CN102477592A

CN102477592A - Biodegradable tissue-engineering fiber

Info

Publication number: CN102477592A
Application number: CN201010553444XA
Authority: CN
Inventors: 杜冲
Original assignee: Dalian Chuangda Technology Trade Market Co Ltd
Current assignee: Dalian Chuangda Technology Trade Market Co Ltd
Priority date: 2010-11-22
Filing date: 2010-11-22
Publication date: 2012-05-30

Abstract

The invention relates to the field of biomedical engineering materials and in particular relates to a biodegradable tissue-engineering fiber. The biodegradable tissue-engineering fiber is made from natural silk as principal raw material. The natural silk is degummed, dissolved and purified to form a silk fibroin solution. And the silk fibroin solution is processed by wet spinning method which controls that the degree of crystallization of silk fibroin is less than 40%, to produce the biodegradable fiber used for tissue-engineering scaffolds. The material is innoxious and harmless, has good biocompatibility, is hardly soluble in water, has strength, elongation, elasticity and other physical properties, and can be used as the material of artificial skin, artificial tendons, artificial cartilages, artificial dura maters and other tissue-engineering scaffolds or used as the surgical repair material.

Description

A kind of biodegradable organizational project fiber

Technical field

The invention belongs to the bio-medical engineering material field, concrete relate to a kind of biodegradable organizational project fiber.

Background technology

Silk is made up of fibroin and the 25 % silk gum of about 75 %; It is quite pure natural protein fiber; To human non-toxic property, have no stimulation; The amino acid of fibroin is formed with human collagen albumen has certain similitude, has excellent biological compatibility, is the comparatively ideal raw material of preparation bio-medical goods.But proof after deliberation, because natural silk degree of crystallinity is higher, adhesion such as the big intramolecule hydrogen bond of silk is stronger in the crystal region; Space structure is tight; Therefore, general silk product is difficult to by biodegradation, and this just makes the application of natural fibroin at biomedical sector; Especially be used as the application of tissue engineering material, received great restriction.

Before the present invention makes; The technology of more employing is as the used in tissue engineering support with artificial materials such as PLAs in the world; Pile up owing to be prone to produce local acidic materials in these material degradation in vivo processes, be unfavorable for adhering to, divide, breeding of cell, and cost an arm and a leg.At home, publication number is in the patent of invention " a kind of Wound surface protection film and preparation method thereof " of CN 1059129C, and disclosing a kind of is raw material with silk, through come unstuck, after the operation such as dissolving, the method for drying and forming-film; Publication number is in the patent of invention " a kind of porous fibroin membrane and preparation method thereof " of CN1260363A; A kind of method for preparing porous fibroin membrane with freeze-drying is disclosed; The fibroin material that above technology provided all is membranaceous; Only can be used as the surface of a wound and cover and artificial skin, be difficult to constitute used in tissue engineering 3 D complex support.At present, utilize the biodegradable tissue engineering bracket material of natural silk fibroin fiber production, do not appear in the newspapers as yet.

Summary of the invention

The object of the present invention is to provide a kind of and human body to have the favorable tissue compatibility, and biodegradable fibre for tissue engineering scaffold and preparation method thereof.

For reaching the foregoing invention purpose; The technical scheme that the present invention adopts is: prepare a kind of fibre for tissue engineering scaffold; It is that main raw material processes with domestic silkworm silk or its goods, and described fibre for tissue engineering scaffold is a long filament shape structure, and wherein natural silk content is 50 %-100 %; Degree of crystallinity is 1 %-40 %, and fiber number is l-40dtex, and tensile break strength is greater than 0.5cN/dtex, and elongation at break is 1-30 %.

In order to reach each item technical performance of above-mentioned fibre for tissue engineering scaffold, the preparation method that the present invention adopts is come unstuck silk earlier, obtains pure natural silk, carries out the processing of following steps again:

A. with pure natural silk dissolving, make the spinning solution of silk concentration after the purification at 10 %-40 %;

B. with concentration is that the organic solvent of 50-99 % or high-hydroscopicity salt that concentration is 20-60 % are prepared into solidification liquid, with spinning solution spinning in coagulating bath, obtains the spun filament cellulose fiber after the cleaning;

C. with concentration is that the organic solvent of 30-90 % or high-hydroscopicity salt that concentration is 10-50 % are prepared into drawing-off liquid; The spun filament cellulose fiber, is carried out once in bathing or drawing-off once in drawing-off; Its draft speed is 2-120 meters/minute, and the drawing-off multiplying power is 0.1-20 times, and drawing temperature is 50-120 ℃; Degree of crystallinity is 0 %-40 %, uses the regenerated silk fiber thereby obtain the biodegradable tissue engineering bracket.

In the technique scheme, described pure natural silk dissolution process, its solvent is the phosphoric acid of 60-85 %, and solution temperature is 20-40 ℃, and dissolution time is 0. 5-72 hours; Pure natural silk dissolution process also can be: the ternary solution that solvent is mixed with by weight the ratio for Australia file 35-50 %, ethanol 45-55 %, water 5-10 %, and solution temperature is 60-90 ℃, dissolution time is 3-5 hours.

Organic solvent in described solidification liquid, the drawing-off liquid is a kind of in methyl alcohol, the ethanol; The high-hydroscopicity salt is that ammonium acetate, acetic acid are received, a kind of in the ammonium sulfate, sodium sulphate.

Described spinning process condition is to be spinning in 20-50 ℃ the coagulating bath with spinning solution in temperature, and nitrogen pressure is 0.1MPa – 0.5MPa, and the spinning plate aperture is 0.2 – 0.8mm, and spinning speed is 1-28 meter/minute.

The present invention is owing to be main raw material with silk; Therefore; The regenerated silk fibroin fiber that makes has natural fibroin protein and the good advantage of human-body biological compatibility: simultaneously; Owing in aggregated structure parameters such as the degree of crystallinity of in spinning process, controlling the regenerated silk fibroin fiber, the degrees of orientation, make regenerated silk fibroin fiber biological degradable, become tissue engineering bracket with desirable fibrous material.

Description of drawings

Accompanying drawing 1 is the sketch map of embodiment of the invention spinning process flow process and apparatus structure.

The specific embodiment

Below in conjunction with accompanying drawing and embodiment, the present invention is further illustrated.

Embodiment one:

With 0.6 kilogram of leftover bits and pieces raw silk (continuous Silk Mill silk cocoon is sewed the byproduct in the silk) aqueous sodium carbonate that to put into 10 liters of concentration be 0.05 %, boiled 0.5 hour earlier, the peripheral silk gum of most silk rope is taken off in reprocessing three times, obtains pure natural silk.

Treat the pure natural silk after nature dries, use 1.5 liters of phosphoric acid that concentration is 80 %, dissolving is 2 hours under 30 ℃ temperature conditions, processes spinning solution through filtration purification, ultrasonic wave froth breaking after 1 hour;

Referring to accompanying drawing 1; Under the effect of 0.4MPa nitrogen, use the spinneret orifice of an aperture, under 25 ℃ temperature conditions as 0.5mm; Speed ejection fibroin albumen spinning solution with per minute 2 grams; Getting into concentration is that the temperature of coagulating bath is 30 ℃ in the 25 % ammonium sulfate solidification liquids, and spinning is frozen into nascent fibroin fiber.To immerse first drawing-off through the nascent fibroin fiber after the washing and bathe, degree of draft is 1.0 times; Immerse second drawing-off again and bathe, degree of draft is 2.0 times.The drawing-off liquid of first and second time drawing-off is the methyl alcohol of concentration 60 %, and drawing temperature is 80 ℃.

At last, batch with the speed of 90 meters of per minutes, process tissue engineering bracket and use the regenerated silk fibroin fiber, its fibroin content is 100 %, and through the X ray diffraction determination, its degree of crystallinity is 3 %.Fibre length is more than 1 meter, fiber number ldtex, and tensile break strength 0.5CN/dtex, elongation at break are 2 %.

Embodiment two:

With 1 kilogram of cocoon layer neutral soap solution that to put into 20 liters of concentration be 0.5 %, boiled 2 hours, take off the peripheral silk gum of most fibroin, after fully washing, hot water obtains pure natural silk.

Dried pure natural silk; Using 1.5 liter weights ratio is 44: 50: 6 lithium bromide, ethanol, the ternary solution of water, under 75 ℃ temperature conditions, stirs 4 hours, is dissolved into the fibroin mixed solution; Purify through filtering, the ultrasonic wave froth breaking was processed spinning solution after 1.5 hours.

Shown in accompanying drawing 1; Under the effect of 0.3MPa nitrogen; Use the aperture as 2 of the spinneret orifices of 0.5mm, under 30 ℃ of temperature conditions, with the speed ejection fibroin albumen spinning solution of per minute 3 grams; Getting into 20 ℃ of methanol concentrations is in the solidification liquid of 60 %, is frozen into nascent fibroin fiber.

Immerse first drawing-off bath through washing back, drawing-off liquid be the acetic acid of skilful % by solution, temperature is 70 ℃, degree of draft is more than 1.5 times; Immerse second drawing-off again and bathe, drawing temperature is 80 ℃, and drawing-off liquid is the ammonium acetate solution of 10 %, and degree of draft is more than 2.0 times.

Batch with the speed of 90 meters of per minutes at last, process fibroin content and be 95 %, degree of crystallinity and be the tissue engineering bracket of 6 % and use the regenerated silk fibroin fiber.

Tissue engineering bracket provided by the invention is used fibroin fiber, has kept the protein composition of natural fibroin, has excellent biological compatibility, and with low cost.Particularly its biodegradability reaches the plasticity of being processed into the used in tissue engineering three-dimensional rack through the road, back; Be expected as replacing expensive biodegradable tissue engineering materials such as import PLA; As artificial skin, tissue engineering rack material or surgical repair materials such as flesh thorax, blood vessel, cartilage, ligament, esophagus, endocranium.

Claims

1. biodegradable organizational project fiber, it is characterized in that: it is that main raw material is processed into long filament shape structure with domestic silkworm silk or its goods, and wherein natural silk content is 50 %-, 100 %; Degree of crystallinity is 1 %-40 %, and fiber number is l-40dtex, and tensile break strength is greater than 0.5cN/dtex, and elongation at break is l-30 %.

2. a kind of biodegradable organizational project fiber according to claim 1 is characterized in that the preparation method is that silk is come unstuck in elder generation, obtains pure natural silk, carries out the processing of following steps again:

(1) with pure natural silk dissolving, solvent is the phosphoric acid of 60-85 %, and dissolving is 0.5-72 hour under 20-40 ℃ temperature conditions, makes the spinning solution of silk concentration at 10 %-40 % after the purification;

(2) using concentration is that the organic solvent of 50-99 % or high-hydroscopicity salt that concentration is 20-60 % are prepared into solidification liquid, with spinning solution spinning in coagulating bath, obtains the spun filament cellulose fiber after the cleaning; Organic solvent in described solidification liquid, the drawing-off liquid is methyl alcohol or ethanol; The high-hydroscopicity salt is that ammonium acetate, acetic acid are received, a kind of in ammonium sulfate or the sodium sulphate;

(3) using concentration is that the organic solvent of 30-90 % or high-hydroscopicity salt that concentration is 10-50 % are prepared into drawing-off liquid; The spun filament cellulose fiber, is carried out once in bathing or drawing-off once in drawing-off; Its draft speed is 2-120 meters/minute, and the drawing-off multiplying power is 0.1-20 times, and drawing temperature is 120 ℃ of 50 –; Degree of crystallinity is 0 %-40 %, uses the regenerated silk fiber thereby obtain the biodegradable tissue engineering bracket.