CN103184570B - A kind of fibroin albumen base antibacterial nano fiber and preparation method thereof - Google Patents
A kind of fibroin albumen base antibacterial nano fiber and preparation method thereof Download PDFInfo
- Publication number
- CN103184570B CN103184570B CN201310120970.0A CN201310120970A CN103184570B CN 103184570 B CN103184570 B CN 103184570B CN 201310120970 A CN201310120970 A CN 201310120970A CN 103184570 B CN103184570 B CN 103184570B
- Authority
- CN
- China
- Prior art keywords
- fibroin
- fibroin albumen
- silk
- nano fiber
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 108010022355 Fibroins Proteins 0.000 title claims abstract description 61
- 239000002121 nanofiber Substances 0.000 title claims abstract description 39
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000009987 spinning Methods 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 16
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 14
- 239000002798 polar solvent Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 19
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 240000000249 Morus alba Species 0.000 claims description 6
- 235000008708 Morus alba Nutrition 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000010041 electrostatic spinning Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001506 calcium phosphate Substances 0.000 claims description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 241000723346 Cinnamomum camphora Species 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 235000003846 Ricinus Nutrition 0.000 claims description 2
- 241000322381 Ricinus <louse> Species 0.000 claims description 2
- 241000124033 Salix Species 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 229960000846 camphor Drugs 0.000 claims description 2
- 229930008380 camphor Natural products 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 230000006196 deacetylation Effects 0.000 claims description 2
- 238000003381 deacetylation reaction Methods 0.000 claims description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 2
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 claims description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 2
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 abstract description 11
- 238000001523 electrospinning Methods 0.000 abstract description 4
- 239000003519 biomedical and dental material Substances 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 7
- 239000003242 anti bacterial agent Substances 0.000 description 7
- 229940088710 antibiotic agent Drugs 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 230000002421 anti-septic effect Effects 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 2
- -1 antibacterial Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 206010011409 Cross infection Diseases 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000235342 Saccharomycetes Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of fibroin albumen base antibacterial nano fiber and preparation method thereof.Described nanofiber comprises fibroin albumen 40 ~ 98 parts in parts by mass, titanium dioxide 1 ~ 10 part, shitosan 1 ~ 60 part; Concrete its preparation method is: by silk through coming unstuck, dry obtain fibroin fiber, treatedly again be prepared into regenerated silk fibroin film, fibroin albumen, titanium dioxide, shitosan are dissolved in polar solvent by certain mass ratio, be prepared into the spinning solution that mass concentration is 0.01% ~ 80%, under adopting electrospinning device room temperature state, obtained average diameter is the fibroin albumen base antibacterial nano fiber of 10 ~ 1000nm.The present invention's fibroin albumen base antibacterial nano fiber antibiotic rate newly developed reaches more than 95%, while having long-term antibacterial, also has good biocompatibility and the mechanical property of excellence, is applicable to bio-medical material.
Description
Technical field
The present invention relates to a kind of nano-fiber material and preparation method thereof, be specifically related to a kind of fibroin albumen base antibacterial nano fiber material and preparation method thereof, belong to field of medical materials.
Background technology
Nano anti-biotic material is the new material that a class possesses bacteriostasis property, due to the special effects of the high-ratio surface sum high reaction activity of antiseptic in material, substantially increase overall antibacterial effect, the Growth and reproduction that microorganism can be made to comprise bacterium, fungi, saccharomycete, algae and virus etc. keeps lower level.With the various goods that anti-biotic material is made, there is health self-cleaning function, effectively can avoid the propagation of bacterium, and the mechanical property of anti-biotic material can be made to be strengthened, nano-antibacterial product not only effectively can stop the bacterium cross infection of person to person, people and thing, thing and thing, can also guide people that health care pattern is changed into ex ante forecasting and prevention from treatment afterwards.Along with the raising that people's living standard and health environment are realized, the production of nano anti-biotic material and products thereof has become important new industry.
Current most of anti-biotic material mainly to adopt in material and directly adds the method such as antiseptic or chemical graft and will have the material of antibacterial functions or group is introduced, or is coated on the material that material surface makes material become to have anti-microbial property.At present the research of relevant anti-biotic material is in the majority with the anti-biotic material report containing Nano Silver or silver ion, and Nano Silver majority is powder additive, complicated process of preparation, and processing cost is high, and when application Nano Silver easily reunite, with material matrix in conjunction with poor; Chinese patent application CN102391738A discloses containing polyvinyl alcohol-based nano composite antibacterial film material of a kind of silver ion and preparation method thereof, first prepare PVA-based nanocomposite coating material, immersed again in liquor argenti nitratis ophthalmicus, stir, through the silver ion that washed with de-ionized water removing is residual, drying at room temperature, obtains the containing polyvinyl alcohol-based nano composite antibacterial film material of silver ion, the method complex process, the antibacterial durability of class coating material prepared therefrom can not be guaranteed.
On the other hand, along with the develop rapidly of nano material technology, nanofiber technology has become forward position and the study hotspot of fibre science, and is applied at industrial fields such as electronics, machinery, biomedicine, chemical industry, weavings.Nanofiber mainly comprises two concepts: one is proper nanofiber, refers to that fibre diameter is less than the superfine fibre of 100 nm; Another concept is by nano particle filling in fiber, carries out modification to fiber, adopts the different nanoparticle of performance, can develop the various functional fibers such as antibacterial, fire-retardant, electromagnetic shielding.
Electrostatic spinning technique prepares the most important method of nanofiber at present.The core of this technology makes charged Polymer Solution or melt flow in electrostatic field and deformation occurs, and then solidify through solvent evaporation or melt cooling, so obtain fibrous material, this process is called for short electrospinning.Natural or synthetic high polymer is adopted to be raw material, the nano-fiber material prepared through electrostatic spinning has been reported, such as: the nano-fiber material prepared for raw material with polyamide, polyvinyl alcohol, polypropylene, cellulose and its derivates etc., but the poor biocompatibility of above-mentioned material, is unsuitable for being used as medical material.
Fibroin albumen is a kind of pure natural macromolecular material, equally has in good body, biocompatibility in vitro is (see Gregory H Altman, et al with collagen, Biomaterials, 2003,401-416), be suitable as biomaterial.Chinese patent application CN1348820A discloses a kind of Coremia-resisting wound protecting film and preparation method thereof, and the method adopts fibroin and the blended method of antiseptic to obtain antibacterial protecting film; Chinese patent application CN102319448A discloses a kind of antibacterial hydrogel material for the preparation of medical wound dressing and preparation method thereof, the method adopts interpolation n-trimethyl chitosan chloride to prepare fibroin albumen anti-bacterial hydrogel, its preparation process is simple, but the mechanical property of material is very poor.
Meanwhile, as antibiotic material in medical use, not only to focus on the antibacterial activity of its wide spectrum, more need to consider its biological safety, biocompatibility and degradability comprehensively, the problem such as acute toxicity, allergic reaction should have been avoided.
Summary of the invention
The object of this invention is to provide a kind of fibroin albumen base antibacterial nano fiber and preparation method thereof, obtained nanofiber has good biocompatibility, excellent mechanical property and long-term antibacterial effect.
For achieving the above object, the technical solution used in the present invention is: a kind of fibroin albumen base antibacterial nano fiber, by parts by mass, comprises following component:
Fibroin albumen 40 ~ 98 parts
Titanium dioxide 1 ~ 10 part
Shitosan 1 ~ 60 part
Wherein, the particle diameter of described titanium dioxide is 5 ~ 1000nm; The diameter of described fibroin albumen base antibacterial nano fiber is 10 ~ 1000 nm.
In technique scheme, the deacetylation of described shitosan is 50% ~ 100%, and molecular weight is 2 × 10
5~ 5 × 10
5, viscosity is 0.7 ~ 1Pa.s.
In technique scheme, described fibroin albumen is one or more in tussah silk, mulberry silk, wild silk yarn, ricinus silk, camphor silk, cassava silkwormsilk, willow silk.
The preparation method of above-mentioned fibroin albumen base antibacterial nano fiber, comprises the following steps:
(1) preparation of fibroin protein film: silk through coming unstuck, dry obtain fibroin fiber, fibroin fiber is treated is prepared into regenerated silk fibroin film;
(2) preparation of spinning solution: the fibroin protein film first step (1) prepared and titanium dioxide are dissolved in polar solvent, again shitosan is added in solution, stirring at room temperature, fully makes uniform spinning solution, concentration of dope 0.01% ~ 80% after mixing; Described polar solvent is one or more in anhydrous formic acid, glacial acetic acid, dimethyl formamide, glacial acetic acid, trifluoroacetic acid, hexafluoroisopropanol;
(3) preparation of nanofiber: spinning solution electrostatic spinning apparatus spinning step (2) prepared, obtains fibroin albumen base antibacterial nano fiber material.
In technique scheme, described step comprises dissolving, dialysis, filtration, dry run to the process of fibroin fiber in (1); The solvent that wherein course of dissolution adopts is selected from LiBr, C
2h
5oH and H
2mixed liquor (the LiBr:C of O
2h
5oH:H
2o=45:44:11 mass ratio), LiBr and H
2mixed liquor (the LiBr:H of O
2o=40:60 mass ratio) or CaCl
2, C
2h
5oH and H
2mixed liquor (the CaCl of O
2: C
2h
5oH:H
2o=1:2:8 mol ratio).
In technique scheme, comprise dissolving, drying, washing, again dry run in described step (1) to the process of fibroin fiber, the solvent that wherein course of dissolution adopts is selected from acid: the mass ratio of salt is the acid of 99:1 ~ 10:90/salt mixed liquor; Described acid is selected from formic acid, phosphoric acid or both mixed liquors; Salt be selected from calcium chloride, calcium hydroxide, calcium carbonate, calcium nitrate, hydroxyapatite, tricalcium phosphate, tetracalcium phosphate, OCP, calcium monohydrogen phosphate, calcium phosphate, lithium bromide, barium chloride, copper chloride, zinc chloride, magnesium chloride one or more.
In technique scheme, in described step (3), the technological parameter of electrostatic spinning is: voltage 1 ~ 50 kilovolt, receiving range 1 ~ 50 centimetre, liquid inventory is 0.01 ~ 20mL/h.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. this invention exploits a kind of multicomponent fibroin albumen base antibacterial nano fiber material, antimicrobial component titanium dioxide and shitosan are dispersed in nanofiber, the antibiotic rate of nanofiber reaches more than 95%, more lasting compared to the antibacterial effect of the material being used alone titanium dioxide or shitosan in prior art, antibiotic rate is higher.
2. the nano-fiber material prepared of the present invention is with natural silk fibroin for matrix, and the mechanical property of the biocompatibility had, good degradability and excellence is a kind of desirable bio-medical material;
3. preparation method of the present invention is simple, and preparation condition is controlled, and can regulate material proportion as required, thus obtains the bio-medical material meeting respective performances, has a good application prospect.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of fibroin albumen base antibacterial nano fiber in the embodiment of the present invention one.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Embodiment one
A kind of fibroin albumen base antibacterial nano fiber, its preparation method comprises the steps:
(1) sodium carbonate liquor of natural mulberry silk mass fraction 0.05% boils 30 min and comes unstuck, and repeats 3 times and obtains pure mulberry silk fibroin fibers afterwards; This fibroin albumen is dissolved in LiBr:C
2h
5oH:H
2o=45:44:11(mass ratio) in mixed liquor, in 70 DEG C of water-baths, stirring and dissolving obtains regenerated silk fibroin solution; Through dialysis, filtration, film forming, form regenerated silk fibroin film;
(2) by the 95:3:2 preparation in mass ratio of regenerated silk fibroin film, titanium dioxide and shitosan, first regenerated silk fibroin film and titanium dioxide are dissolved in formic acid, then, then shitosan are added in above-mentioned solution, stirring at room temperature 4h, is prepared into the spinning solution that mass fraction is 10%;
(3) by above-mentioned obtained spinning solution, under room temperature state, utilize electrospinning device to carry out spinning, fibroin albumen base antibacterial nano fiber can be obtained.During spinning, technological parameter is: spinning speed is 0.2ml/h; Spinning voltage is 15kV; Receiving range is 10cm.
Accompanying drawing 1 is the scanning electron microscope (SEM) photograph of above-mentioned obtained fibroin albumen base antibacterial nano fiber, and see Fig. 1, the diameter of antibacterial nano fiber is 99 ~ 173 nm.
Embodiment two
A kind of fibroin albumen base antibacterial nano fiber, its preparation method comprises the steps:
(1) sodium carbonate liquor of natural mulberry silk mass fraction 0.05% boils 30 min and comes unstuck, and repeats 3 times and obtains pure mulberry silk fibroin fibers afterwards; This fibroin albumen is dissolved in CaCl
2: C
2h
5oH:H
2o=1:2:8(mol ratio) in mixed liquor, in 70 DEG C of water-baths, stirring and dissolving obtains regenerated silk fibroin solution; Through dialysis, filtration, film forming, form regenerated silk fibroin film;
(2) by the 70:15:15 preparation in mass ratio of regenerated silk fibroin film, titanium dioxide and shitosan, first regenerated silk fibroin film and titanium dioxide are dissolved in formic acid, then, then shitosan are added in above-mentioned solution, stirring at room temperature 6h, is prepared into the spinning solution that mass fraction is 20%;
(3) by above-mentioned obtained spinning solution, under room temperature state, utilize electrospinning device to carry out spinning, fibroin albumen base antibacterial nano fiber can be obtained; During spinning, technological parameter is: spinning speed is 0.15ml/h; Spinning voltage is 20kV; Receiving range is 12cm.
Claims (3)
1. a fibroin albumen base antibacterial nano fiber, is characterized in that, by parts by mass, comprises following component:
Fibroin albumen 40 ~ 98 parts
Titanium dioxide 1 ~ 10 part
Shitosan 1 ~ 60 part
Wherein, the particle diameter of described titanium dioxide is 5 ~ 1000nm; The diameter of described fibroin albumen base antibacterial nano fiber is 10 ~ 1000 nm;
The preparation method of described fibroin albumen base antibacterial nano fiber, comprises the following steps:
(1) preparation of fibroin protein film: silk through coming unstuck, dry obtain fibroin fiber, fibroin fiber is treated is prepared into regenerated silk fibroin film;
(2) preparation of spinning solution: the fibroin protein film first step (1) prepared and titanium dioxide are dissolved in polar solvent, again shitosan is added in solution, stirring at room temperature, fully makes uniform spinning solution, concentration of dope 0.01% ~ 80% after mixing; Described polar solvent is one or more in anhydrous formic acid, glacial acetic acid, dimethyl formamide, trifluoroacetic acid, hexafluoroisopropanol;
(3) preparation of nanofiber: spinning solution electrostatic spinning apparatus spinning step (2) prepared, obtains fibroin albumen base antibacterial nano fiber material;
Comprise dissolving, drying, washing, again dry run to the process of fibroin fiber in described step (1), the solvent that wherein course of dissolution adopts is selected from acid: the mass ratio of salt is the acid of 99:1 ~ 10:90/salt mixed liquor; Described acid is selected from formic acid, phosphoric acid or both mixed liquors; Salt be selected from calcium chloride, calcium hydroxide, calcium carbonate, calcium nitrate, hydroxyapatite, tricalcium phosphate, tetracalcium phosphate, OCP, calcium monohydrogen phosphate, calcium phosphate, lithium bromide, barium chloride, copper chloride, zinc chloride, magnesium chloride one or more.
2. fibroin albumen base antibacterial nano fiber according to claim 1, is characterized in that: the deacetylation of described shitosan is 50% ~ 100%, and molecular weight is 2 × 10
5~ 5 × 10
5, viscosity is 0.7 ~ 1Pas.
3. fibroin albumen base antibacterial nano fiber according to claim 1, is characterized in that: described fibroin albumen is one or more in tussah silk, mulberry silk, wild silk yarn, ricinus silk, camphor silk, cassava silkwormsilk, willow silk.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310120970.0A CN103184570B (en) | 2013-04-09 | 2013-04-09 | A kind of fibroin albumen base antibacterial nano fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310120970.0A CN103184570B (en) | 2013-04-09 | 2013-04-09 | A kind of fibroin albumen base antibacterial nano fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103184570A CN103184570A (en) | 2013-07-03 |
| CN103184570B true CN103184570B (en) | 2015-08-26 |
Family
ID=48676004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310120970.0A Expired - Fee Related CN103184570B (en) | 2013-04-09 | 2013-04-09 | A kind of fibroin albumen base antibacterial nano fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103184570B (en) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103341214B (en) * | 2013-07-08 | 2014-12-31 | 苏州大学 | Silk fibroin membrane and preparation method thereof |
| CN103341209B (en) * | 2013-07-08 | 2015-04-08 | 苏州大学 | Silk fibroin nanofiber membrane and preparation method thereof |
| CN103319731B (en) * | 2013-07-08 | 2015-04-29 | 苏州大学 | Regenerated silk fibroin solution and preparation method thereof |
| CN103320886B (en) * | 2013-07-15 | 2015-04-29 | 苏州大学 | Bionic regenerated silk fibroin filament fiber and preparation method thereof |
| CN103436985A (en) * | 2013-07-22 | 2013-12-11 | 苏州三和开泰花线织造有限公司 | Preparation method of silk fibroin/chitosan blend nanofiber |
| CN104562263B (en) * | 2015-02-03 | 2017-04-12 | 广东绮瑞制衣实业有限公司 | Novel negative ion regenerated silk fiber and preparation method thereof |
| CN107735406A (en) | 2015-04-09 | 2018-02-23 | 丝芭博株式会社 | Polar solvent solution and its manufacture method |
| WO2016163336A1 (en) | 2015-04-09 | 2016-10-13 | Ｓｐｉｂｅｒ株式会社 | Polar solvent solution and production method thereof |
| CN105061637B (en) * | 2015-09-07 | 2017-08-08 | 安徽农业大学 | A kind of water-soluble antibacterial mono carboxylic chitosan and its preparation method and application |
| CN105616323A (en) * | 2016-01-21 | 2016-06-01 | 苏州印丝特纺织数码科技有限公司 | Silk sponge product for nourishing and caring skin and preparation method thereof |
| CN105664225A (en) * | 2016-02-24 | 2016-06-15 | 苏州思彬纳米科技有限公司 | Nano-silver, chitosan and fibroin compound biological dressing and preparation method thereof |
| CN106192064B (en) * | 2016-06-21 | 2018-07-06 | 胡剑锋 | Medical material |
| CN106732808A (en) * | 2016-11-25 | 2017-05-31 | 江苏爱西施科技服务咨询股份有限公司 | A kind of fibroin albumen/TiO2The preparation method of composite catalyst |
| CN106592012B (en) * | 2016-12-06 | 2019-02-19 | 宁波芸生纺织品科技有限公司 | A kind of biological fiber material and preparation method thereof |
| CN106637484B (en) * | 2016-12-08 | 2019-01-22 | 浙江百惠生物科技有限公司 | A kind of preparation method of green plum ferment collagenous shreds |
| CN106676670A (en) * | 2016-12-09 | 2017-05-17 | 天长市天龙泵阀成套设备厂 | Hyaluronic acid/silk fibroin nano-fibre and preparation method thereof |
| CN106674982A (en) * | 2016-12-12 | 2017-05-17 | 成都育芽科技有限公司 | Polyurethane antibacterial biomedical composite material and preparation method thereof |
| CN107475807A (en) * | 2017-08-30 | 2017-12-15 | 常州豫春化工有限公司 | A kind of preparation method of the fiber of modification of nylon 6 |
| CN108385182A (en) * | 2018-02-10 | 2018-08-10 | 海盐县硕创服装研究所 | Silk-fibroin-based antibacterial nanofiber and preparation method thereof |
| CN108505143A (en) * | 2018-04-10 | 2018-09-07 | 郑州智锦电子科技有限公司 | A kind of nanofiber and preparation method thereof |
| CN108714237A (en) * | 2018-06-01 | 2018-10-30 | 苏州先蚕丝绸有限公司 | A kind of natural silk adhesive bandage |
| CN109097851A (en) * | 2018-06-27 | 2018-12-28 | 苏州市贝克生物科技有限公司 | Fibroin material and preparation method thereof |
| CN108978038B (en) * | 2018-08-15 | 2021-01-01 | 浙江法来福无纺布有限公司 | Preparation method of novel non-woven fabric with antibacterial effect |
| CN108914388B (en) * | 2018-08-15 | 2020-06-23 | 安徽利通达纤维新材料有限公司 | High-strength composite non-woven fabric with antibacterial effect |
| CN109183193B (en) * | 2018-09-27 | 2021-03-12 | 浙江和也健康科技有限公司 | Antibacterial and deodorant nanofiber and preparation method thereof |
| CN109518299A (en) * | 2018-11-13 | 2019-03-26 | 河南工程学院 | A kind of preparation method of tussah silk peptide/chitosan composite nano fibre |
| CN111455489A (en) * | 2019-01-20 | 2020-07-28 | 泽塔纳米科技（苏州）有限公司 | Antibacterial nano protein fiber and preparation method thereof |
| CN111455494A (en) * | 2019-01-20 | 2020-07-28 | 泽塔纳米科技（苏州）有限公司 | Antibacterial nanofiber and preparation method and application thereof |
| CN111455497A (en) * | 2019-01-20 | 2020-07-28 | 泽塔纳米科技（苏州）有限公司 | Antibacterial nanofiber and preparation method thereof |
| CN110229384B (en) * | 2019-06-19 | 2021-07-23 | 安徽农业大学 | A kind of silver-loaded diamoxime cellulose/chitosan/silk fibroin composite aerogel and preparation method thereof |
| CN116212096A (en) * | 2022-09-09 | 2023-06-06 | 苏州大学 | Preparation method of a long-acting antibacterial regenerated silk fibroin-based composite surgical suture |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1904159A (en) * | 2006-07-13 | 2007-01-31 | 苏州大学 | Anti bacteria natural silk composite nano-fiber material and its preparation method |
| CN101077473A (en) * | 2007-06-22 | 2007-11-28 | 上海兰度科技有限公司 | Novel environmental protection fiber film material and its preparation method |
| CN102477592A (en) * | 2010-11-22 | 2012-05-30 | 大连创达技术交易市场有限公司 | Biodegradable tissue-engineering fiber |
| CN102605460A (en) * | 2011-12-22 | 2012-07-25 | 苏州大学 | Silk fibroin/hydroxyapatite nanofiber material and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0670702A (en) * | 1992-08-27 | 1994-03-15 | Shinano Kenshi Kk | Production of silk powder |
| JP2010024196A (en) * | 2008-07-22 | 2010-02-04 | Shinano Kenshi Co Ltd | Method of preparing silk fibroin powder |
| CN101358382A (en) * | 2008-08-26 | 2009-02-04 | 东华大学 | A kind of antibacterial nanofiber material and preparation method thereof |
| CN102002854B (en) * | 2010-12-06 | 2012-01-25 | 中原工学院 | Multifunctional textile finishing agent, preparation method thereof and cotton textile finishing method |
| CN102552964B (en) * | 2012-01-09 | 2014-04-09 | 李育强 | Nano silver chitosan composite antibacterial composition, adhesive bandage and preparation method of adhesive bandage |
| CN102677465B (en) * | 2012-05-23 | 2013-11-13 | 辽东学院 | Modified tussah silk fabric with functionalized nanometer chitosan and nanometer titanium dioxide |
-
2013
- 2013-04-09 CN CN201310120970.0A patent/CN103184570B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1904159A (en) * | 2006-07-13 | 2007-01-31 | 苏州大学 | Anti bacteria natural silk composite nano-fiber material and its preparation method |
| CN101077473A (en) * | 2007-06-22 | 2007-11-28 | 上海兰度科技有限公司 | Novel environmental protection fiber film material and its preparation method |
| CN102477592A (en) * | 2010-11-22 | 2012-05-30 | 大连创达技术交易市场有限公司 | Biodegradable tissue-engineering fiber |
| CN102605460A (en) * | 2011-12-22 | 2012-07-25 | 苏州大学 | Silk fibroin/hydroxyapatite nanofiber material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 路艳华等.壳聚糖在柞蚕丝改性中的应用.《壳聚糖及纳米材料在柞蚕丝功能改性中的应用 第1版》.中国纺织出版社,2012,第16、21、144、146、148页. * |
| 郑学晶等.蚕丝蛋白的提取.《天然高分子材料 第1版》.化学工艺出版社,2010,第205-206页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103184570A (en) | 2013-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103184570B (en) | A kind of fibroin albumen base antibacterial nano fiber and preparation method thereof | |
| EP2627813B1 (en) | Hydrogel fibres and fibrous structures | |
| CN106048892B (en) | A kind of preparation method for the GO/SA/PVA composite nano-fiber membranes being loaded with nano silver particles | |
| KR100727086B1 (en) | Functional polymer material and preparation method thereof | |
| CN104631118B (en) | A kind of absorbable antibacterial alginate fibre | |
| CN107708754B (en) | Antibacterial Nanofibers | |
| CA2788221C (en) | Chitosan fiber | |
| Barani | Antibacterial continuous nanofibrous hybrid yarn through in situ synthesis of silver nanoparticles: preparation and characterization | |
| CN102086565A (en) | Polylactic acid antibacterial nanofiber membrane and preparation method thereof | |
| JP2011208286A (en) | Silk composite nanofiber and method for producing the same | |
| CN104562236A (en) | Antibacterial colored profiled ultrafine denier polyester filament and preparation method thereof | |
| JP6450237B2 (en) | Cross-linked body, cross-linking agent composition, fibrous cross-linked body, manufacturing method of fibrous cross-linked body, cell culture bed, cell culturing method using cell culture bed, and manufacturing method of cell sheet for transplantation using cell culture bed | |
| CN114318680A (en) | Antibacterial degradable film material and preparation method and application thereof | |
| Sadri et al. | Retracted: Fast and efficient electrospinning of chitosan‐Poly (ethylene oxide) nanofibers as potential wound dressing agents for tissue engineering | |
| WO2012175164A1 (en) | Stable aqueous protein solution or protein dispersion, method for the production of said stable aqueous solution or dispersion, and method for the production of molded articles or sheet material, impregnations or coatings from the stable aqueous protein solution or protein dispersion, and use thereof | |
| Thillaipandian et al. | Biofunctional textile fibres and their applications | |
| WO2012175153A2 (en) | Stable aqueous protein solution or protein dispersion, method for the production of said stable aqueous solution or dispersion, and method for the production of molded articles or sheet material, impregnations, or coatings from the stable aqueous protein solution or protein dispersion, and use thereof | |
| KR100652496B1 (en) | Antimicrobial nanofibers using chitosan, manufacturing method and apparatus thereof | |
| Korkmaz et al. | Fabrication of cross-linked gelatin electrospun nanofibers containing rosemary oil for antibacterial application | |
| CN108992700A (en) | A kind of PBS/ Graphene antibiosis operation stitching wire rod and preparation method | |
| TWI855962B (en) | Quantum nano ultra thin fiber membrane and applications thereof | |
| Gospodinova et al. | Investigation of the Fiber-Forming Properties from Ternary Solutions Containing PVA and Nutraceptics Additives on Electrospinning Process | |
| Abid et al. | Electrospun Materials and Polymeric Membranes Research Group, National Textile University, Faisalabad, Pakistan à Corresponding author. Email: m. sharjeel. abid@ gmail. com | |
| Islam | Application of nanotechnology for wool and wool blends in medical textiles utilising biopolymers | |
| Ali et al. | Antibacterial Electrospun Nanofibres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: NANJING WEISAI MEDICAL TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: GUANGZHOU WEISAI BIOMEDICINE CO., LTD. Effective date: 20131112 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 215125 SUZHOU, JIANGSU PROVINCE TO: 210046 NANJING, JIANGSU PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20131112 Address after: Qixia District of Nanjing City, Jiangsu province 210046 Xianlin streets latitude road No. 9, F6 building 120 houses Applicant after: Nanjing Weisai Medical Technology Co., Ltd. Address before: Suzhou City, Jiangsu Province, Suzhou Industrial Park 215125 Xinghu Street No. 218 Applicant before: Suzhou Weisai Biological Pharmaceutical Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: NANJING EUROMONITOR MEDICAL TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: NANJING WEISAI MEDICAL TECHNOLOGY CO., LTD. Effective date: 20150818 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20150818 Address after: Qixia District of Nanjing City, Jiangsu province Xianlin streets latitude road No. 9 building 120 building F6 Patentee after: Nanjing Ourui Medicine Technology Co., Ltd. Address before: Qixia District of Nanjing City, Jiangsu province 210046 Xianlin streets latitude road No. 9, F6 building 120 houses Patentee before: Nanjing Weisai Medical Technology Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150826 Termination date: 20160409 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |