CN109610020A - A kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket optimizing mechanical property - Google Patents

A kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket optimizing mechanical property Download PDF

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Publication number
CN109610020A
CN109610020A CN201811632027.7A CN201811632027A CN109610020A CN 109610020 A CN109610020 A CN 109610020A CN 201811632027 A CN201811632027 A CN 201811632027A CN 109610020 A CN109610020 A CN 109610020A
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CN
China
Prior art keywords
fibroin albumen
mechanical property
bioengineered tissue
bracket
ethyl alcohol
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Pending
Application number
CN201811632027.7A
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Chinese (zh)
Inventor
罗杰
张耀鹏
吕悦光
谢啸锋
林嘉栋
张敏
熊帮云
余明光
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Foshan University
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Foshan University
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Priority to CN201811632027.7A priority Critical patent/CN109610020A/en
Publication of CN109610020A publication Critical patent/CN109610020A/en
Priority to PCT/CN2019/113149 priority patent/WO2020134443A1/en
Pending legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D13/00Complete machines for producing artificial threads
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01CCHEMICAL OR BIOLOGICAL TREATMENT OF NATURAL FILAMENTARY OR FIBROUS MATERIAL TO OBTAIN FILAMENTS OR FIBRES FOR SPINNING; CARBONISING RAGS TO RECOVER ANIMAL FIBRES
    • D01C3/00Treatment of animal material, e.g. chemical scouring of wool
    • D01C3/02De-gumming silk
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00Treatment of filament-forming or like material
    • D01D1/02Preparation of spinning solutions
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D7/00Collecting the newly-spun products
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06BTREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B1/00Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
    • D06B1/02Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by spraying or projecting
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating 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
    • D06M13/144Alcohols; Metal alcoholates
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/10Animal fibres
    • D06M2101/12Keratin fibres or silk
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2211/00Protein-based fibres, e.g. animal fibres
    • D10B2211/20Protein-derived artificial fibres
    • D10B2211/22Fibroin

Abstract

The technical program discloses a kind of molten spray Preparation Method of fibroin albumen bioengineered tissue bracket for optimizing mechanical property, it include that post-processing step is carried out to fibre spinning in the preparation method, its detailed process are as follows: spraying treatment is carried out to fibre spinning using ethyl alcohol spraying device, wherein the ethyl alcohol spray velocity in the ethyl alcohol spraying device is 100~1000mL/min, and the bioprotein tissue engineering bracket is made.The technical program, which handles fibroin albumen spinning fibre, can promote the random conformation in fibroin albumen to β-pleated sheet conformation transition, to obtain the uniform fibroin albumen bioengineered tissue bracket of Macro Texture;Fibroin albumen bioengineered tissue bracket made from the technical program can be used for the tissue engineering brackets such as blood vessel, urethra, cartilage, bone, can also be used for blood filtration after surface treated.

Description

A kind of molten spray for the fibroin albumen bioengineered tissue bracket optimizing mechanical property is standby Method
Technical field
The technical program belongs to biomedical material technology, in particular to a kind of fibroin albumen for optimizing mechanical property The molten spray Preparation Method of bioengineered tissue bracket.
Background technique
Silk is made of fibroin albumen and silk gum two parts, and silk gum packet accounts for about weight in the outside of fibroin albumen 25%, there are also 5% or so impurity in silk, fibroin albumen is main component part in silk, accounts for about the 70% of weight.Silk Fibroin forms the microfibre that diameter is about 10nm based on antiparallel folded conformation (β-pleated sheet), and countless microfibres are close It cuts in conjunction with the fine fibre that diameter is about 1Lm is formed, it is about 10Lm~18Lm's that about 100 fine fibres, which are arranged to make up diameter, Single fiber, i.e. fibroin fiber.
Structure and function of the fibroin albumen bioengineered tissue bracket because that can imitate extracellular matrix to a certain extent be Cell provides the microenvironment of ideal growth, proliferation and differentiation, in recent years, be widely used in include cartilage, bone, The every field of the Tissue Engineering Studies such as blood vessel, skin.But many of structure nothing in the fibroin fiber film of existing preparation It advises conformation to exist, the presence of random conformation can seriously affect the mechanical property of fibroin fiber film.
Summary of the invention
The technical program provides a kind of standby side of molten spray of fibroin albumen bioengineered tissue bracket for optimizing mechanical property Method, the animal spinning process of preparation method energy natural imitation circle, and the fibroin albumen for leading to the preparation method preparation is raw The mechanical property of object tissue engineering bracket is good.
To achieve the above object, following technological means that the technical program uses.
A kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket optimizing mechanical property, the preparation method In include to fibre spinning carry out post-processing step, detailed process are as follows: fibre spinning is sprayed using ethyl alcohol spraying device The fibroin albumen is made wherein the ethyl alcohol spray velocity in the ethyl alcohol spraying device is 100~1000mL/min in mist processing Bioengineered tissue bracket.
Further, the concentration of ethyl alcohol is 50~100% in the ethyl alcohol spraying device
A kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket optimizing mechanical property, is carrying out fiber spinning It is further comprising the steps of before silk post-processing:
(1) silk fibroin protein solution that concentration is 8~45% is obtained by after boiled silk dissolution dialysis with solvent;
(2) using silk fibroin protein solution made from step (1) as spinning solution, the pressure-air for being 37~120 DEG C in temperature Injection stream is pulling motion, carries out molten spray spinning, and receive fibre spinning with fiber receiver;The silk prepared using above-mentioned steps The diameter of fibroin fiber in fibroin bioengineered tissue bracket is micron and sub-micron rank, it might even be possible to reach and receive Meter level is other, can farthest imitate the structure of human body cell epimatrix;In preparation method described in the technical program not Voltage is needed, and the preparation method does not use organic solvent, operability and highly-safe and environmentally friendly, energy Large-scale application in the industrial production;And above-mentioned preparation method can be by adjusting machined parameters, so that the fibroin egg of preparation Porosity in white bioengineered tissue bracket meets the needs of different cells growth;The fibroin prepared using the preparation method Protein biology tissue engineering bracket has high porosity and good hole link, and also has big specific surface area, Good microenvironment can be provided for the growth of cell, be conducive to the adherency, differentiation and proliferation of cell.
Further, the solvent of the dissolution boiled silk is LiBr aqueous solution or ethyl alcohol/CaCl aqueous solution.
Further, a kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket optimizing mechanical property also wraps It includes following steps: pH adjusting agent being added to silk fibroin protein solution made from step (1) and carries out pH value adjusting, the pH value of addition Regulator is metal ion or inorganic nanometer powder.
Further, the metal ion is one of calcium ion, silver ion.
Further, the inorganic nanometer powder is one of hydroxyapatite, tricalcium phosphate.
Further, when the fiber receiver receives plate using fiber, fibroin albumen non-woven fibre film is obtained.
Further, it when the fiber receiver receives roller using fiber, obtains simple tension and one direction has The fibroin albumen continuous fiber film of sequence arrangement.
Further, pressure-air injection stream described in step (2) is by dry compressed air, relative humidity It is 10%~40%, the injection pressure of pressure-air injection stream used is 10MPa~30MPa.
The technical program has the beneficial effect that there are three types of conformation, random conformations, α spiral, β-pleated sheet, at this in fibroin albumen β-pleated sheet conformation is a kind of structure that peptide chain quite stretches in three kinds of conformations, and wherein peptide chain arranges layer by layer, by adjacent peptide chains The hydrogen bond that > C=0 and > N-H is formed is come the structure for maintaining its stable, and β-pleated sheet conformation is a kind of rock-steady structure, and fibroin albumen Fibroin albumen conformation in tunica fibrosa is mainly based on β-pleated sheet, and β-pleated sheet conformation is more in fibroin fiber film, then silk The mechanical property of fibroin tunica fibrosa is then better;
The technical program carries out spraying treatment to fibre spinning using ethyl alcohol spraying device, wherein the ethyl alcohol spraying device In ethyl alcohol spray velocity be 100~1000mL/min, fibroin can be promoted in this way by handling fibroin albumen spinning fibre Random conformation in albumen is to β-pleated sheet conformation transition, to obtain the uniform fibroin fiber film of Macro Texture;This technology side Fibroin bioengineered tissue bracket made from case can be used for the tissue engineering brackets such as blood vessel, urethra, cartilage, bone, can also be through surface Blood filtration is used for after processing.
Specific embodiment
Technical solution of the present invention is further illustrated combined with specific embodiments below.It should be understood that these embodiments are only used for Illustrate the present invention rather than limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, this Field technical staff can make various changes or modifications the present invention, and such equivalent forms equally fall within right appended by the application and want Seek book limited range.
Embodiment 1
A kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket optimizing mechanical property, including following step It is rapid: (1) by silk cocoon aqueous sodium carbonate degumming, to obtain boiled silk, dissolved by solvent of the lithium bromide water solution of 9mol/L Boiled silk, and dissolved boiled silk 2 hours under 40 DEG C of water baths, obtain silk fibroin water solution;(2) through centrifugation, mistake After filter, dialysis and concentration, the fibroin albumen spinning solution that concentration is 12wt% is obtained;(3) with 120 DEG C of temperature, relative humidity is 10% pressure-air injection stream is pulling motion, and the injection pressure of pressure-air injection stream used is 30MPa, and is connect with fiber It is closed flat plate and receives spinning, fiber is received and post-processed equipped with ethyl alcohol spraying device to fibre spinning above plate, the ethyl alcohol Ethyl alcohol spray velocity in spraying device is 100mL/min, and concentration of alcohol is 80%, and fibroin albumen non-woven fibre film is made, And fibroin fiber average diameter is 6 μm.
Embodiment 2
A kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket optimizing mechanical property, including following step It is rapid: (1) by silk cocoon aqueous sodium carbonate degumming, to obtain boiled silk, dissolved by solvent of the lithium bromide water solution of 9mol/L Boiled silk dissolves boiled silk 2 hours under 40 DEG C of water baths, obtains silk fibroin water solution;(2) through centrifugation, filtering, After dialysis and concentration, the fibroin albumen spinning solution that concentration is 12wt% is obtained;(3) with 120 DEG C of temperature, relative humidity is 10% Pressure-air injection stream is pulling motion, and the injection pressure of pressure-air injection stream used is 20MPa, and receives plate with fiber Spinning is received, fiber is received and post-processed equipped with ethyl alcohol spraying device to fibre spinning above plate, and the ethyl alcohol fills by spraying Ethyl alcohol spray velocity in setting is 100mL/min, and concentration of alcohol is 50%, and fibroin albumen non-woven fibre film, and fibroin is made Azelon average diameter is 6 μm.
Embodiment 3
A kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket optimizing mechanical property, including following step It is rapid: (1) by silk cocoon aqueous sodium carbonate degumming, to obtain boiled silk, dissolved by solvent of the lithium bromide water solution of 9mol/L Boiled silk dissolves boiled silk 12 hours under 40 DEG C of water baths, obtains silk fibroin water solution;(2) through centrifugation, mistake After filtering, dialysing and be concentrated into 20wt%, adding CaCl calcium ion concentration into silk fibroin water solution is 0.3mol/L, is continued dense Being reduced to fibroin albumen concentration is 45wt%;(3) with 37 DEG C of temperature, the pressure-air injection stream that humidity is 50wt% is to stretch to move Power, the injection pressure of pressure-air injection stream used are 30MPa, and receive plate with fiber and receive spinning, and fiber receives plate Top is equipped with ethyl alcohol spraying device and post-processes to fibre spinning, and the ethyl alcohol spray velocity in the ethyl alcohol spraying device is 100mL/min, and concentration of alcohol is 100%, fibroin albumen non-woven fibre film is made, and fibroin fiber average diameter is 3 μ m。
Embodiment 4
A kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket optimizing mechanical property, including following step It is rapid: (1) by silk cocoon aqueous sodium carbonate degumming, boiled silk to be obtained, using calcium chloride/ethanol water of 7mol/L as solvent Boiled silk is dissolved, is dissolved boiled silk 6 hours under 40 DEG C of water baths, obtains silk fibroin water solution;(2) be centrifuged, Filtering, dialysis and concentration obtain the spinning solution that fibroin albumen concentration is 30wt%;(3) with 100 DEG C of temperature, humidity 25wt% Pressure-air injection stream be pulling motion, the injection pressure of pressure-air injection stream used is 25MPa, and is received with fiber flat Plate receives spinning, and fiber receives plate and post-processes equipped with ethyl alcohol spraying device to fibre spinning, the ethyl alcohol spraying device In ethyl alcohol spray velocity be 1000mL/min, and concentration of alcohol is 80%, and fibroin albumen non-woven fibre film, and fibroin egg is made White fiber average diameter is 5 μm.
Embodiment 5
A kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket optimizing mechanical property, including following step It is rapid: (1) by silk cocoon aqueous sodium carbonate degumming, boiled silk to be obtained, using calcium chloride/ethanol water of 7mol/L as solvent Boiled silk is dissolved, is dissolved boiled silk 12 hours under 40 DEG C of water baths, obtains silk fibroin water solution;(2) be centrifuged, Filtering, dialysis and concentration obtain the spinning solution that fibroin albumen concentration is 12wt%;(3) with 100 DEG C of temperature, humidity 10wt% Pressure-air injection stream be pulling motion, the injection pressure of pressure-air injection stream used is 20MPa, and is received with fiber flat Plate receives spinning, and fiber is received and post-processed equipped with ethyl alcohol spraying device to fibre spinning above plate, and the ethyl alcohol is spraying Ethyl alcohol spray velocity in device is 1000mL/min, and concentration of alcohol is 80%, and fibroin albumen non-woven fibre film, and silk is made Fibroin average fibre diameter is 200nm.
The better embodiment of the technical program is illustrated above, but the technical program be not limited to it is described Embodiment, those skilled in the art can also make various equivalent changes under the premise of without prejudice to the technical program spirit Type or replacement, these equivalent variation or replacement are all included in the scope defined by the claims of the present application.

Claims (10)

1. a kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket for optimizing mechanical property, which is characterized in that institute State in preparation method includes carrying out post-processing step, detailed process to fibre spinning are as follows: using ethyl alcohol spraying device to fiber Spinning carries out spraying treatment, wherein the ethyl alcohol spray velocity in the ethyl alcohol spraying device is 100~1000mL/min, institute is made State bioprotein tissue engineering bracket.
2. a kind of molten spray of fibroin albumen bioengineered tissue bracket for optimizing mechanical property according to claim 1 is standby Method, which is characterized in that the concentration of ethyl alcohol is 50~100% in the ethyl alcohol spraying device.
3. a kind of molten spray of fibroin albumen bioengineered tissue bracket for optimizing mechanical property according to claim 1 Preparation Method, which is characterized in that further comprising the steps of before carrying out fibre spinning post-processing:
(1) silk fibroin protein solution that concentration is 8~45% is obtained by after boiled silk dissolution dialysis with solvent;
(2) it using silk fibroin protein solution made from step (1) as spinning solution, is sprayed in the pressure-air that temperature is 37~120 DEG C Stream is pulling motion, carries out molten spray spinning, and receive fibre spinning with fiber receiver.
4. a kind of molten spray of fibroin albumen bioengineered tissue bracket for optimizing mechanical property according to claim 3 is standby Method, which is characterized in that the solvent of the dissolution boiled silk is LiBr aqueous solution or ethyl alcohol/CaCl aqueous solution.
5. a kind of molten spray of fibroin albumen bioengineered tissue bracket for optimizing mechanical property according to claim 3 is standby Method, which is characterized in that further comprising the steps of: pH adjusting agent is added to silk fibroin protein solution made from step (1) and is carried out PH value is adjusted, and the pH adjusting agent of addition is metal ion or inorganic nanometer powder.
6. a kind of molten spray of fibroin albumen bioengineered tissue bracket for optimizing mechanical property according to claim 5 is standby Method, which is characterized in that the metal ion is one of calcium ion, silver ion.
7. a kind of molten spray of fibroin albumen bioengineered tissue bracket for optimizing mechanical property according to claim 5 is standby Method, which is characterized in that the inorganic nanometer powder is one of hydroxyapatite, tricalcium phosphate.
8. a kind of molten spray of fibroin albumen bioengineered tissue bracket for optimizing mechanical property according to claim 3 is standby Method, which is characterized in that when the fiber receiver receives plate using fiber, obtain fibroin albumen non-woven fibre film.
9. a kind of molten spray of fibroin albumen bioengineered tissue bracket for optimizing mechanical property according to claim 3 is standby Method, which is characterized in that when the fiber receiver receives roller using fiber, obtain simple tension and one direction is orderly The fibroin albumen continuous fiber film of arrangement.
10. a kind of molten spray of fibroin albumen bioengineered tissue bracket for optimizing mechanical property according to claim 3 Preparation Method, which is characterized in that pressure-air injection stream described in step (2) is to pass through dry compressed air, relatively wet Degree is 10%~40%, and the injection pressure of pressure-air injection stream used is 10MPa~30MPa.
CN201811632027.7A 2018-12-28 2018-12-28 A kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket optimizing mechanical property Pending CN109610020A (en)

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CN201811632027.7A CN109610020A (en) 2018-12-28 2018-12-28 A kind of molten spray Preparation Method for the fibroin albumen bioengineered tissue bracket optimizing mechanical property
PCT/CN2019/113149 WO2020134443A1 (en) 2018-12-28 2019-10-25 Solution-spraying preparation method for silk fibroin biological tissue engineering stent with optimized mechanical properties

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CN114705734A (en) * 2022-04-30 2022-07-05 陕西云康智汇科技有限公司 Humidity sensor and manufacturing method thereof

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CN114705734A (en) * 2022-04-30 2022-07-05 陕西云康智汇科技有限公司 Humidity sensor and manufacturing method thereof

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