CN1904159A - Anti bacteria natural silk composite nano-fiber material and its preparation method - Google Patents
Anti bacteria natural silk composite nano-fiber material and its preparation method Download PDFInfo
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- CN1904159A CN1904159A CN 200610041016 CN200610041016A CN1904159A CN 1904159 A CN1904159 A CN 1904159A CN 200610041016 CN200610041016 CN 200610041016 CN 200610041016 A CN200610041016 A CN 200610041016A CN 1904159 A CN1904159 A CN 1904159A
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Abstract
This invention discloses a compound antibacterial silk nanometer fibrous material, accounting for weight its component proportion are: Sericin protein 58-90%; chitosan or chitin 0-40%, antibacterial agent 0-5%, electric conduction 1-4%,crossing linking 1-4%. Its process is: dissolve the pure sericin protein, antibiotics separately in polar solvent, join electric conduction medicinal preparation and crosslinking agent, using the static electricity spinning technique, making the average aperture for 0.5-5.0 micron, factor of porosity 60-90%, the mean diameter is 40-100nm and the material is nanometer textile fiber adhesive-bonded membrane. This invention has good organization compatibility with human body, Antibiotics and sericin insoluble is in homogeneous solvent, massive holes among the nanometer textile fiber adhesive-bonded membrane, which has outstanding aqueous percolation permeability, antibacterial agent distributes evenly in the nanometer textile fiber, and the medicine release effect is perfect, so it can be a kind of ideal resist bacteria injured medical material.
Description
Technical field
The present invention relates to a kind of biomaterial for medical purpose and preparation method thereof, nanofiber anti-biotic material that particularly a kind of fibroin albumen and antiseptic etc. are composited and preparation method thereof belongs to technical field of polymer materials.
Background technology
Before the present invention makes, utilizing natural or synthetic high polymer is main raw material, make the existing report in nanofiber nonwoven film aspect through electrostatic spinning, for example: raw material is polyacrylonitrile, polyamide, polyvinyl alcohol, cellulose and derivative thereof etc., but it is poor with human compatibility that above-mentioned material has, the fiber that is spun into that has is thicker, and average diameter reaches hundreds of to several thousand nanometers, is not suitable as medical material.
Fibroin is a kind of quite pure native protein, form by 18 seed amino acids, with the collagen of human body bigger similitude is arranged, it is nontoxic, non-stimulated, have excellent biological compatibility, so fibroin is the desirable basic material of preparation biomaterial for medical purpose.Also utilize fibroin to make nanofiber nonwoven film through electrostatic spinning, but it does not have antibiotic performance, the scope of application has been subjected to certain restriction.
Publication number is the Chinese invention patent " a kind of Coremia-resisting wound protecting film and preparation method thereof " of CN1348820A, disclosing with silk is main film forming raw material, add antiseptic and additive, the Coremia-resisting wound protecting film that adopts the hydrostomia method to make through the processing of layering coating heated-air drying, this is the dense film that forms by heated-air drying, though have good antibacterial action, can influence the pliability of fibroin Wound surface protection film because of heated-air drying; Because of film densification, nothing perforation hole influence its water-permeable and air permeable, be unfavorable for the healing of the surface of a wound again, effect has been subjected to certain influence.
Summary of the invention
Purpose of the present invention overcomes the deficiency that prior art exists, and provides a kind of both good with human compatibility, has medical antibacterial surface of a wound cladding material of excellent antibiotic property, water-permeable and air permeable and preparation method thereof again.
A kind of anti bacteria natural silk composite nano-fiber material of the present invention is characterized in that: it is a nanofiber nonwoven membrane structure, and average pore size is 0.5～5.0 μ m, and porosity is 60～90%, and the average diameter of fiber is 40～100nm; Its component and each component ratio by weight are: fibroin albumen 58～90%, shitosan or chitin 0～40%, antiseptic 0～5%, conductive agent 1～4%, crosslinking agent 1～4%; Described antiseptic is quaternary ammonium salt, guanidine class, poly-guanidine class and contains Ag
+, Zn
2+In the salt of metal ion one or more; Described conductive agent is one or more in borate, acetate, the silicate; Described crosslinking agent is one or more in tannic acid, citric acid, pentaerythrite, the boric acid.
The method for preparing anti bacteria natural silk composite nano-fiber material, earlier with silk through come unstuck, dissolving, dialysis, purifying, drying, obtain pure fibroin albumen, it is characterized in that carrying out again the processing of following steps:
A, the fibroin albumen with pure, shitosan or chitin or antiseptic are dissolved in the polar solvent respectively, make homogeneous solution after they fully being mixed, described polar solvent is one or more in glacial acetic acid, dimethyl formamide, anhydrous formic acid, the trifluoroethanol again;
B, in above-mentioned solution, add conductive agent, crosslinking agent, the preparation quality mark is 8～20% spinning solution, component in the solute and each component ratio by weight are: fibroin albumen 58～90%, shitosan or chitin 0～40%, antiseptic 0～5%, conductive agent 1～4%, crosslinking agent 1～4%;
C, above-mentioned spinning solution is adopted electrostatic spinning process, obtaining average pore size on dash receiver is 0.5～5.0 μ m, and porosity is 60～90%, and average fibre diameter is the anti bacteria natural silk composite nano-fiber nonwoven film of 40～100nm.
The process conditions of above-mentioned electrostatic spinning are: voltage 15～35KV, spinning distance 7～20cm, spinning solution feed quantity 0.1～3.0ml/h.
With the above-mentioned anti bacteria natural silk composite nano-fiber nonwoven film that makes again through gamma-ray irradiation.
Compared with prior art, the advantage of anti bacteria natural silk composite nano-fiber material provided by the invention is:
1, it is main raw material with silk, and silk is a kind of quite pure native protein, with human body the good tissue compatibility is arranged, nontoxic, non-stimulated and sensitization, and therefore, the surface of a wound medical material and the surface of a wound made have good bonding force.
2, compound shitosan or chitin and antiseptic in fibroin, and shitosan or chitin are a kind of natural high polymers with antibiotic property; Used antiseptic is the non-antibiotic class, its has a broad antifungal spectrum, to staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa have excellent killing action, little to the human body side effect, toxicity is low, skin is had no stimulation, light, Heat stability is good, they and fibroin dissolve in the homogeneous solvent, form uniform spinning solution, in the composite nano fiber nonwoven film that electrostatic spinning forms, shitosan, antiseptic etc. can with the even compound blend of fibroin albumen in nanofiber nonwoven film, because the nanofiber specific area is big, the shitosan class shows excellent bactericidal properties by the effect of contact obstacle sterilization mechanism; Because antiseptic is uniformly distributed in the nanofiber, fiber finer, specific area is big, and therefore, its initial release concentration is big, the bactericidal action that makes release concentration surpass the medicine minimum bactericidal concentration and have excellence, because of this nonwoven film is to intersect stacking forming in length and breadth by many nanofibers, medicine needs outwards to discharge gradually from fibrous inside, therefore again, the sustainable release of antiseptic in the film, and the persistence of maintenance drug effect.
3, because therefore the intermembranous hole that a large amount of up/down perforations are arranged of nanofiber nonwoven that electrostatic spinning forms, has excellent water-permeable and air permeable, help Wound treating.Also because electrostatic spinning at room temperature carries out, therefore, antiseptic can not be subjected to Temperature Influence and cause that the composition of medicine changes, and guarantees good result of use.
4, this anti bacteria natural silk composite nano-fiber material as surface of a wound medical material, its appearance white, thickness be even, smooth, smooth, soft behind irradiation sterilization, not cracky, use very convenient.
Description of drawings
Fig. 1 is ESEM (SEM) figure of the anti bacteria natural silk composite nano-fiber material that makes by the technical scheme that the embodiment of the invention 1 is provided;
Fig. 2 is the SEM figure of the anti bacteria natural silk composite nano-fiber material for preparing by the technical scheme that the embodiment of the invention 3 is provided.
The specific embodiment
The invention will be further elaborated below in conjunction with embodiment.
Embodiment one:
1. 0.1 kilogram of leftover bits and pieces silk is put into 3 mass per liter marks and be 0.05% aqueous sodium carbonate, boiled 0.5 hour, the silk gum of most silk periphery is taken off in reprocessing three times, obtains fibroin;
2. with after the gained fibroin drying, be 1: 8: 2 calcium chloride, water, ethanolic solution with 0.6 liter of mol ratio, become fibroin solution 78 ± 2 ℃ of following heating for dissolving;
3. above-mentioned fibroin solution is poured in the cellulose pellicle,,,, filtered with the multilayer absorbent gauze again, make pure silk fibroin solution to remove ethanol and the calcium chloride micromolecule in the solution again with the deionized water dialysis earlier with the running water dialysis;
4. getting 100ml pure silk fibroin solution respectively, to pour area into be 20 * 20cm
2Polystyrene (ABS) dish in, drying and forming-film under 25 ℃, the constant temperature and humidity condition of RH65%, it is stand-by to take off the pack of regenerated silk film;
5. 3.6 gram shitosans are added in the 16 gram glacial acetic acid, stir and made chitosan-acetic acid solution in 30 minutes;
6. join in the 72 gram anhydrous formic acids with above-mentioned regenerated silk film 8.04 grams, stirred 45 minutes;
7. the chitosan-acetic acid solution with step 5 gained adds in the regenerated silk formic acid solution of step 6 gained, after fully stirring, add each 0.18 gram of Boratex and tannic acid again, continue stirring and dissolving to forming uniform spinning solution 100 grams, its spinning solution mass fraction is 12%;
8. prepared 100 gram spinning solutions are injected in the spin duct by micro-injection pump;
9. the electrostatic pressure of regulating electrostatic generator is that 30kV, spinning distance are 12cm, the feed quantity of micro-injection pump spinning solution is 0.5ml/h, the metal needle of spinning solution before by spin duct sprays continuously, polar solvent glacial acetic acid and anhydrous formic acid volatilize in air, can collect 12 gram silk/chitosan composite nano fibre nonwoven films on dash receiver, can make area is 15 * 15cm
2, thickness is about about 25 of the medical antibacterial surface of a wound films of 0.015mm.Principle according to electrostatic spinning, the feed quantity of mass fraction that can be by regulating spinning solution, electrostatic pressure, spinning distance, spinning solution and spinning time etc. are with the parameter requests such as thickness of the diameter, aperture, porosity and the nonwoven film thereof that satisfy needed nanofiber.
With prepared nonwoven film behind vacuum drying chamber balance 12h, pack and on the high frequency sealing machine, seal with the double-layer plastic bag, standby with gamma-ray irradiation sterilization then.
Referring to accompanying drawing 1, by the anti bacteria natural silk composite nano-fiber material that the technical scheme that present embodiment provided makes, the average diameter of its fiber is about 82nm, as seen from Figure 1, the intermembranous hole with up/down perforation of nanofiber nonwoven, average pore size are about 0.6 μ m, porosity is about 75%.
Embodiment two:
1. 0.2 kilogram of useless mulberry silk is put into 6 mass per liter marks and be 0.05% aqueous sodium carbonate, boiled 0.5 hour, the silk gum of most silk periphery is taken off in reprocessing three times, obtains fibroin, dries under the room temperature;
2. be 1: 8: 2 calcium chloride, water, ethanolic solution with dry fibroin with 1.2 liters of mol ratios, become fibroin solution 78 ± 2 ℃ of following heating for dissolving;
3. the fibroin solution that step 2 is made is poured in the cellulose bag filter, earlier with the running water dialysis, again with the deionized water dialysis, to remove ethanol and the calcium chloride in the solution, filters with absorbent gauze again, makes pure silk fibroin solution;
4. get 100ml pure silk fibroin solution and pour in the stainless steel disc, freezing 12h under-25 ℃ places vacuumize 24h in the freeze drier again, makes spongy fibroin membrane, packs stand-by;
5. will join in the trifluoroethanol of 73 grams by spongy fibroin membrane 6.7 grams of step 4 gained, stirred 45 minutes;
6. take by weighing 3.0 gram chitins and join in the 17 gram trifluoroethanols, stirred 30 minutes;
7. the chitin solution with gained in the step 6 adds in the silk fibroin solution of step 5 gained, after fully stirring, adds each 0.15 gram of cerous acetate and pentaerythrite again, continues to be stirred to form uniform spinning solution 100 grams, and the spinning solution mass fraction is 10%;
8. the prepared 100 gram spinning solutions of step 7 are added micro-injection pump, spinning solution is injected spin duct by pump;
9. the anode of electrostatic generator is fixed on the metal needle before the spin duct, negative electrode is connected on the metal dash receiver, the electrostatic pressure of regulating electrostatic generator is 32kV, the spinning distance is 15cm, open electrostatic generator and micro-injection pump, it is 1.0ml/h that the adjusting micro-injection pump makes the feed quantity of spinning solution, the metal needle of spinning solution before by spin duct sprays continuously, the polar solvent trifluoroethanol volatilizees in air, on dash receiver, can collect 10 gram silk/chitin composite nano fiber nonwoven films, the average diameter of its fiber is 98nm, the hole that has up/down perforation between fiber, average pore size is 1.0 μ m, porosity is 78%, can make area and be about 15 * 15cm
2, thickness is about 20 of the nonwoven films of 0.015mm;
With the prepared nonwoven film of step 9 behind vacuum drying chamber balance 24h, pack and on the high frequency sealing machine, seal with the double-layer plastic bag, standby with gamma-ray irradiation sterilization then.
Above-mentioned two anti bacteria natural silk composite nano-fiber materials that embodiment obtained, after tested, they are respectively 97.8% (6h), 96.2% (6h) and 100% (24h) to the bacteriostasis rate of staphylococcus aureus; Colibacillary bacteriostasis rate is respectively 99.1% (6h), 97.6% (6h) and 100% (24h), has excellent antibiotic property.The micropore that has a large amount of up/down perforations owing to this film has excellent water-permeable and air permeable, therefore, can be used as medical materials such as antibiotic surface of a wound medical dressing and antibacterial mask.
Embodiment three:
1. 0.2 kilogram of useless mulberry silk is put into 6 mass per liter marks and be 0.05% aqueous sodium carbonate, boiled 0.5 hour, the silk gum of most silk periphery is taken off in reprocessing three times, obtains fibroin, dries under the room temperature;
2. be 1: 8: 2 calcium chloride, water, ethanolic solution with dry fibroin with 1.2 liters of mol ratios, become fibroin solution 78 ± 2 ℃ of following heating for dissolving;
3. the fibroin solution that step 2 is made is poured in the cellulose bag filter, earlier with the running water dialysis, again with the deionized water dialysis, to remove ethanol and the calcium chloride in the solution, filters with absorbent gauze again, makes pure silk fibroin solution;
4. get 100ml pure silk fibroin solution and pour in the stainless steel disc, freezing 8h under-18 ℃ places vacuumize 18h in the freeze drier again, makes the fibroin albumen powder, packs stand-by;
5. will join in the anhydrous formic acid of 73.8 grams by fibroin powder 16.2 grams of step 4 gained, stirred 45 minutes;
6. select for use antiseptic biguanides acetate 0.54 gram to join in the 8.2 gram glacial acetic acid, stirring and dissolving makes antimicrobial;
7. above-mentioned antimicrobial is joined in the solution that step 5 makes, after fully stirring, add each 0.63 gram of Boratex and boric acid more respectively, continue stirring and dissolving to forming uniform spinning solution 100 grams; The spinning solution mass fraction is 18%;
8. the prepared 100 gram spinning solutions of step 6 are injected in the spin duct by micro-injection pump;
9. the electrostatic pressure of regulating electrostatic generator is that 32kV, spinning distance are 15cm, open electrostatic generator and micro-injection pump, it is 0.8ml/h that the adjusting micro-injection pump makes the feed quantity of spinning solution, the metal needle of spinning solution before by spin duct sprays continuously, polar solvent glacial acetic acid and anhydrous formic acid volatilize in air, on dash receiver, can collect 18 gram silk/antimicrobial composite nano fiber nonwoven films, can make 15 * 15cm
2, thickness is about 30 of the nonwoven films of 0.02mm.Contain 0.1～1.5 milligram of antimicrobial on every square centimeter of nanofiber nonwoven film;
10. after placing vacuum desiccator to vacuumize 8h the prepared fiber non-woven film of step 9, pack and on the high frequency sealing machine, seal with the double-layer plastic bag, standby with the gamma-ray irradiation sterilization then.
Referring to accompanying drawing 2, by the anti bacteria natural silk composite nano-fiber material that the technical scheme that present embodiment provided makes, its fibre diameter is about 96nm, the intermembranous hole with up/down perforation of nanofiber nonwoven, and average pore size is about 1.2 μ m, porosity is about 80%.
After tested, this nano fibrous membrane is to staphylococcus aureus and colibacillary inhibition zone is respectively 16mm and 13mm (presses testing standard, inhibition zone greater than 7mm for having antibiotic property), and the inhibition zone of pure silk nanofiber nonwoven film is 0, this shows to have the antibiotic property of excellence by the nano-fiber material of present embodiment technical scheme preparation.Through the test shows of Release Performance, release concentration has reached the minimum bactericidal concentration of medicine in this anti bacteria natural silk composite nano-fiber material 1 hour, and the 48h medicine still discharges continuing, and keeps lasting drug effect.Rate of release can be controlled by the diameter of regulating nanofiber, and diameter is little then to be accelerated greatly to discharge because of specific area, thereby reaches the effect of control release.The micropore that has a large amount of up/down perforations owing to this nonwoven film has excellent water-permeable and air permeable again, therefore can be used as medical materials such as antibiotic surface of a wound medical dressing and film for treating oral ulcer.
Claims (4)
1. anti bacteria natural silk composite nano-fiber material is characterized in that: it is nanofiber nonwoven membrane structure, and average pore size is 0.5～5.0 μ m, and porosity is 60～90%, and the average diameter of fiber is 40～100nm; Its component and each component ratio by weight are: fibroin albumen 58～90%, shitosan or chitin 0～40%, antiseptic 0～5%, conductive agent 1～4%, crosslinking agent 1～4%; Described antiseptic is quaternary ammonium salt, guanidine class, poly-guanidine class and contains Ag
+, Zn
2+In the salt of metal ion one or more; Described conductive agent is one or more in borate, acetate, the silicate; Described crosslinking agent is one or more in tannic acid, citric acid, pentaerythrite, the boric acid.
2. the method for preparing anti bacteria natural silk composite nano-fiber material, earlier with silk through come unstuck, dissolving, dialysis, purifying, drying, obtain pure fibroin albumen, it is characterized in that carrying out again the processing of following steps:
A. be dissolved in pure fibroin albumen, shitosan or chitin or antiseptic in the polar solvent respectively, make homogeneous solution after they fully being mixed, described polar solvent is one or more in glacial acetic acid, dimethyl formamide, anhydrous formic acid, the trifluoroethanol again;
B. in above-mentioned solution, add conductive agent, crosslinking agent, the preparation quality mark is 8～20% spinning solution, component in the solute and each component ratio by weight are: fibroin albumen 58～90%, shitosan or chitin 0～40%, antiseptic 0～5%, conductive agent 1～4%, crosslinking agent 1～4%;
C. above-mentioned spinning solution is adopted electrostatic spinning process, obtaining average pore size on dash receiver is 0.5～5.0 μ m, and porosity is 60～90%, and average fibre diameter is the anti bacteria natural silk composite nano-fiber nonwoven film of 40～100nm.
3. the method for preparing anti bacteria natural silk composite nano-fiber material according to claim 2 is characterized in that described electrostatic spinning process condition is: voltage 15～35KV, spinning distance 7～20cm, spinning solution feed quantity 0.1～3.0ml/L.
4. the method for preparing anti bacteria natural silk composite nano-fiber material according to claim 2 is characterized in that: with the anti bacteria natural silk composite nano-fiber nonwoven film that makes again through gamma-ray irradiation.
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