WO2020134443A1 - Solution-spraying preparation method for silk fibroin biological tissue engineering stent with optimized mechanical properties - Google Patents

Solution-spraying preparation method for silk fibroin biological tissue engineering stent with optimized mechanical properties Download PDF

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WO2020134443A1
WO2020134443A1 PCT/CN2019/113149 CN2019113149W WO2020134443A1 WO 2020134443 A1 WO2020134443 A1 WO 2020134443A1 CN 2019113149 W CN2019113149 W CN 2019113149W WO 2020134443 A1 WO2020134443 A1 WO 2020134443A1
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silk fibroin
mechanical properties
fiber
silk
solution
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PCT/CN2019/113149
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French (fr)
Chinese (zh)
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罗杰
张耀鹏
吕悦光
谢啸峰
林嘉栋
张敏
熊帮云
余明光
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佛山科学技术学院
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D13/00—Complete machines for producing artificial threads
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01C—CHEMICAL OR BIOLOGICAL TREATMENT OF NATURAL FILAMENTARY OR FIBROUS MATERIAL TO OBTAIN FILAMENTS OR FIBRES FOR SPINNING; CARBONISING RAGS TO RECOVER ANIMAL FIBRES
    • D01C3/00—Treatment of animal material, e.g. chemical scouring of wool
    • D01C3/02—De-gumming silk
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D7/00—Collecting the newly-spun products
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
    • D06B1/02—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by spraying or projecting
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2211/00—Protein-based fibres, e.g. animal fibres
    • D10B2211/20—Protein-derived artificial fibres
    • D10B2211/22—Fibroin

Definitions

  • the technical scheme belongs to the technical field of biomedical materials, and particularly relates to a method for preparing a silk fibroin bio-tissue engineering scaffold with optimized mechanical properties by melt spraying.
  • Silk is composed of silk fibroin and sericin. Sericin is wrapped on the outside of silk fibroin and accounts for about 25% of the weight. There are also about 5% impurities in silk.
  • Silk fibroin is the main component of silk , About 70% of the weight.
  • Silk fibroin is based on the antiparallel folding chain conformation ( ⁇ -sheet) to form microfibers with a diameter of about 10nm. Numerous microfibers are closely combined to form fine fibers with a diameter of about 1Lm. About 100 fine fibers are arranged to form a diameter of about 10Lm. ⁇ 18Lm single fiber, namely silk protein fiber.
  • Silk fibroin bio-tissue engineering scaffolds can mimic the structure and function of extracellular matrix to a certain extent, and provide ideal microenvironment for cells to grow, proliferate and differentiate. In just a few years, they have been widely used in cartilage, Various fields of tissue engineering research such as bone, blood vessel and skin. However, there are many random conformations in the structure of the currently prepared silk fibroin fiber membrane, and the existence of the random conformation will seriously affect the mechanical properties of the silk fibroin fiber membrane.
  • the technical solution provides a solution spray preparation method of a silk fibroin biological tissue engineering scaffold with optimized mechanical properties.
  • the preparation method can imitate the animal spinning process in nature, and the silk fibroin biological tissue engineering prepared by the preparation method The mechanical properties of the bracket are good.
  • a solution spray preparation method of silk fibroin biotissue engineering scaffold with optimized mechanical properties includes a post-processing step for fiber spinning, the specific process is: using an ethanol spray device to spray treatment of fiber spinning , Wherein the ethanol spraying speed in the ethanol spraying device is 100-1000 mL/min, and the silk fibroin biological tissue engineering scaffold is prepared.
  • the concentration of ethanol in the ethanol spray device is 50-100%
  • a method for dissolving spray preparation of silk fibroin biological tissue engineering scaffold with optimized mechanical properties includes the following steps before fiber spinning post-treatment:
  • step (2) Using the silk fibroin solution prepared in step (1) as a spinning solution, a high-pressure air jet at a temperature of 37 to 120° C. is used as the drawing power to perform melt-spinning spinning, and receive fiber spinning with a fiber receiver Silk; the silk fibroin fibers in the silk fibroin biotissue engineering scaffold prepared by the above steps have a diameter of micron and sub-micron level, and even can reach the nanometer level, which can imitate the structure of human extracellular matrix to the greatest extent; this technical solution No voltage is required in the preparation method described in, and the preparation method does not use an organic solvent, which has high operability and safety, is environmentally friendly, and can be applied in large-scale industrial production; and the preparation method can be adjusted by Processing parameters, so that the porosity of the prepared silk fibroin biological tissue engineering scaffold meets the needs of different cell growth; the silk fibroin biological tissue engineering scaffold prepared by the preparation method has high porosity and good pore connectivity, And it also has a large specific surface area, which can provide a good microenviron
  • the solvent for dissolving the degummed silk is LiBr aqueous solution or ethanol/CaCl aqueous solution.
  • a solution spray preparation method of silk fibroin biotissue engineering scaffold with optimized mechanical properties further includes the following steps: adding a pH adjusting agent to the silk fibroin solution prepared in step (1) to adjust the pH, and adding
  • the pH adjusting agent is metal ion or inorganic nano powder.
  • the metal ion is one of calcium ion and silver ion.
  • the inorganic nano powder is one of hydroxyapatite and tricalcium phosphate.
  • the fiber receiver uses a fiber receiving plate, a silk fibroin nonwoven fiber membrane is obtained.
  • the fiber receiver uses a fiber receiving drum, a continuous filament film of silk fibroin that is unidirectionally stretched and ordered in one direction is obtained.
  • the high-pressure air jet described in step (2) is dried compressed air with a relative humidity of 10% to 40%, and the jet pressure of the high-pressure air jet used is 10 MPa to 30 MPa.
  • the beneficial effects of this technical solution are: there are three conformations in the silk fibroin, random conformation, ⁇ helix, ⁇ fold.
  • the ⁇ -sheet conformation is a stable structure, while the silk fibroin conformation in the silk fibroin membrane is mainly Mainly ⁇ -sheeting, and the more ⁇ -sheet conformation in the silk fibroin fiber membrane, the better the mechanical properties of the silk fibrin membrane;
  • the technical solution adopts an ethanol spray device to spray the fiber spinning, wherein the ethanol spray speed in the ethanol spray device is 100-1000 mL/min, so that the treatment of the silk fibroin spinning fiber can promote the The random conformation changes to the ⁇ -fold conformation to obtain a silk fibroin fiber membrane with a uniform macroscopic texture;
  • the silk fibroin tissue engineering scaffold prepared by the technical scheme can be used for tissue engineering scaffolds such as blood vessels, urethra, cartilage, bone, etc. Used for blood filtration after surface treatment.
  • a solution spray preparation method of silk fibroin biotissue engineering scaffold with optimized mechanical properties includes the following steps: (1) Degumming silkworm cocoons with an aqueous solution of sodium carbonate to obtain degummed silk, and dissolving the degummed silk with 9mol/L lithium bromide aqueous solution as a solvent And dissolve the degummed silk in a 40°C water bath environment for 2 hours to obtain an aqueous solution of silk fibroin; (2) after centrifugation, filtration, dialysis and concentration, a silk fibroin spinning solution with a concentration of 12 wt% is obtained; (3) The high-pressure air jet with a temperature of 120°C and a relative humidity of 10% is used as the drawing power.
  • the jet pressure of the high-pressure air jet used is 30 MPa, and the fiber receiving plate is used to receive spinning.
  • An ethanol spray device is provided above the fiber receiving plate to spin the fiber.
  • the silk was post-treated, the ethanol spraying speed in the ethanol spraying device was 100 mL/min, and the ethanol concentration was 80%, a silk fibroin nonwoven fiber membrane was prepared, and the average diameter of the silk fibrin fiber was 6 ⁇ m.
  • a solution spray preparation method of silk fibroin biotissue engineering scaffold with optimized mechanical properties includes the following steps: (1) Degumming silkworm cocoons with an aqueous solution of sodium carbonate to obtain degummed silk, and dissolving the degummed silk with 9mol/L lithium bromide aqueous solution as a solvent , Dissolve the degummed silk for 2 hours in a 40°C water bath environment to obtain an aqueous solution of silk fibroin; (2) After centrifugation, filtration, dialysis and concentration, obtain a silk fibroin spinning solution with a concentration of 12wt%; (3) at a temperature 120 ⁇ , the high-pressure air jet with relative humidity of 10% is the drawing power, the jet pressure of the high-pressure air jet used is 20MPa, and the fiber receiving plate receives spinning, and the fiber receiving plate is provided with an ethanol spray device to spin the fiber After the post-treatment, the ethanol spraying speed in the ethanol spraying device was 100 mL/min, and the ethanol concentration was 50%,
  • a solution spray preparation method of silk fibroin biotissue engineering scaffold with optimized mechanical properties includes the following steps: (1) Degumming silkworm cocoons with an aqueous solution of sodium carbonate to obtain degummed silk, and dissolving the degummed silk with 9mol/L lithium bromide aqueous solution as a solvent Dissolve the degummed silk for 12 hours in a 40°C water bath environment to obtain a silk fibroin aqueous solution; (2) After centrifugation, filtration, dialysis and concentration to 20wt%, add CaCl to the calcium ion concentration in the silk fibroin aqueous solution to be 0.3mol/ L, continue to concentrate until the silk fibroin concentration is 45% by weight; (3) Use a high-pressure air jet with a temperature of 37°C and a humidity of 50% by weight as the stretching power, and the jet pressure of the high-pressure air jet used is 30 MPa, and use a fiber receiving plate After receiving spinning, an ethanol spray device is provided above the fiber receiving plate to perform
  • a solution spray preparation method of silk fibroin bio-tissue engineering scaffold with optimized mechanical properties includes the following steps: (1) Degumming silkworm cocoons with aqueous sodium carbonate solution to obtain degummed silk, using 7mol/L calcium chloride/ethanol aqueous solution as Solvent dissolves the degummed silk and dissolves the degummed silk in a water bath environment at 40°C for 6 hours to obtain an aqueous solution of silk fibroin; (2) After centrifugation, filtration, dialysis and concentration, a spinning solution with a silk fibroin concentration of 30% by weight is obtained; (3 ) The high-pressure air jet with a temperature of 100°C and a humidity of 25wt% is used as the drawing power.
  • the jet pressure of the high-pressure air jet used is 25MPa, and the fiber receiving plate is used for spinning.
  • the fiber receiving plate is provided with an ethanol spray device to spin the fiber.
  • the silk was post-treated, the ethanol spraying speed in the ethanol spraying device was 1000 mL/min, and the ethanol concentration was 80%, a silk fibroin nonwoven fiber membrane was prepared, and the average diameter of the silk fibrin fiber was 5 ⁇ m.
  • a solution spray preparation method of silk fibroin bio-tissue engineering scaffold with optimized mechanical properties includes the following steps: (1) Degumming silkworm cocoons with aqueous sodium carbonate solution to obtain degummed silk, using 7mol/L calcium chloride/ethanol aqueous solution as Solvent dissolves the degummed silk and dissolves the degummed silk for 12 hours in a 40°C water bath environment to obtain an aqueous solution of silk fibroin; (2) centrifugation, filtration, dialysis and concentration to obtain a spinning solution with a silk fibroin concentration of 12% by weight; (3 ) The high-pressure air jet with a temperature of 100°C and a humidity of 10wt% is used as the drawing power.
  • the jet pressure of the high-pressure air jet used is 20MPa, and the fiber receiving plate is used for spinning.
  • An ethanol spray device is provided above the fiber receiving plate to treat the fibers. After spinning, the post-treatment is performed.
  • the ethanol spray speed in the ethanol spray device is 1000 mL/min, and the ethanol concentration is 80%.
  • a silk fibroin nonwoven fiber membrane is prepared, and the average diameter of the silk fibrin fiber is 200 nm.

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Abstract

Provided is a solution-spraying preparation method for silk fibroin biological tissue engineering stent with optimized mechanical properties, the preparation method includes a post-processing step for fiber spinning, the specific process is: using an ethanol spraying device to perform spraying treatment to the fiber spinning, wherein the ethanol spraying speed in the ethanol spraying device is 100-1000 mL/min, preparing the bioprotein tissue engineering stent. Spraying treatment of silk fibroin spinning fiber can promote the random conformation of silk fibroin to β-sheet conformation, thus, a silk fibroin biological tissue engineering stent with uniform macroscopic texture is obtained; the prepared silk fibroin biological tissue engineering stent can be used for tissue engineering stent of blood vessels, urethra, cartilage, bone and the like, and can also be used for blood filtration after surface treatment.

Description

一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法Dissolved spray preparation method of silk fibroin biological tissue engineering scaffold with optimized mechanical properties 技术领域Technical field
本技术方案属于生物医用材料技术领域，特别涉及一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法。The technical scheme belongs to the technical field of biomedical materials, and particularly relates to a method for preparing a silk fibroin bio-tissue engineering scaffold with optimized mechanical properties by melt spraying.
背景技术Background technique
蚕丝是由丝素蛋白和丝胶两部分组成，丝胶包在丝素蛋白的外部，约占重量的25％，蚕丝中还有5％左右的杂质，丝素蛋白是蚕丝中主要的组成部分，约占重量的70％。丝素蛋白以反平行折叠链构象(β折叠)为基础，形成直径大约为10nm的微纤维，无数微纤维密切结合组成直径大约为1Lm的细纤维，大约100根细纤维排列构成直径大约为10Lm～18Lm的单纤维，即蚕丝蛋白纤维。Silk is composed of silk fibroin and sericin. Sericin is wrapped on the outside of silk fibroin and accounts for about 25% of the weight. There are also about 5% impurities in silk. Silk fibroin is the main component of silk , About 70% of the weight. Silk fibroin is based on the antiparallel folding chain conformation (β-sheet) to form microfibers with a diameter of about 10nm. Numerous microfibers are closely combined to form fine fibers with a diameter of about 1Lm. About 100 fine fibers are arranged to form a diameter of about 10Lm. ~18Lm single fiber, namely silk protein fiber.
丝素蛋白生物组织工程支架因能在一定程度上模仿细胞外基质的结构和功能，为细胞提供理想的生长、增殖和分化的微环境，在短短几年内，已被广泛应用于包括软骨、骨、血管、皮肤等组织工程研究的各个领域。但现有制备的丝素蛋白纤维膜中结构中有许多无规构象存在，无规构象的存在会严重影响丝素蛋白纤维膜的力学性能。Silk fibroin bio-tissue engineering scaffolds can mimic the structure and function of extracellular matrix to a certain extent, and provide ideal microenvironment for cells to grow, proliferate and differentiate. In just a few years, they have been widely used in cartilage, Various fields of tissue engineering research such as bone, blood vessel and skin. However, there are many random conformations in the structure of the currently prepared silk fibroin fiber membrane, and the existence of the random conformation will seriously affect the mechanical properties of the silk fibroin fiber membrane.
发明内容Summary of the invention
本技术方案提供一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，所述制备方法能模仿自然界的动物纺丝过程，并且通所述制备方法制备的丝素蛋白生物组织工程支架的力学性能好。The technical solution provides a solution spray preparation method of a silk fibroin biological tissue engineering scaffold with optimized mechanical properties. The preparation method can imitate the animal spinning process in nature, and the silk fibroin biological tissue engineering prepared by the preparation method The mechanical properties of the bracket are good.
为实现上述目的，本技术方案采用的下述技术手段。In order to achieve the above purpose, the following technical means adopted by the present technical solution.
一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，所述制备方法中包括对纤维纺丝进行后处理步骤，其具体过程为：采用乙醇喷雾装置对纤维纺丝进行喷雾处理，其中所述乙醇喷雾装置中的乙醇喷雾速度为 100～1000mL/min，制得所述丝素蛋白生物组织工程支架。A solution spray preparation method of silk fibroin biotissue engineering scaffold with optimized mechanical properties, the preparation method includes a post-processing step for fiber spinning, the specific process is: using an ethanol spray device to spray treatment of fiber spinning , Wherein the ethanol spraying speed in the ethanol spraying device is 100-1000 mL/min, and the silk fibroin biological tissue engineering scaffold is prepared.
进一步地，所述乙醇喷雾装置中乙醇的浓度为50～100％Further, the concentration of ethanol in the ethanol spray device is 50-100%
一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，在进行纤维纺丝后处理之前还包括以下步骤：A method for dissolving spray preparation of silk fibroin biological tissue engineering scaffold with optimized mechanical properties includes the following steps before fiber spinning post-treatment:
(1)用溶剂将脱胶蚕丝溶解透析后，获得浓度为8～45％的丝素蛋白溶液；(1) After dissolving and dialysis the degummed silk with a solvent, a silk fibroin solution with a concentration of 8 to 45% is obtained;
(2)将步骤(1)制得的丝素蛋白溶液作为纺丝液，在温度为37～120℃的高压空气喷射流为拉伸动力，进行溶喷纺丝，并用纤维接收器接收纤维纺丝；采用上述步骤制备的丝素蛋白生物组织工程支架中的丝素蛋白纤维的直径为微米和亚微米级别，甚至可以达到纳米级别，可以最大程度地模仿人体细胞外基质的结构；本技术方案中所述的制备方法中不需要电压，并且所述制备方法不采用有机溶剂，其操作性及安全性高，并且对环境友好，能在工业生产中大规模应用；并且上述制备方法可以通过调节加工参数，使得制备的丝素蛋白生物组织工程支架中的孔隙率满足不同细胞生长的需求；采用所述制备方法制备的丝素蛋白生物组织工程支架具有高的孔隙率和良好的孔道连通性，并且也具有大的比表面积，能为细胞的生长提供良好的微环境，有利于细胞的粘附、分化和增殖。(2) Using the silk fibroin solution prepared in step (1) as a spinning solution, a high-pressure air jet at a temperature of 37 to 120° C. is used as the drawing power to perform melt-spinning spinning, and receive fiber spinning with a fiber receiver Silk; the silk fibroin fibers in the silk fibroin biotissue engineering scaffold prepared by the above steps have a diameter of micron and sub-micron level, and even can reach the nanometer level, which can imitate the structure of human extracellular matrix to the greatest extent; this technical solution No voltage is required in the preparation method described in, and the preparation method does not use an organic solvent, which has high operability and safety, is environmentally friendly, and can be applied in large-scale industrial production; and the preparation method can be adjusted by Processing parameters, so that the porosity of the prepared silk fibroin biological tissue engineering scaffold meets the needs of different cell growth; the silk fibroin biological tissue engineering scaffold prepared by the preparation method has high porosity and good pore connectivity, And it also has a large specific surface area, which can provide a good microenvironment for the growth of cells, which is conducive to cell adhesion, differentiation and proliferation.
进一步地，所述溶解脱胶蚕丝的溶剂为LiBr水溶液或乙醇/CaCl水溶液。Further, the solvent for dissolving the degummed silk is LiBr aqueous solution or ethanol/CaCl aqueous solution.
进一步地，一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法还包括以下步骤：对步骤(1)制得的丝素蛋白溶液加入pH值调节剂进行pH值调节，其添加的pH值调节剂为金属离子或无机纳米粉体。Further, a solution spray preparation method of silk fibroin biotissue engineering scaffold with optimized mechanical properties further includes the following steps: adding a pH adjusting agent to the silk fibroin solution prepared in step (1) to adjust the pH, and adding The pH adjusting agent is metal ion or inorganic nano powder.
进一步地，所述金属离子为钙离子、银离子中的一种。Further, the metal ion is one of calcium ion and silver ion.
进一步地，所述无机纳米粉体为羟基磷灰石、磷酸三钙中的一种。Further, the inorganic nano powder is one of hydroxyapatite and tricalcium phosphate.
进一步地，所述纤维接收器采用的是纤维接收平板时，获得丝素蛋白无纺纤维膜。Further, when the fiber receiver uses a fiber receiving plate, a silk fibroin nonwoven fiber membrane is obtained.
进一步地，所述纤维接收器采用的是纤维接收滚筒时，获得单向拉伸且单方向有序排列的丝素蛋白连续长纤维膜。Further, when the fiber receiver uses a fiber receiving drum, a continuous filament film of silk fibroin that is unidirectionally stretched and ordered in one direction is obtained.
进一步地，步骤(2)中所述的高压空气喷射流为经过干燥的压缩空气，其相对湿度为10％～40％，所用高压空气喷射流的喷射压力为10MPa～30MPa。Further, the high-pressure air jet described in step (2) is dried compressed air with a relative humidity of 10% to 40%, and the jet pressure of the high-pressure air jet used is 10 MPa to 30 MPa.
本技术方案的有益效果为：丝素蛋白中有三种构象，无规构象、α螺旋、β折叠，在这三种构象中β折叠构象是一种肽链相当伸展的结构，其中肽链层层排列，依靠相邻肽链上的＞C＝0与＞N-H形成的氢键来维持其稳定的结构，β折叠构象是一种稳定结构，而丝素蛋白纤维膜中的丝素蛋白构象主要是以β折叠为主，且丝素蛋白纤维膜中β折叠构象越多，则丝素蛋白纤维膜的力学性能则越好；The beneficial effects of this technical solution are: there are three conformations in the silk fibroin, random conformation, α helix, β fold. Among these three conformations, the β fold conformation is a structure with fairly stretched peptide chains, in which the peptide chains are layer by layer. The arrangement depends on the hydrogen bond formed by >C=0 and >NH on the adjacent peptide chain to maintain its stable structure. The β-sheet conformation is a stable structure, while the silk fibroin conformation in the silk fibroin membrane is mainly Mainly β-sheeting, and the more β-sheet conformation in the silk fibroin fiber membrane, the better the mechanical properties of the silk fibrin membrane;
本技术方案采用乙醇喷雾装置对纤维纺丝进行喷雾处理，其中所述乙醇喷雾装置中的乙醇喷雾速度为100～1000mL/min，这样对丝素蛋白纺丝纤维进行处理能够促使丝素蛋白中的无规构象向β折叠构象转变，从而得到宏观质地均匀的丝素蛋白纤维膜；本技术方案制得的丝素生物组织工程支架可用于血管、尿道、软骨、骨等组织工程支架，还可经表面处理后用于血液过滤。The technical solution adopts an ethanol spray device to spray the fiber spinning, wherein the ethanol spray speed in the ethanol spray device is 100-1000 mL/min, so that the treatment of the silk fibroin spinning fiber can promote the The random conformation changes to the β-fold conformation to obtain a silk fibroin fiber membrane with a uniform macroscopic texture; the silk fibroin tissue engineering scaffold prepared by the technical scheme can be used for tissue engineering scaffolds such as blood vessels, urethra, cartilage, bone, etc. Used for blood filtration after surface treatment.
具体实施方式detailed description
下面结合具体实施例进一步说明本发明的技术方案。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。The technical solution of the present invention is further described below with reference to specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that, after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，包括以下步骤：(1)将蚕茧用碳酸钠水溶液脱胶，得到脱胶蚕丝，以9mol/L的溴化锂水溶液为溶剂溶解脱胶蚕丝，并在40℃水浴环境下溶解脱胶蚕丝2小时，得到丝素蛋白水溶液；(2)经离心、过滤、透析和浓缩后，获得浓度为12wt％的丝素蛋白纺丝液；(3)以温度120℃，相对湿度为10％的高压空气喷射流为拉伸动力，所用高压空气喷射流的喷射压力为30MPa，并用纤维接收平板接收纺丝，纤维接收平板上方设有乙醇喷雾装置对纤维纺丝进行后处理，所述乙醇喷雾装置中的乙醇喷雾速度为100mL/min，且乙醇浓度为80％，制得丝素蛋白无纺纤维膜，且丝素蛋白纤维平均直径为6μm。A solution spray preparation method of silk fibroin biotissue engineering scaffold with optimized mechanical properties includes the following steps: (1) Degumming silkworm cocoons with an aqueous solution of sodium carbonate to obtain degummed silk, and dissolving the degummed silk with 9mol/L lithium bromide aqueous solution as a solvent And dissolve the degummed silk in a 40°C water bath environment for 2 hours to obtain an aqueous solution of silk fibroin; (2) after centrifugation, filtration, dialysis and concentration, a silk fibroin spinning solution with a concentration of 12 wt% is obtained; (3) The high-pressure air jet with a temperature of 120°C and a relative humidity of 10% is used as the drawing power. The jet pressure of the high-pressure air jet used is 30 MPa, and the fiber receiving plate is used to receive spinning. An ethanol spray device is provided above the fiber receiving plate to spin the fiber. The silk was post-treated, the ethanol spraying speed in the ethanol spraying device was 100 mL/min, and the ethanol concentration was 80%, a silk fibroin nonwoven fiber membrane was prepared, and the average diameter of the silk fibrin fiber was 6 μm.
实施例2Example 2
一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，包括以下步骤：(1)将蚕茧用碳酸钠水溶液脱胶，得到脱胶蚕丝，以9mol/L的溴化锂水溶液为溶剂溶解脱胶蚕丝，在40℃水浴环境下溶解脱胶蚕丝2小时，得到丝素蛋白水溶液；(2)经离心、过滤、透析和浓缩后，获得浓度为12wt％的丝素蛋白纺丝液；(3)以温度120□，相对湿度为10％的高压空气喷射流为拉伸动力，所用高压空气喷射流的喷射压力为20MPa，并用纤维接收平板接收纺丝，纤维接收平板上方设有乙醇喷雾装置对纤维纺丝进行后处理，所述乙醇喷雾装置中的乙醇喷雾速度为100mL/min，且乙醇浓度为50％，制得丝素蛋白无纺纤维膜，且丝素蛋白纤维平均直径为6μm。A solution spray preparation method of silk fibroin biotissue engineering scaffold with optimized mechanical properties includes the following steps: (1) Degumming silkworm cocoons with an aqueous solution of sodium carbonate to obtain degummed silk, and dissolving the degummed silk with 9mol/L lithium bromide aqueous solution as a solvent , Dissolve the degummed silk for 2 hours in a 40°C water bath environment to obtain an aqueous solution of silk fibroin; (2) After centrifugation, filtration, dialysis and concentration, obtain a silk fibroin spinning solution with a concentration of 12wt%; (3) at a temperature 120□, the high-pressure air jet with relative humidity of 10% is the drawing power, the jet pressure of the high-pressure air jet used is 20MPa, and the fiber receiving plate receives spinning, and the fiber receiving plate is provided with an ethanol spray device to spin the fiber After the post-treatment, the ethanol spraying speed in the ethanol spraying device was 100 mL/min, and the ethanol concentration was 50%, a silk fibroin nonwoven fiber membrane was prepared, and the average diameter of the silk fibrin fiber was 6 μm.
实施例3Example 3
一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，包括以下步骤：(1)将蚕茧用碳酸钠水溶液脱胶，得到脱胶蚕丝，以9mol/L的溴化锂水溶液为溶剂溶解脱胶蚕丝，在40℃水浴环境下溶解脱胶蚕丝12小时，得到丝素蛋白水溶液；(2)经离心、过滤、透析和浓缩至20wt％后，添加CaCl至丝素蛋白水溶液中钙离子浓度为0.3mol/L，继续浓缩至丝素蛋白浓度为45wt％；(3)以温度37℃，湿度为50wt％的高压空气喷射流为拉伸动力，所用高压空气喷射流的喷射压力为30MPa，并用纤维接收平板接收纺丝，纤维接收平板上方设有乙醇喷雾装置对纤维纺丝进行后处理，所述乙醇喷雾装置中的乙醇喷雾速度为100mL/min，且乙醇浓度为100％，制得丝素蛋白无纺纤维膜，且丝素蛋白纤维平均直径为3μm。A solution spray preparation method of silk fibroin biotissue engineering scaffold with optimized mechanical properties includes the following steps: (1) Degumming silkworm cocoons with an aqueous solution of sodium carbonate to obtain degummed silk, and dissolving the degummed silk with 9mol/L lithium bromide aqueous solution as a solvent Dissolve the degummed silk for 12 hours in a 40°C water bath environment to obtain a silk fibroin aqueous solution; (2) After centrifugation, filtration, dialysis and concentration to 20wt%, add CaCl to the calcium ion concentration in the silk fibroin aqueous solution to be 0.3mol/ L, continue to concentrate until the silk fibroin concentration is 45% by weight; (3) Use a high-pressure air jet with a temperature of 37°C and a humidity of 50% by weight as the stretching power, and the jet pressure of the high-pressure air jet used is 30 MPa, and use a fiber receiving plate After receiving spinning, an ethanol spray device is provided above the fiber receiving plate to perform post-processing on the fiber spinning. The ethanol spray speed in the ethanol spray device is 100 mL/min, and the ethanol concentration is 100%. Fiber membrane, and the average diameter of silk fibroin fiber is 3 μm.
实施例4Example 4
一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，包括以下步骤：(1)将蚕茧用碳酸钠水溶液脱胶，得到脱胶蚕丝，以7mol/L的氯化钙/乙醇水溶液为溶剂溶解脱胶蚕丝，在40℃水浴环境下溶解脱胶蚕丝6小时，得到丝素蛋白水溶液；(2)经离心、过滤、透析和浓缩，得到丝素蛋白浓度为30wt％的纺丝液；(3)以温度100℃，湿度为25wt％的高压空气喷射流为拉伸动力，所用高压空气喷射流的喷射压力为25MPa，并用纤维接收平板接收纺丝，纤维接收平板设有乙醇喷雾装置对纤维纺丝进行后处理， 所述乙醇喷雾装置中的乙醇喷雾速度为1000mL/min，且乙醇浓度为80％，制得丝素蛋白无纺纤维膜，且丝素蛋白纤维平均直径为5μm。A solution spray preparation method of silk fibroin bio-tissue engineering scaffold with optimized mechanical properties includes the following steps: (1) Degumming silkworm cocoons with aqueous sodium carbonate solution to obtain degummed silk, using 7mol/L calcium chloride/ethanol aqueous solution as Solvent dissolves the degummed silk and dissolves the degummed silk in a water bath environment at 40℃ for 6 hours to obtain an aqueous solution of silk fibroin; (2) After centrifugation, filtration, dialysis and concentration, a spinning solution with a silk fibroin concentration of 30% by weight is obtained; (3 ) The high-pressure air jet with a temperature of 100°C and a humidity of 25wt% is used as the drawing power. The jet pressure of the high-pressure air jet used is 25MPa, and the fiber receiving plate is used for spinning. The fiber receiving plate is provided with an ethanol spray device to spin the fiber. The silk was post-treated, the ethanol spraying speed in the ethanol spraying device was 1000 mL/min, and the ethanol concentration was 80%, a silk fibroin nonwoven fiber membrane was prepared, and the average diameter of the silk fibrin fiber was 5 μm.
实施例5Example 5
一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，包括以下步骤：(1)将蚕茧用碳酸钠水溶液脱胶，得到脱胶蚕丝，以7mol/L的氯化钙/乙醇水溶液为溶剂溶解脱胶蚕丝，在40℃水浴环境下溶解脱胶蚕丝12小时，得到丝素蛋白水溶液；(2)经离心、过滤、透析和浓缩，得到丝素蛋白浓度为12wt％的纺丝液；(3)以温度100℃，湿度为10wt％的高压空气喷射流为拉伸动力，所用高压空气喷射流的喷射压力为20MPa，并用纤维接收平板接收纺丝，纤维接收平板上方设有乙醇喷雾装置对纤维纺丝进行后处理，所述乙醇喷雾装置中的乙醇喷雾速度为1000mL/min，且乙醇浓度为80％，制得丝素蛋白无纺纤维膜，且丝素蛋白纤维平均直径为200nm。A solution spray preparation method of silk fibroin bio-tissue engineering scaffold with optimized mechanical properties includes the following steps: (1) Degumming silkworm cocoons with aqueous sodium carbonate solution to obtain degummed silk, using 7mol/L calcium chloride/ethanol aqueous solution as Solvent dissolves the degummed silk and dissolves the degummed silk for 12 hours in a 40°C water bath environment to obtain an aqueous solution of silk fibroin; (2) centrifugation, filtration, dialysis and concentration to obtain a spinning solution with a silk fibroin concentration of 12% by weight; (3 ) The high-pressure air jet with a temperature of 100°C and a humidity of 10wt% is used as the drawing power. The jet pressure of the high-pressure air jet used is 20MPa, and the fiber receiving plate is used for spinning. An ethanol spray device is provided above the fiber receiving plate to treat the fibers. After spinning, the post-treatment is performed. The ethanol spray speed in the ethanol spray device is 1000 mL/min, and the ethanol concentration is 80%. A silk fibroin nonwoven fiber membrane is prepared, and the average diameter of the silk fibrin fiber is 200 nm.
以上对本技术方案的较佳实施方式进行了具体说明，但本技术方案并不限于所述实施例，熟悉本领域的技术人员在不违背本技术方案精神的前提下还可作出种种的等同变型或替换，这些等同的变型或替换均包含在本申请权利要求所限定的范围内。The preferred embodiments of the technical solution have been described above in detail, but the technical solution is not limited to the embodiments. Those skilled in the art can make various equivalent modifications or without changing the spirit of the technical solution. Substitutions, these equivalent variations or substitutions are included within the scope defined by the claims of the present application.

Claims (10)

  1. 一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，其特征在于，所述制备方法中包括对纤维纺丝进行后处理步骤，其具体过程为：采用乙醇喷雾装置对纤维纺丝进行喷雾处理，其中所述乙醇喷雾装置中的乙醇喷雾速度为100～1000mL/min，制得所述生物蛋白组织工程支架。A method for dissolving spray preparation of silk fibroin biotissue engineering scaffold with optimized mechanical properties is characterized in that the preparation method includes a post-processing step for fiber spinning, and the specific process is: using an ethanol spray device to spin the fiber The silk is sprayed, wherein the ethanol spraying speed in the ethanol spraying device is 100-1000 mL/min, and the biological protein tissue engineering scaffold is prepared.
  2. 根据权利要求1所述的一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，其特征在于，所述乙醇喷雾装置中乙醇的浓度为50～100％。The method for dissolving spray preparation of silk fibroin biotissue engineering scaffold with optimized mechanical properties according to claim 1, characterized in that the concentration of ethanol in the ethanol spraying device is 50-100%.
  3. 根据权利要求1中所述的一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，其特征在于，在进行纤维纺丝后处理之前还包括以下步骤：The method for dissolving spray preparation of silk fibroin biotissue engineering scaffold with optimized mechanical properties according to claim 1, characterized in that the method further comprises the following steps before fiber spinning post-treatment:
    (1)用溶剂将脱胶蚕丝溶解透析后，获得浓度为8～45％的丝素蛋白溶液；(1) After dissolving and dialysis the degummed silk with a solvent, a silk fibroin solution with a concentration of 8 to 45% is obtained;
    (2)将步骤(1)制得的丝素蛋白溶液作为纺丝液，在温度为37～120℃的高压空气喷射流为拉伸动力，进行溶喷纺丝，并用纤维接收器接收纤维纺丝。(2) Using the silk fibroin solution prepared in step (1) as a spinning solution, a high-pressure air jet at a temperature of 37 to 120° C. is used as the drawing power to perform melt-spinning spinning, and receive fiber spinning with a fiber receiver wire.
  4. 根据权利要求3所述的一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，其特征在于，所述溶解脱胶蚕丝的溶剂为LiBr水溶液或乙醇/CaCl水溶液。The method for preparing a silk fibroin biotissue engineering scaffold with optimized mechanical properties according to claim 3, wherein the solvent for dissolving the degummed silk is an aqueous LiBr solution or an aqueous ethanol/CaCl solution.
  5. 根据权利要求3所述的一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，其特征在于，还包括以下步骤：对步骤(1)制得的丝素蛋白溶液加入pH值调节剂进行pH值调节，其添加的pH值调节剂为金属离子或无机纳米粉体。The method for preparing a silk fibroin biotissue engineering scaffold with optimized mechanical properties according to claim 3, further comprising the following steps: adding a pH value to the silk fibroin solution prepared in step (1) The regulator adjusts the pH, and the added pH regulator is a metal ion or inorganic nano powder.
  6. 根据权利要求5所述的一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，其特征在于，所述金属离子为钙离子、银离子中的一种。The method for preparing a silk fibroin biotissue engineering scaffold with optimized mechanical properties according to claim 5, wherein the metal ion is one of calcium ion and silver ion.
  7. 根据权利要求5所述的一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，其特征在于，所述无机纳米粉体为羟基磷灰石、磷酸三钙中的一种。The method for preparing a silk fibroin biotissue engineering scaffold with optimized mechanical properties according to claim 5, wherein the inorganic nano-powder is one of hydroxyapatite and tricalcium phosphate.
  8. 根据权利要求3所述的一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，其特征在于，所述纤维接收器采用的是纤维接收平板时，获得丝素蛋白无纺纤维膜。The method for dissolving spray preparation of silk fibroin biological tissue engineering scaffold with optimized mechanical properties according to claim 3, characterized in that when the fiber receiver uses a fiber receiving plate, the silk fibroin nonwoven fiber is obtained membrane.
  9. 根据权利要求3所述的一种优化力学性能的丝素蛋白生物组织工程支架的溶喷制备方法，其特征在于，所述纤维接收器采用的是纤维接收滚筒时，获得单向拉伸且单方向有序排列的丝素蛋白连续长纤维膜。The method for dissolving spray preparation of silk fibroin biotissue engineering scaffold with optimized mechanical properties according to claim 3, characterized in that, when the fiber receiver uses a fiber receiving drum, unidirectional stretching and single The continuous fibrillar membrane of silk fibroin arranged in order.
  10. 根据权利要求3所述的一种生物组织工程支架的溶喷制备方法，其特征在于，步骤(2)中所述的高压空气喷射流为经过干燥的压缩空气，其相对湿度为10％～40％，所用高压空气喷射流的喷射压力为10MPa～30MPa。The solution spray preparation method for biological tissue engineering scaffolds according to claim 3, characterized in that the high-pressure air jet in step (2) is dried compressed air, and its relative humidity is 10% to 40 %, the injection pressure of the high-pressure air jet used is 10 MPa to 30 MPa.
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CN102397582A (en) * 2011-11-04 2012-04-04 无锡中科光远生物材料有限公司 Preparation method for silk fibroin nanofiber intravascular stent
WO2014125505A1 (en) * 2013-02-14 2014-08-21 Council Of Scientific & Industrial Research Silk based porous scaffold and a process for the preparation thereof
CN106046135A (en) * 2016-08-08 2016-10-26 南通大学 Silk fibroins with different degradation rates and use thereof
CN109529117A (en) * 2018-12-28 2019-03-29 佛山科学技术学院 A kind of molten spray Preparation Method of activity fibroin albumen bioengineered tissue bracket
CN109610020A (en) * 2018-12-28 2019-04-12 佛山科学技术学院 A kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket optimizing mechanical property

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