CN101187111B - Composite nanometer fiber felt containing nano silver gelatin/chitosan for medical dressing and its preparation - Google Patents
Composite nanometer fiber felt containing nano silver gelatin/chitosan for medical dressing and its preparation Download PDFInfo
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- CN101187111B CN101187111B CN2007101713241A CN200710171324A CN101187111B CN 101187111 B CN101187111 B CN 101187111B CN 2007101713241 A CN2007101713241 A CN 2007101713241A CN 200710171324 A CN200710171324 A CN 200710171324A CN 101187111 B CN101187111 B CN 101187111B
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Abstract
The invention relates to a silver glutin or chitose compound nanometer fiber felt containing nanometer silver for medical dressing and its process method, wherein the compound nanometer fiber felt is composed of glutin or chitose nanometer fiber which contains nanometer silver, the nanometer silver contained is evenly laid out on the nanometer fiber surface, the glutin or chitose nanometer fiber containing nanometer silver has a diameter as 50 to 180nm, the nanometer silver particle diameter is 6 to 40 nm. The process method comprises mixing the glutin solution with the chitose solution in certain proportion with formylic acid as solvent; charging silver nitrate to continue mixing till the silver nitrate totally dissolved, processing the electrostatic spinning on the obtained glutin or chitose or silver nitrate solution and receiving the nanometer thread by the aluminium foil or cloth; lightening the obtained nanometer fiber felt by ultraviolet light for photoreduction to turn the silver ion in the fiber into the nanometer silver particle. The nanometer silver particle has a diameter as low as several nanometers; the particles are evenly distributed in the fiber felt and can be processed into the medical dressing by use of the strong antibiotic effect of the nanometer silver.
Description
Technical field
The invention belongs to the nanofiber field, particularly relate to the composite nanometer fiber felt containing nano silver gelatin/chitosan and the preparation thereof that are used for medical dressing.
Background technology
The nonwoven that utilizes nanofiber to make is furnished with very high porosity, therefore has the feature of highly-breathable, adds nanofiber and has big surface area, is commonly used to make medical dressing and restores to promote wound.Nanofiber mats is made the evaporation that helps wound fluid when medical dressing is used for treatment of wounds, avoid surface of a wound hydrops, helping oxygen simultaneously sees through, also help the growth and the regeneration of wound tissue cellular respiration, epithelial tissue, can significantly accelerate healing [the Khil M S of wound, Cha D L, Kim H Y, et al.Electrospun nanofibrous polyurethane membrane as wound dressing.Journal ofBiomedical Material Research.Part B:2003,67B:675-679; Chong E J, Phan T T, Lim I J, et al.Evaluation of electrospun PCL/gelatin nanofibrous scaffold for wound healing and layereddermal reconstitution.ACTA Biomaterial.2007,3:321-330].
Silver has the function of broad-spectrum antiseptic, and uses safer.Make or form the fine particle of nanometer-level silver with the nanometer technology form, can make the activity of silver become big, antibacterial effect strengthens.Nano Silver is compound to makes antiseptic dressing in the medical dressing, have many effects [Yu H J such as sterilization, anti-inflammatory, promotion wound healing, Xu X Y, Chen X S.Preparation andantibacterial effects of PVA-PVP hydrogels containing silver nanoparticles.Journal of AppliedPolymer Science.2007,103:125-133; IP M, Lui S L, Poon V K M, et al.Antimicrobial activitiesof silver dressings:an in vitro comparison.Journal of Medical Microbiology.2006,55:59-63].Adopt the method for electrostatic spinning can in nanofiber, mix silver ion, be reduced into nano-Ag particles then, strengthened antibacterial effect, can be used for making medical dressing [Xu X Y, Yang Q B, Wang Y Z, et al.Biodegradable electrospunpoly (L-lactide) fibers containing antibacterial silver nanoparticles.European PolymerJournal.2006,42:2081-2087; Hong K H.Preparation and properties of electrspun poly (vinylalcohol)/silver fiber web as wound dressings.Polymer Engineering andScience.2007,47:43-49].
Gelatin and shitosan all are biocompatibility natural macromolecular materials preferably, both use separately or compoundly are used to prepare the existing many reports of medical dressing, and be to make spongy dressing mostly, has good result of treatment [Deng C M, He LZ, Zhao M.Biological properties of the chitosan-gelatin sponge wound dressing.CarbohydratePolymer.2007,69:583-589; Huang Zhilin. the gelatin/chitosan wound dressing is to the inotropic influence of the fresh surface of a wound. Chinese clinical rehabilitation .2005 (30): 49-54; He Lanzhen. the preparation and the performance study of shitosan-gelfoam shape wound dressing. medicine biotechnology .2006,13 (1): 45-48].In addition, gelatin [Ki C S, Baek D H, Gang K D, et al.Charaterization of gelatin nanofiber prepared from gelatin-formic acid solution.Polymer.2005,46:5094-5102; Huang Z M, Zhang Y Z.Electrospinning and mechanicalcharacterization of gelatin nanofibers.Polymer.2004,45:5361-5368] and shitosan [Geng X Y, KwonOH-Hyeong, Jang J h.Electrospinng of chitosan dissolved in concentrated acetic acid solution.Biomaterials.2005,26:5427-5432; Ohkawa K, Cha D, Kim H, et al.Electrospinning of chitosan.Macromolecular Rapid Communications.2004,25:1600-1605] successfully static be spun into nanofiber, can be used for the bio-medical field.Adopt hexafluoroisopropanol and trifluoroacetic acid as solvent as people such as Mo Xiumei, with electrostatic spinning behind gelatin and the chitosan blend prepare bionical organization bracket [Mo Xiumei, Qian Yongfang. be used for the preparation method of the gelatin/chitosan blend of bionic extracellular matrix fiber stent.CN?1952227A,2007】。But up to now, prepare the gelatin/chitosan blend material that contains Nano Silver and yet there are no report by electrostatic spinning.
Summary of the invention
The purpose of this invention is to provide a kind of composite nanometer fiber felt containing nano silver gelatin/chitosan that is used for medical dressing and preparation method thereof, this nanofiber mats is a base material with natural macromolecular material gelatin and chitosan compound, by electrostatic spinning silver ion is incorporated in the gelatin/chitosan composite nano fiber non-woven mat structure, make silver ion reduction become nano-Ag particles by UV-irradiation then, improve the anti-microbial property of fibrofelt.
A kind of composite nanometer fiber felt containing nano silver gelatin/chitosan that is used for medical dressing of the present invention, form by the gelatin/chitosan nanofiber that contains Nano Silver, the mass ratio of gelatin and shitosan is 16: 1~5: 1, wherein Nano Silver is uniformly distributed in the surface of nanofiber, the gelatin/chitosan nanofiber diameter that contains Nano Silver is 50~180nm, and the diameter of nano-Ag particles is 6~40nm.
The preparation method of the composite nanometer fiber felt containing nano silver gelatin/chitosan of medical dressing of the present invention comprises the following steps:
(1) preparation gelatin solution
Gelatin is dissolved in the formic acid (quality volumetric concentration 88%), and magnetic agitation obtains the gelatin solution that concentration is 14%~22% (g/ml) to dissolving fully;
(2) preparation chitosan solution
Shitosan is dissolved in the formic acid (quality volumetric concentration 88%), and magnetic agitation obtains the chitosan solution that concentration is 1%~3% (g/ml) to dissolving fully;
(3) preparation gelatin/chitosan/liquor argenti nitratis ophthalmicus
Get gelatin solution and chitosan solution, by gelatin and chitosan mass ratio is to mix in 16: 1~5: 1, and magnetic agitation evenly back adds the silver nitrate powder, addition be in the mixed solution gelatin and shitosan gross mass 0.5%~5%, continue to stir 0.5~1h, dissolve fully to silver nitrate;
(4) gelatin/chitosan/liquor argenti nitratis ophthalmicus with preparation in the step (3) carries out electrostatic spinning, receive nano silk with aluminium foil or cloth, the electrostatic spinning process parameter is: voltage is 18~35kV, accepting distance is 8~22cm, spinning speed is 0.4ml/h, spinneret orifice internal diameter 0.7mm, spinning is at room temperature carried out;
(5) nanofiber mats that electrostatic spinning is made adopts UV-irradiation 2~3h to carry out photo-reduction, makes the silver ion in the fiber become nano-Ag particles, and wherein the nano-Ag particles major part is distributed in the surface of fiber.
The present invention utilizes formic acid as solvent, presoma with Nano Silver---silver nitrate joins and makes uniform spinning solution in the gelatin/chitosan solution, by electrostatic spinning silver ion is incorporated in the fiber, makes the silver ion reduction in the fiber become nano-Ag particles by UV-irradiation then.The nano-Ag particles diameter that obtains like this is very little, is low to moderate several nanometers, and nano-Ag particles is evenly distributed in the fibrofelt, can utilize the strong antimicrobial effect of Nano Silver to make medical dressing, artificial skin etc.
Beneficial effect of the present invention:
The containing the nano silver fibre felt and can make Nano Silver and nanofiber once-forming of electrospinning process of the present invention preparation, allow nano-Ag particles attached in gelatin/chitosan composite nano fiber surface or the embedding fiber, can reduce coming off and agglomeration of Nano Silver effectively like this, avoided direct adding nano silver powder, and can reduce the silver-colored addition of making nano silver fibre, the Nano Silver of formation is distributed in fibrofelt more equably.Utilize the strong antimicrobial effect of Nano Silver, this gelatin/chitosan composite nanometer fiber felt that contains Nano Silver can be applicable to make medical dressing.
Description of drawings
Fig. 1 is the sem photograph of the nanofiber felt material that makes of embodiment 1;
Fig. 2 is the sem photograph of the nanofiber felt material that makes of embodiment 2;
Fig. 3 is the transmission electron microscope picture of the nanofiber felt material that makes of embodiment 1;
Fig. 4 is the transmission electron microscope picture of the nanofiber felt material that makes of embodiment 2.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Accurately taking by weighing 1.600g gelatin and 0.300g shitosan, respectively to be dissolved in 10ml quality volumetric concentration respectively be in 88% the formic acid solution, and sealing back normal temperature lower magnetic force is stirred to shitosan and all dissolves fully with gelatin.Get the 9.1g gelatin solution mix with the 4.35g chitosan solution back magnetic agitation even, add 0.024g silver nitrate powder then, 0.5h is continued to stir in the sealing back, treat that silver nitrate dissolves the back fully and forms light yellow transparency liquid, carry out electrostatic spinning after leaving standstill 15min, voltage is 28.8kV, the syringe pump fltting speed is 0.4ml/h, the employing aluminium foil receives, and receiving range is 15cm, and orifice diameter is 0.7mm, receive with aluminium foil or cotton, obtain static and spin the gelatin/chitosan blend nanofiber mats that contains Nano Silver, vacuumize is placed on irradiation 3h under the uviol lamp, obtains containing the gelatin/chitosan composite nanometer fiber felt of Nano Silver.Wherein average fibre diameter is 106nm, and the average diameter of silver-colored particle is 10nm.
Embodiment 2
Accurately taking by weighing 1.600g gelatin and 0.300g shitosan, respectively to be dissolved in 10ml quality volumetric concentration respectively be in 88% the formic acid solution, and sealing back normal temperature lower magnetic force is stirred to shitosan and all dissolves fully with gelatin.Get the 9.1g gelatin solution mix with the 4.35g chitosan solution back magnetic agitation even, add 0.048g silver nitrate powder then, 0.5h is continued to stir in the sealing back, treat that silver nitrate dissolves the back fully and forms light yellow transparency liquid, carry out electrostatic spinning after leaving standstill 15min, voltage is 28.8kV, the syringe pump fltting speed is 0.4ml/h, the employing aluminium foil receives, and receiving range is 15cm, and orifice diameter is 0.7mm, receive with aluminium foil or cotton, obtain static and spin the gelatin/chitosan blend nanofiber mats that contains Nano Silver, vacuumize is placed on irradiation 3h under the uviol lamp, obtains containing the gelatin/chitosan composite nanometer fiber felt of Nano Silver.Wherein average fibre diameter is 93nm, and the average diameter of silver-colored particle is 17nm.
Embodiment 3
Accurately taking by weighing 1.600g gelatin and 0.300g shitosan, respectively to be dissolved in 10ml quality volumetric concentration respectively be in 88% the formic acid solution, and sealing back normal temperature lower magnetic force is stirred to shitosan and all dissolves fully with gelatin.Get the 9.1g gelatin solution mix with the 4.35g chitosan solution back magnetic agitation even, add 0.012g silver nitrate powder then, 0.5h is continued to stir in the sealing back, treat that silver nitrate dissolves the back fully and forms light yellow transparency liquid, carry out electrostatic spinning after leaving standstill 15min, voltage is 28.8kV, the syringe pump fltting speed is 0.4ml/h, the employing aluminium foil receives, and receiving range is 15cm, and orifice diameter is 0.7mm, receive with aluminium foil or cotton, obtain static and spin the gelatin/chitosan blend nanofiber mats that contains Nano Silver, vacuumize is placed on irradiation 3h under the uviol lamp, obtains containing the gelatin/chitosan composite nanometer fiber felt of Nano Silver.Wherein average fibre diameter is 130nm, and the average diameter of silver-colored particle is 8nm.
Claims (1)
1. composite nanometer fiber felt containing nano silver gelatin/chitosan that is used for medical dressing, it is characterized in that: this composite nanometer fiber felt is made up of the gelatin/chitosan nanofiber that contains Nano Silver, the mass ratio of gelatin and shitosan is 16: 1~5: 1, Nano Silver is uniformly distributed in the surface of nanofiber, the gelatin/chitosan nanofiber diameter that contains Nano Silver is 50~180nm, and the diameter of nano-Ag particles is 6~40nm.
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