CN104857569A - Preparation method of fibroin and graphene oxide composite bracket material - Google Patents
Preparation method of fibroin and graphene oxide composite bracket material Download PDFInfo
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- CN104857569A CN104857569A CN201510227779.5A CN201510227779A CN104857569A CN 104857569 A CN104857569 A CN 104857569A CN 201510227779 A CN201510227779 A CN 201510227779A CN 104857569 A CN104857569 A CN 104857569A
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Abstract
The invention discloses a preparation method of a fibroin and graphene oxide composite bracket material. The preparation method comprises the steps of: performing dissolution, filtration, dialysis and centrifugation on degumming fibrous fibroin in sequence, and then condensing to obtain a silk fibroin aqueous solution; dispersing graphene oxide aqueous solution ultrasonically; filtering in a vacuum manner to remove impurities; mixing the graphene oxide aqueous solution with the silk fibroin solution; mixing uniformly; oscillating at the presence of ultrasonic waves for mutual crosslinking; then centrifuging to obtain a mixed solution; then preparing by adopting a freeze-drying method so as to obtain the porous fibroin and graphene oxide composite bracket material. The high-concentration fibroin and the graphene oxide blended aqueous solution has good mixing property, the obtained composite bracket material is excellent in air permeability and drug-carrying ability, is good in hygroscopic property and waste liquid removal effect, and has wide application foreground.
Description
Technical field
The present invention relates to a kind of preparation method of composite, especially relate to the preparation method of a kind of fibroin and graphene oxide compound support frame material, belong to technical field of biomedical materials.
Background technology
Fibroin albumen is as a kind of natural fiber albumen, containing 18 seed amino acids human body being had to nutritive value, By Juvenile Hormone is because of the mechanical property of its uniqueness and good biocompatibility, controlled degradation, antibiotic property, stability, and reduced immunogenicity, have a wide range of applications in technical field of biological material, as membranaceous, porous support, gel, the various ways such as Powdered, fibrous can be prepared into, be applied to the research of immobilized enzyme, antigen-antibody carrier, slow releasing carrier of medication and anticoagulant material etc.Regenerated Silk Fibroin Film, comparatively strong to the adhesiveness of cell, epidermis cell, fibroblast, mescenchymal stem cell and other adult cell can grow well on fibroin membrane, play its function.Therefore after fibroin biological support can be used for operation, wound dressing, wound dressing of burn use, contribute to wound healing and non-stimulated, simultaneously, fibroin biological support by providing a suitable microenvironment in conjunction with cell or somatomedin for repairing impaired osseous tissue, can serve as interim bone alternate material.Therefore the biologic bracket material based on fibroin albumen has good application prospect in technical field of biological material.
Graphene oxide is a kind of derivant of Graphene, and microstructure can expand to some tens of pm at any time on lateral dimension, therefore, and its construct trans typical size of general chemistry and material science.Containing a lot of oxy radical on graphene oxide lamella, have amphipathic, present from graphene platelet edge to central authorities hydrophilic to hydrophobic property distribution, graphene oxide can as interfacial agent Presence of an interface, and the energy reduced between interface, there is superior dispersibility in water.Graphene oxide contains a large amount of oxygen-content active groups, as carbonyl, carboxyl, hydroxyl and epoxy radicals etc.Therefore, for the interaction between graphene oxide and fibroin albumen provides a large amount of binding sites.
The oxygen-content active group chemistry of Graphene is different, can carry out multiple covalent reaction with multiple fibroin peptide chain molecule, also there is the combination of the non-covalent bond such as ionic bond and hydrogen bond simultaneously.Many researcheres, by being undertaken blended by Graphene or graphene oxide and silk fibroin protein solution, attempt to prepare fibroin/graphene oxide film material that mechanical property improves.As graphene oxide and regenerated silk fibroin solution are alternately spin-coated in polystyrene substrate as preparing a kind of enhancement mode composite membrane [K Hu etc. of high fracture strength by spin coating technique by the people such as Kesong Hu, Ultra ?Robust Graphene Oxide ?Silk Fibroin NanocompositeMembranes, Advanced Materials 25 (16), 2301-230].But in the research that these are relevant, the composite prepared be all atresia or the film material for less porous, or the porous support materials be short of for mechanical property.Also unprecedented by silk fibroin water solution and graphene oxide blended, then preparation has the biologic bracket material of excellent mechanical property and high porosity, for the report that other tissues such as human body trauma skin, defective bone are repaired.
Summary of the invention
For the deficiency existed in conventional fabrication techniques, improved, the invention provides the preparation method of a kind of fibroin and graphene oxide compound support frame material, technique is simple, and process is convenient.The present invention is with natural macromolecular material fibroin albumen and graphene oxide for carrier, and the biologic bracket material made, is mainly used in the reparation of skin wound and the reparation of osseous tissue, is a kind of desirable biologic bracket material.
Feature of the present invention adopts following steps:
1) by the fibrous fibroin that obtains after degumming silkworm cocoons successively through dissolving, filtering, dialysis and centrifugal after, be concentrated into the silk fibroin water solution that mass percent is 1% ~ 25%;
2) disperse ultrasonic for graphene oxide water solution, vacuum filtration removes impurity;
3) after filtering with by step 1) concentrate the silk fibroin protein solution that obtains and mix, the mass ratio of graphene oxide and fibroin albumen is 1:10 ~ 1:1000, silk fibroin solution is made to be dispersed in graphene oxide solution, stir, vibrate 5 ~ 30min again under ultrasound wave, make to be cross-linked with each other between graphene oxide and fibroin albumen, centrifugal 5-40min, obtains mixed solution afterwards;
4) by step 3) in the mixed solution that obtains adopt freeze-drying to prepare the compound support frame material of porous fibroin and graphene oxide.The cryogenic temperature scope of freeze-drying can be-20 DEG C to-60 DEG C.
Described compound support frame material is used for being combined with human fibroblast preparing skin wound dressing, and human fibroblast be inoculated in described compound support frame material, show good ability of cell proliferation, cell morphology has major diameter distribution of orientations.
Described compound support frame material is used for being combined with human mesenchymal stem cell preparing engineering material of bone tissue, human mesenchymal stem cell is seeded in described compound support frame material, show good ability of cell proliferation, both high adherent effect had been shown after within one day, cultivating, after within two weeks, cultivating, can promote that cell secretes Type Ⅱ collagen and extracellular matrix associated protein in a large number, show good promotion cell tissue repairing effect.
Described step 1) the middle employing of fibroin albumen raw material domestic silkworm silk, tussah, spider silk or transgenic silk.
Described tussah is tussah silk, ricinus silk or cassava silkwormsilk.
Described step 2) in graphene oxide water solution, add SDS solution obtain disperseing homogeneous water solution system to make graphene oxide water solution, extend ultrasonic time.
Described step 2) in order to make graphene oxide water solution obtain disperseing homogeneous water solution system, the concentration of the graphene oxide water solution obtained after described filtration is 0.1 ~ 10mg/mL.
Described compound support frame material, by directly to add or covalence graft is added with the medicine of cell growth factor, antiseptic or antibacterial, forms the compound support frame material with sustained drug release effect.
Described compound support frame material to strengthen mechanical property and to improve degradability in aqueous through alcohols process, refers to compound support frame material to join in alcohol solution through alcohols process and carries out soaking or steam treatment.
The microstructure of described compound support frame material shows as cellular (high concentration fibroin) or netted (low concentration fibroin) loose structure, has very large specific surface area.
Compound support frame material of the present invention has good ductility and pull resistance, still because of elastic return to original appearance, can provide the gravity burden reaching hundreds of times than own wt after compression.
Compound support frame material of the present invention has excellent medicament slow release effect, slowly (for the formation of cambium reserves growing space) can be degraded in SBF solution, can be applicable to repair tissue wound, also can be applicable to as: the research in the fields such as biomaterial for medical purpose, artificial organ pipe, adhesive bandage, beauty mask, isolated by filtration material, pharmaceutical carrier and energy storage device, is with a wide range of applications.
Compared with prior art, the present invention has following outstanding feature:
(1) high concentration fibroin and the blended aqueous solution of graphene oxide have good Combination; Namely there is crosslinked and Supramolecular self assembly in the Contact of graphene oxide and fibroin albumen, without the need to adding cross-linking agent again and regulating pH, overcomes the shapeless problem that prior art exists, provide a kind of technique simple, and be suitable for the innovative approach of suitability for industrialized production.
(2) permeability and drug carrying ability excellent; Due to the three-dimensional porous structure containing tactical rule in fibroin-graphene oxide biological support, good permeability, the release of multiple somatomedin can be promoted after adding medicine, promote the regeneration of trauma skin, bone or other tissue, repair and reconstruction, wound surface and defective tissue healing rate are accelerated.
(3) hygroscopicity is respond well with eliminating waste liquid; Fibroin and graphene oxide all have high water retention performance, thus have good affine performance to tissue, and water absorption is splendid; Because Graphene and dressing materials all have huge specific surface area, a large amount of tissue secretion things and pus can be absorbed, reduce the generation of inflammation.
(4) lower cost, environment friendly and pollution-free; The material used be all can commercialization, large-scale production raw material, do not use other poisonous and hazardous chemical reagent,
(5) be with a wide range of applications; The research in other field such as other biomaterial for medical purpose, artificial organ pipe, adhesive bandage, beauty mask, isolated by filtration material, touch screen, energy storage device except repairing skin and osseous tissue can be applied to.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail, and following examples are explanation of the invention and the present invention is not limited to following examples.
Embodiments of the invention are as follows:
Embodiment 1:
(1) the fibrous fibroin just formed after degumming silkworm cocoons is dissolved in the LiBr solution of 9.3mol/L, through filtering, dialysis, centrifugal, and then is concentrated into the silk fibroin water solution that mass percent is 10%.
(2) 0.1mg/mL graphene oxide water solution is ultrasonic disperses, graphene oxide water solution is mixed with silk fibroin protein solution (mass ratio of mixing rear oxidation Graphene and fibroin albumen is 1:1000), graphene oxide is made to be dispersed in silk fibroin solution, stir, vibrate 5min under ultrasound wave, make to be cross-linked with each other between graphene oxide and fibroin albumen, the mixed solution obtained.
(3) dry through freezer dryer after the solution that obtains in (2) is freezing through-20 DEG C, namely obtain the spongy compound support frame material of graphene oxide and fibroin.
(4) dissolution experiment shows: compared with the fibroin sponge prepared with same concentrations, the biologic bracket material of graphene oxide and fibroin is in PBS, deionized water and SBF buffer solution, do not dissolve for a long time, and namely simple traditional fibroin sponge a few minutes dissolve.
Embodiment 2:
(1) by the fibrous fibroin that formed after degumming silkworm cocoons in the CaCl2 solution of 50% (w/w), through filtering, dialysis, centrifugal, and then be concentrated into the silk fibroin water solution that mass percent is 10%.
(2) disperse ultrasonic for 1mg/mL graphene oxide water solution, vacuum filtration; Silk fibroin protein solution in (1) is mixed with it (mass ratio of mixing rear oxidation Graphene and fibroin albumen is 1:50), silk fibroin solution is made to be dispersed in graphene oxide solution, stir for a long time, vibrate 10min under ultrasound wave, make to be cross-linked with each other between graphene oxide and fibroin albumen, low-speed centrifugal 20min afterwards, the mixed solution obtained.
(3) freeze-drying is adopted to prepare the membranaceous material of porous fibroin/graphene oxide the mixed solution obtained in (2).
(4) Mechanical test results shows: compare with the fibroin membrane of ratio with same concentrations, and tension failure distance increases by 50%, and can bear maximum stress increases by 113%, obviously strengthens the mechanical property of fibroin dressing.
Embodiment 3:
(1) the fibrous fibroin formed after degumming silkworm cocoons is dissolved, through filtering, dialysing, centrifugal, and then be concentrated into the silk fibroin water solution that mass percent is 5%;
(2) 2mg/mL graphene oxide water solution is added the SDS solution that mass fraction is 1%, more ultrasonicly carry out dispersion 15 minutes, vacuum filtration;
(3) silk fibroin protein solution in (1) is mixed with the graphene oxide solution in (2) (mass ratio mixing rear oxidation Graphene and fibroin albumen is 1:50), silk fibroin solution is made to be dispersed in graphene oxide solution, stir for a long time, vibrate 20min under ultrasound wave, make to be cross-linked with each other between graphene oxide and fibroin albumen, low-speed centrifugal 5min afterwards, the mixed solution obtained.
(4) pour the mixed solution obtained in (3) into column type mould, adopt freeze-drying to prepare porous fibroin/graphene oxide three-dimensional porous rack material, the Ethanol Treatment of 75%.
(5) human mesenchymal stem cell inoculation is obtained in porous fibroin/graphene oxide three-dimensional porous rack material in (4); Short-term cell culture, show good ability of cell proliferation (cell quantity is more than matched group), cell morphology has major diameter distribution of orientations, and fluorescence staining can be found out has obvious cell adhesion speckle outside cell membrane, illustrates that cell can secrete a large amount of extracellular matrix proteins in dressing; 2 weeks cultivate after, human mesenchymal stem cell is divided into osteoblast on this support, and starts the lamination having calcified tissue, and mescenchymal stem cell be seeded in simple fibroin three-dimensional porous rack material do not occur differentiation.
Embodiment 4:
(1) the fibrous fibroin formed after degumming silkworm cocoons is dissolved, through filtering, dialysing, centrifugal, and then be concentrated into the silk fibroin water solution that mass percent is 25%;
(2) 2mg/mL graphene oxide water solution is added the SDS solution that mass fraction is 1%, more ultrasonicly carry out dispersion 15 minutes, vacuum filtration;
(3) silk fibroin protein solution in (1) is mixed with the graphene oxide solution in (2) (mass ratio mixing rear oxidation Graphene and fibroin albumen is 1:100), silk fibroin solution is made to be dispersed in graphene oxide solution, stir for a long time, vibrate 20min under ultrasound wave, make to be cross-linked with each other between graphene oxide and fibroin albumen, low-speed centrifugal 10min afterwards, the mixed solution obtained.
(4) freeze-drying is adopted to prepare porous fibroin/graphene oxide three-dimensional porous rack material, the Ethanol Treatment of 75% mixed solution obtained in (3).
(5) people's fibrocyte can on three-dimensional porous rack normal growth and propagation.
Embodiment 5:
(1) the fibrous fibroin formed after degumming silkworm cocoons is dissolved, through filtering, dialysing, centrifugal, and then be concentrated into the silk fibroin water solution that mass percent is 1%;
(2) 10mg/mL graphene oxide water solution is added the SDS solution that mass fraction is 1%, more ultrasonicly carry out dispersion 15 minutes, vacuum filtration;
(3) silk fibroin protein solution in (1) is mixed with the graphene oxide solution in (2) (mass ratio mixing rear oxidation Graphene and fibroin albumen is 1:10), silk fibroin solution is made to be dispersed in graphene oxide solution, stir for a long time, vibrate 20min under ultrasound wave, make to be cross-linked with each other between graphene oxide and fibroin albumen, low-speed centrifugal 10min, obtains mixed solution afterwards.
(4) freeze-drying is adopted to prepare porous fibroin/graphene oxide three-dimensional porous rack material the mixed solution obtained in (3).
Embodiment 6:
(1) the fibrous fibroin formed after degumming silkworm cocoons is dissolved, through filtering, dialysing, centrifugal, and then be concentrated into the silk fibroin water solution that mass percent is 2%;
(2) in 1mg/mL graphene oxide water solution, add the SDS solution that mass fraction is 1%, more ultrasonicly carry out dispersion 15 minutes, vacuum filtration;
(3) silk fibroin protein solution in (1) is mixed with the graphene oxide solution in (2) (mass ratio mixing rear oxidation Graphene and fibroin albumen is 1:20), silk fibroin solution is made to be dispersed in graphene oxide solution, stir for a long time, vibrate 5min under ultrasound wave, make to be cross-linked with each other between graphene oxide and fibroin albumen, low-speed centrifugal 5min, obtains mixed solution afterwards.
(4) freeze-drying is adopted to prepare porous fibroin/graphene oxide three-dimensional porous rack material the mixed solution obtained in (3).
(5) three-dimensional porous rack material finally prepared has the specific surface area of superelevation, has very strong water suction, water retaining function.
Thus, present invention process is simple, and namely crosslinked and Supramolecular self assembly occur the Contact of graphene oxide and fibroin albumen, without the need to adding cross-linking agent again and regulating pH, overcomes the shapeless problem that prior art exists, is suitable for suitability for industrialized production; The biological support finally obtained is of many uses, permeability and drug carrying ability excellent, hygroscopicity and discharge opeing effective, can be used for skin, bone or other tissue; And lower cost, environment friendly and pollution-free, there is outstanding significant technique effect.
Finally, it is also to be noted that enumerate above be only specific embodiments of the invention son.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (9)
1. a preparation method for fibroin and graphene oxide compound support frame material, is characterized in that adopting following steps:
1) by the fibrous fibroin that obtains after degumming silkworm cocoons successively through dissolving, filtering, dialysis and centrifugal after, be concentrated into the silk fibroin water solution that mass percent is 1% ~ 25%;
2) disperse ultrasonic for graphene oxide water solution, vacuum filtration removes impurity;
3) after filtering with step 1) is concentrated the silk fibroin protein solution obtained and mixes, the mass ratio of graphene oxide and fibroin albumen is 1:10 ~ 1:1000, silk fibroin solution is made to be dispersed in graphene oxide solution, stir, vibrate 5 ~ 30min again under ultrasound wave, make to be cross-linked with each other between graphene oxide and fibroin albumen, then centrifugal 5-40min, obtains mixed solution;
4) freeze-drying is adopted to prepare the compound support frame material of porous fibroin and graphene oxide the mixed solution obtained in step 3).
2. the preparation method of a kind of fibroin according to claim 1 and graphene oxide compound support frame material, is characterized in that: described compound support frame material is used for being combined with human fibroblast preparing skin wound dressing.
3. the preparation method of a kind of fibroin according to claim 1 and graphene oxide compound support frame material, is characterized in that: described compound support frame material is used for being combined with human mesenchymal stem cell preparing engineering material of bone tissue.
4. the preparation method of a kind of fibroin according to claim 1 and graphene oxide compound support frame material, is characterized in that: in described step 1), fibroin albumen raw material adopts domestic silkworm silk, tussah, spider silk or transgenic silk.
5. the preparation method of a kind of fibroin according to claim 1 and graphene oxide compound support frame material, is characterized in that: described step 2) in graphene oxide water solution, add SDS solution obtain disperseing homogeneous water solution system to make graphene oxide water solution.
6. the preparation method of a kind of fibroin according to claim 1 and graphene oxide compound support frame material, is characterized in that: described step 2) in filter after the concentration of graphene oxide water solution that obtains be 0.1 ~ 10 mg/mL.
7. the preparation method of a kind of fibroin according to claim 1 and graphene oxide compound support frame material, it is characterized in that: described compound support frame material, by directly to add or covalence graft is added with the medicine of cell growth factor, antiseptic or antibacterial, forms the compound support frame material with sustained drug release effect.
8. the preparation method of a kind of fibroin according to claim 1 and graphene oxide compound support frame material, it is characterized in that: described compound support frame material to strengthen mechanical property and to improve degradability in aqueous through alcohols process, refers to compound support frame material to join in alcohol solution through alcohols process and carries out soaking or steam treatment.
9. the preparation method of a kind of fibroin according to claim 1 and graphene oxide compound support frame material, is characterized in that: the microstructure of described compound support frame material shows as cellular or reticulated porous structures.
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| CN111925557B (en) * | 2020-07-31 | 2022-10-11 | 淮阴工学院 | Preparation method of silk fibroin wound dressing based on MXene enhancement |
| CN111939318A (en) * | 2020-08-23 | 2020-11-17 | 苏州宣医智慧医疗科技有限公司 | Preparation method of reduced graphene oxide silk fibroin composite membrane |
| CN113499481B (en) * | 2021-06-18 | 2022-07-19 | 广东省科学院健康医学研究所 | Porous scaffold and preparation method and application thereof |
| CN113499481A (en) * | 2021-06-18 | 2021-10-15 | 广东省科学院健康医学研究所 | Porous scaffold and preparation method and application thereof |
| CN113842505A (en) * | 2021-09-13 | 2021-12-28 | 南通大学 | Preparation method of porous double-network nano conductive hydrogel nerve scaffold for nerve repair |
| CN115245601A (en) * | 2022-01-18 | 2022-10-28 | 郑州大学第一附属医院 | Tympanic membrane repair material and preparation method thereof |
| CN115245601B (en) * | 2022-01-18 | 2023-08-22 | 郑州大学第一附属医院 | Tympanic membrane repair material and preparation method thereof |
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Application publication date: 20150826 |