by the volume ratio configuration mixing solutions of 5%-95%, after standing and defoaming, inject the mould with specified shape and size, adopt casting method to form tight zone film under fixed temperature and humidity condition;
(3) Keratin sulfate II solution and silk fibroin protein solution is got, by certain volume ratio configuration mixing solutions, add a certain amount of additive and accelerate albumen plastic, slowly be laid on the tight zone film described in step (2), under fixed temperature and humidity condition, form Keratin sulfate/silk fibroin plural gel;
(4) the plural gel pre-freeze under the low temperature of-20 ~-80 DEG C step (3) obtained, the pre-freeze time is 4 ~ 24 hours, and then vacuum-drying forms Keratin sulfate/silk fibroin duplicature under cryogenic.
8. the preparation method of a kind of Keratin sulfate/silk fibroin blend film according to claim 7, is characterized in that: the concentration of the keratin solution and silk fibroin protein solution of preparing gained in described step (1) is 1 ~ 20%.
9. the preparation method of a kind of Keratin sulfate/silk fibroin blend film according to claim 7, it is characterized in that: the fixed temperature and humidity condition forming dense film and gel in the mixing solutions described in described step (2) is as follows: temperature is 20 ~ 70 DEG C, humidity is 30 ~ 70%.
10. the preparation method of a kind of Keratin sulfate/silk fibroin duplicature according to claim 7, it is characterized in that: for accelerating the transformation of solution-gel state in described step (3), can add with mixing solutions mass ratio is the additive of 1%-10%, this additive is mainly alcohols, as ethanol, propyl alcohol etc., mass concentration is 1 ~ 20%.
The preparation method of 11. a kind of Keratin sulfate/silk fibroin duplicatures according to claim 7, it is characterized in that: as follows to the lyophilisation condition of plural gel: temperature-90 ~-105 DEG C, equipment internal gas pressure is 1 ~ 10bar, and freeze-drying time is 24 ~ 48 hours.
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| CN106084256A (en) * | 2016-06-15 | 2016-11-09 | 中原工学院 | A kind of preparation method of self assembly protein nano composite micelle |
| CN107641204A (en) * | 2017-10-10 | 2018-01-30 | 东华大学 | A kind of keratin and its promotion fibroin albumen Rapid gelation, preparation method and applications rich in sulfydryl |
| CN108273132A (en) * | 2018-03-15 | 2018-07-13 | 南通纺织丝绸产业技术研究院 | A kind of fibroin albumen/keratin composite porous material and preparation method thereof |
| CN109431971A (en) * | 2018-10-19 | 2019-03-08 | 广州医科大学 | A kind of injectable carries liquid medicine gel and preparation method thereof |
| CN109504082A (en) * | 2018-10-08 | 2019-03-22 | 中原工学院 | A kind of preparation method of albumen self-assembled nanometer aperture film |
| CN110354307A (en) * | 2019-07-16 | 2019-10-22 | 西南大学 | Based on the albumen sericin gel and its preparation method and application for turning vectors containing human platelet-derived growth gene silk |
| CN111662472A (en) * | 2020-07-02 | 2020-09-15 | 西南大学 | Ultrathin transparent silk fibroin film, preparation method and application |
| CN113304732A (en) * | 2021-06-08 | 2021-08-27 | 苏州大学 | Porous composite material, preparation method and application thereof |
| CN113321845A (en) * | 2021-06-22 | 2021-08-31 | 上海电机学院 | Device and method for preparing biomedical material |
| CN113354840A (en) * | 2021-06-21 | 2021-09-07 | 内蒙古工业大学 | Keratin hydrogel and preparation method thereof, and keratin sponge scaffold and preparation method and application thereof |
| CN115845115A (en) * | 2023-03-03 | 2023-03-28 | 西湖大学 | Silk protein-based double-layer material and preparation method and application thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084256B (en) * | 2016-06-15 | 2018-10-30 | 中原工学院 | A kind of preparation method of self assembly protein nano composite micelle |
| CN106084256A (en) * | 2016-06-15 | 2016-11-09 | 中原工学院 | A kind of preparation method of self assembly protein nano composite micelle |
| CN107641204A (en) * | 2017-10-10 | 2018-01-30 | 东华大学 | A kind of keratin and its promotion fibroin albumen Rapid gelation, preparation method and applications rich in sulfydryl |
| CN108273132A (en) * | 2018-03-15 | 2018-07-13 | 南通纺织丝绸产业技术研究院 | A kind of fibroin albumen/keratin composite porous material and preparation method thereof |
| CN109504082B (en) * | 2018-10-08 | 2021-03-16 | 中原工学院 | Preparation method of protein self-assembly nano-aperture membrane |
| CN109504082A (en) * | 2018-10-08 | 2019-03-22 | 中原工学院 | A kind of preparation method of albumen self-assembled nanometer aperture film |
| CN109431971A (en) * | 2018-10-19 | 2019-03-08 | 广州医科大学 | A kind of injectable carries liquid medicine gel and preparation method thereof |
| CN109431971B (en) * | 2018-10-19 | 2021-12-21 | 广州医科大学 | Injectable drug-loaded hydrogel and preparation method thereof |
| CN110354307A (en) * | 2019-07-16 | 2019-10-22 | 西南大学 | Based on the albumen sericin gel and its preparation method and application for turning vectors containing human platelet-derived growth gene silk |
| CN111662472A (en) * | 2020-07-02 | 2020-09-15 | 西南大学 | Ultrathin transparent silk fibroin film, preparation method and application |
| CN111662472B (en) * | 2020-07-02 | 2022-08-02 | 西南大学 | Ultrathin transparent silk fibroin film, preparation method and application |
| CN113304732A (en) * | 2021-06-08 | 2021-08-27 | 苏州大学 | Porous composite material, preparation method and application thereof |
| CN113354840A (en) * | 2021-06-21 | 2021-09-07 | 内蒙古工业大学 | Keratin hydrogel and preparation method thereof, and keratin sponge scaffold and preparation method and application thereof |
| CN113321845A (en) * | 2021-06-22 | 2021-08-31 | 上海电机学院 | Device and method for preparing biomedical material |
| CN115845115A (en) * | 2023-03-03 | 2023-03-28 | 西湖大学 | Silk protein-based double-layer material and preparation method and application thereof |
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