CN101914815A - Anti-bacterium fibre material and application of silk to preparation of same - Google Patents
Anti-bacterium fibre material and application of silk to preparation of same Download PDFInfo
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- CN101914815A CN101914815A CN 201010254804 CN201010254804A CN101914815A CN 101914815 A CN101914815 A CN 101914815A CN 201010254804 CN201010254804 CN 201010254804 CN 201010254804 A CN201010254804 A CN 201010254804A CN 101914815 A CN101914815 A CN 101914815A
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Abstract
The invention discloses a new application of silk, relating to the application of silk to the preparation of an anti-bacterium fibre material. The invention also provides an anti-bacterium fibre material with good biocompatibility and the function of self bacterium resistance, and a preparation method thereof. The average pore size of the anti-bacterium fibre material is 0.5-5.0 micrometers, the porosity is 60-90%, and the average diameter of the fibre is 40-100 nanometres. The anti-bacterium fibre material comprises the following components by weight percent: 65-98% of silk fibroin, 0-5% of silver particle, 1-15% of conductive agent and 1-15% of cross-linking agent. The anti-bacterium fibre material has the inhibiting effect on pseudomonas aeruginosa, colon bacillus and staphylococcus aureus by experimental evidence, specifically on staphylococcus aureus. Therefore, the anti-bacterium fibre material can be produced into medical gauze, dressing sticks and anti-bacterium and anti-wound masks.
Description
Technical field
The present invention relates to the application of silk in preparation anti-bacterial fibre material, and a kind of anti-bacterial fibre material that is composited by fibroin albumen and Nano Silver and preparation method thereof.
Background technology
Silver is that anti-biotic material is that a class has persistence, broad spectrum activity, good heat resistance, safe, the difficult inorganic antibacterial material that produces characteristics such as drug resistance.But the fungistatic effect of common silvery agent a little less than, argent is processed into can produces powerful bactericidal action behind the Nano Silver, this has opened up wide application prospect for silvery agent of extensive use.
Fibroin albumen is a kind of natural biological protein from various silks.In recent years, nontoxic, harmless to human body, be easy to absorb because it has excellent biocompatibility, and be widely used in fields such as health food, cosmetics, artificial skin, immobilised enzymes material, medicament slow release material.Fibroin protein is made up of 18 seed amino acids such as glycine, alanine, serine, tyrosine, phenylalanines, and wherein to generate nano-metal particle immobilized in fibroin albumen because of the p-cresol base that contains strong reducing power can reduce some metal ions for tyrosine residue.Thereby the design feature of utilizing fibroin albumen prepares and fixing Nano Silver, and the nano anti-biotic material of development of new has bigger practical value for the Application Areas of expansion wire fibroin and nano silver antimicrobials.
In the prior art report that utilizes silk to prepare the anti-bacterial fibre material is not arranged at present.
Summary of the invention
At above-mentioned prior art, the invention provides a kind of new purposes of silk, i.e. the application of silk in preparation anti-bacterial fibre material, the present invention also provide a kind of biocompatibility good and have an anti-bacterial fibre material from antibacterial functions, and preparation method thereof.
The present invention is achieved by the following technical solutions:
The application of silk in preparation anti-bacterial fibre material.
A kind of anti-bacterial fibre material, its average pore size are 0.5~5.0 μ m, and porosity is 60~90%, and average fibre diameter is 40~100nm; The percentage by weight of its component and each component is: fibroin albumen 65~98%, silver particles 0~5%, conductive agent 1~15%, crosslinking agent 1~15%.
Described conductive agent is a kind of in borate, acetate, the silicate.
Described crosslinking agent is a kind of in tannic acid, citric acid, the boric acid.
A kind of is the method for feedstock production anti-bacterial fibre material with silk, and step is as follows:
(1) silk obtains silk fibroin water solution after coming unstuck, dissolve, dialysing;
(2) liquor argenti nitratis ophthalmicus is joined in the silk fibroin water solution, form mixed liquor, adjust pH value to 6~10, reaction obtains the Nano Silver silk fibroin protein solution;
(3) in the Nano Silver silk fibroin protein solution, add conductive agent and crosslinking agent, obtain to carry the anti-bacterial fibre material of silver by method of electrostatic spinning; Or: in silk fibroin water solution, add conductive agent and crosslinking agent, obtain not carry the anti-bacterial fibre material of silver by method of electrostatic spinning.
Described step (1) is specially: silk is boiled in the 0.02mol/L sodium carbonate liquor, spend deionised water, drying then, remove the sericin that tissue is had sensitivity response; Then the above-mentioned fibroin albumen that comes unstuck after handling is dissolved in the lysate, the pellicle of packing into then carries out dialysis treatment under the room temperature, obtains silk fibroin water solution.
Silk in the described step (1) is one or more in domestic silkworm silk, tussah, tussah silk or the ricinus silk.
The used lysate of dissolving is watery hydrochloric acid, dilute sulfuric acid, CaCl in the described step (1)
2Or a kind of in the KBr aqueous solution, wherein the concentration of each solution is preferably 0.1~0.2mol/L.
The concentration of the silver nitrate aqueous solution in the described step (2) is 0.01~0.1mol/L; Adopt hydrochloric acid or sodium hydroxide solution to adjust the pH value; Reaction time is 4~10h, and reaction temperature is 15~40 ℃.
In the described step (3), the amount that adds conductive agent and crosslinking agent accounts for respectively and adds 1~5% and 1~5% of back gross mass.
In the described step (3), the technological parameter of method of electrostatic spinning is: voltage 15~35kV, spinning distance 7~20cm, spinning solution feed quantity 0.1~3.0ml/h.
Anti-bacterial fibre material of the present invention, the experiment proved that, all inhibited to pseudomonas aeruginosa, Escherichia coli, staphylococcus aureus, staphylococcus aureus especially, therefore, can be made into hospital gauze, topical application of drug subsides, the use of antibiotic surface of a wound film.
The present invention utilizes the fibroin protein amino acid residue directly to reduce liquor argenti nitratis ophthalmicus, and fibroin protein is not only made reductant but also cook protective agent, and therefore, silver particles has the dispersed and stable of height in the anti-bacterial fibre material of formation; In addition, 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; Because gained nonwoven film (anti-bacterial fibre material) is to form by many nanofibers are cross layered in length and breadth, medicine need discharge to external diffusion gradually from fibrous inside, therefore, and the sustainable release of antiseptic in the film, thereby the persistence of maintenance drug effect.
Description of drawings
The exterior appearance figure of the anti-bacterial fibre material that carries silver that Fig. 1 prepares for embodiment 1;
The electron-microscope scanning figure of the anti-bacterial fibre material that carries silver that Fig. 2 prepares for embodiment 1;
The electron-microscope scanning figure of the anti-bacterial fibre material that carries silver that Fig. 3 prepares for embodiment 2;
The electron-microscope scanning figure of the anti-bacterial fibre material that carries silver that Fig. 4 prepares for embodiment 3;
The electron-microscope scanning figure of the anti-bacterial fibre material that carries silver that Fig. 5 prepares for embodiment 5;
Fig. 6 is the antibacterial ring schematic diagram of anti-bacterial fibre material, wherein, and A: pseudomonas aeruginosa; B: Escherichia coli; C: staphylococcus aureus;
Fig. 7 is the antibacterial ring schematic diagram of embodiment 6 gained samples, wherein, and A: pseudomonas aeruginosa; B: Escherichia coli; C: staphylococcus aureus.
The specific embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1: prepare a kind of anti-bacterial fibre material, step is as follows:
(1) mulberry silk is placed the 0.02mol/L sodium carbonate liquor handle and boil 30min, spend deionised water, drying then, remove the sericin that tissue is had sensitivity response; The fibroin albumen that will come unstuck then after handling is dissolved in 0.1mol/LCaCl
2In the aqueous solution, the pellicle of packing into then, 10% silk fibroin water solution is made fibroin albumen concentration and is in dialysis desalting, dilution;
(2) get above-mentioned silk fibroin water solution 10g, dropwise be added dropwise in the silver nitrate aqueous solution of 20ml0.01mol/L, regulating mixed solution pH value by 20%NaOH solution is that 8~9,25 ℃ of reaction 4h obtain the Nano Silver silk fibroin protein solution;
(3) take by weighing each 0.18g of Boratex and tannic acid, it is joined in the Nano Silver silk fibroin protein solution, stirring and dissolving is to forming uniform spinning solution, and wherein, the spinning solution mass fraction is 10% (the spinning solution mass fraction is meant that (fibroin+Ag+ conductive agent+crosslinking agent) is as overall mass fraction); The gained spinning solution is injected in the spin duct, and the electrostatic pressure of regulating electrostatic generator is 30kV, and flight lead is 12cm, the feed quantity of micro-injection pump spinning solution is 0.5ml/h, prepare the antibiotic surface of a wound film that thickness is about 0.015mm, be the anti-bacterial fibre material that carries silver, exterior appearance as shown in Figure 1, electron-microscope scanning figure as shown in Figure 2, as can be seen, load has silver particles on the fibroin albumen, and its average pore size is 0.5~5.0 μ m, porosity is 60~90%, and average fibre diameter is 40~100nm; In the gained anti-bacterial fibre material, the mass percent of each material is respectively: fibroin 72.4%, silver particles 1.6%, conductive agent 13.0%, crosslinking agent 13.0%;
(4) with gained nonwoven film (antibiotic surface of a wound film) behind vacuumize 12h, with double-layer plastic bag packaging seal, with the gamma-ray irradiation sterilization, standby then.
Embodiment 2: prepare a kind of anti-bacterial fibre material, step is as follows:
(1) mulberry silk is placed the 0.02mol/L sodium carbonate liquor handle and boil 30min, spend deionised water, drying then, remove the sericin that tissue is had sensitivity response; The fibroin albumen that will come unstuck then after handling is dissolved in the 0.1mol/L KBr aqueous solution, the pellicle of packing into then, and 10% silk fibroin water solution is made fibroin albumen concentration and is in dialysis desalting, dilution;
(2) get above-mentioned silk fibroin water solution 10g, dropwise be added dropwise in the silver nitrate aqueous solution of 30ml0.01mol/L, regulating mixed solution pH value by 20%NaOH solution is that 8~9,25 ℃ of reaction 4h obtain the Nano Silver silk fibroin protein solution;
(3) take by weighing each 0.20g of cerous acetate and tannic acid, it is joined in the Nano Silver silk fibroin protein solution, stirring and dissolving is to forming uniform spinning solution, and wherein, the spinning solution mass fraction is 15%; The gained spinning solution is injected in the spin duct, and the electrostatic pressure of regulating electrostatic generator is 30kV, and flight lead is 12cm, the feed quantity of micro-injection pump spinning solution is 0.5ml/h, prepare the antibiotic surface of a wound film that thickness is about 0.015mm, be the anti-bacterial fibre material, its Electronic Speculum figure as shown in Figure 3; In the gained anti-bacterial fibre material, the mass percent of each material is respectively: fibroin 69.8%, silver particles 2.2%, conductive agent 14.0%, crosslinking agent 14.0%;
(4) with gained nonwoven film (antibiotic surface of a wound film) behind vacuumize 12h, with double-layer plastic bag packaging seal, with the gamma-ray irradiation sterilization, standby then.
Embodiment 3: prepare a kind of anti-bacterial fibre material, step is as follows:
(1) mulberry silk is placed the 0.02mol/L sodium carbonate liquor handle and boil 30min, spend deionised water, drying then, remove the sericin that tissue is had sensitivity response; The fibroin albumen that will come unstuck then after handling is dissolved in the 0.1mol/L hydrochloric acid, the pellicle of packing into then, and 10% silk fibroin water solution is made fibroin albumen concentration and is in dialysis desalting, dilution;
(2) get above-mentioned silk fibroin water solution 10g, dropwise be added dropwise in the silver nitrate aqueous solution of 3ml0.1mol/L, regulating mixed solution pH value by 20%NaOH solution is that 6,25 ℃ of reaction 10h obtain the Nano Silver silk fibroin protein solution;
(3) take by weighing each 0.18g of Boratex and boric acid, it is joined in the Nano Silver silk fibroin protein solution, stirring and dissolving is to forming uniform spinning solution, and wherein, the spinning solution mass fraction is 10%; The gained spinning solution is injected in the spin duct, and the electrostatic pressure of regulating electrostatic generator is 35kV, and flight lead is 20cm, the feed quantity of micro-injection pump spinning solution is 3.0ml/h, prepare the antibiotic surface of a wound film that thickness is about 0.012mm, be the anti-bacterial fibre material, its Electronic Speculum figure as shown in Figure 4; In the gained anti-bacterial fibre material, the mass percent of each material is respectively: fibroin 73.4%, silver particles 0.2%, conductive agent 13.2%, crosslinking agent 13.2%;
(4) with gained nonwoven film (antibiotic surface of a wound film) behind vacuumize 12h, with double-layer plastic bag packaging seal, with the gamma-ray irradiation sterilization, standby then.
Embodiment 4: prepare a kind of anti-bacterial fibre material, step is as follows:
(1) mulberry silk is placed the 0.02mol/L sodium carbonate liquor handle and boil 30min, spend deionised water, drying then, remove the sericin that tissue is had sensitivity response; The fibroin albumen that will come unstuck then after handling is dissolved in the 0.1mol/L sulfuric acid, the pellicle of packing into then, and 10% silk fibroin water solution is made fibroin albumen concentration and is in dialysis desalting, dilution;
(2) get above-mentioned silk fibroin water solution 10g, dropwise be added dropwise in the silver nitrate aqueous solution of 5ml0.05mol/L, regulating mixed solution pH value by 20%NaOH solution is that 10,25 ℃ of reaction 8h obtain the Nano Silver silk fibroin protein solution;
(3) take by weighing each 0.02g of sodium metasilicate and citric acid, it is joined in the Nano Silver silk fibroin protein solution, stirring and dissolving is to forming uniform spinning solution, and wherein, the spinning solution mass fraction is 10%; The gained spinning solution is injected in the spin duct, and the electrostatic pressure of regulating electrostatic generator is 15kV, and flight lead is 7cm, and the feed quantity of micro-injection pump spinning solution is 2.0ml/h, prepares the antibiotic surface of a wound film that thickness is about 0.012mm, is the anti-bacterial fibre material; In the gained anti-bacterial fibre material, the mass percent of each material is respectively: fibroin 93.7%, silver particles 2.5%, conductive agent 1.9%, crosslinking agent 1.9%;
(4) with gained nonwoven film (antibiotic surface of a wound film) behind vacuumize 12h, with double-layer plastic bag packaging seal, with the gamma-ray irradiation sterilization, standby then.
Embodiment 5: prepare a kind of anti-bacterial fibre material, step is as follows:
(1) mulberry silk is placed the 0.02mol/L sodium carbonate liquor handle and boil 30min, spend deionised water, drying then, remove the sericin that tissue is had sensitivity response; The fibroin albumen that will come unstuck then after handling is dissolved in the 0.2mol/L hydrochloric acid, the pellicle of packing into then, and 10% silk fibroin water solution is made fibroin albumen concentration and is in dialysis desalting, dilution;
(2) get above-mentioned silk fibroin water solution 10g, dropwise be added dropwise in the silver nitrate aqueous solution of 5ml0.1mol/L, regulating mixed solution pH value by 20%NaOH solution is that 9,30 ℃ of reaction 8h obtain the Nano Silver silk fibroin protein solution;
(3) take by weighing each 0.1g of sodium metasilicate and citric acid, it is joined in the Nano Silver silk fibroin protein solution, stirring and dissolving is to forming uniform spinning solution, and wherein, the spinning solution mass fraction is 10%; The gained spinning solution is injected in the spin duct, and the electrostatic pressure of regulating electrostatic generator is 20kV, and flight lead is 12cm, the feed quantity of micro-injection pump spinning solution is 0.5ml/h, prepare the antibiotic surface of a wound film that thickness is about 0.013mm, be the anti-bacterial fibre material, its Electronic Speculum figure as shown in Figure 5; In the gained anti-bacterial fibre material, the mass percent of each material is respectively: fibroin 79.7%, silver particles 4.3%, conductive agent 8.0%, crosslinking agent 8.0%;
(4) with gained nonwoven film (antibiotic surface of a wound film) behind vacuumize 12h, with double-layer plastic bag packaging seal, with the gamma-ray irradiation sterilization, standby then.
Embodiment 6: prepare a kind of anti-bacterial fibre material, step is as follows:
(1) mulberry silk is placed the 0.02mol/L sodium carbonate liquor handle and boil 30min, spend deionised water, drying then, remove the sericin that tissue is had sensitivity response; The fibroin albumen that will come unstuck then after handling is dissolved in 0.2mol/LCaCl
2In, the pellicle of packing into then, 10% silk fibroin water solution is made fibroin albumen concentration and is in dialysis desalting, dilution;
(2) take by weighing each 0.2g of sodium acetate and boric acid, it is joined in the silk fibroin water solution, stirring and dissolving is to forming uniform spinning solution; The gained spinning solution is injected in the spin duct, and the electrostatic pressure of regulating electrostatic generator is 30kV, and flight lead is 15cm, and the feed quantity of micro-injection pump spinning solution is 2.5ml/h, prepares the antibiotic surface of a wound film that thickness is about 0.010mm, is the anti-bacterial fibre material; In the gained anti-bacterial fibre material, the mass percent of each material is respectively: fibroin 71.4%, conductive agent 14.3%, crosslinking agent 14.3%;
(3) with gained nonwoven film (antibiotic surface of a wound film) behind vacuumize 12h, with double-layer plastic bag packaging seal, with the gamma-ray irradiation sterilization, standby then.
Test the bacteriostatic experiment of 1 fibroin
Get culture dish, inoculate pseudomonas aeruginosa, Escherichia coli, staphylococcus aureus respectively with dull and stereotyped coating method, get the silk support of embodiment 1,2,3,4,5,6 preparations then, make sample (diameter 6mm), place on the culture medium, cultivate after 24 hours, observe antibacterial ring, result such as Fig. 6, shown in Figure 7, wherein, sample among Fig. 6 arranges from top to bottom, by the left-to-right sample that is followed successively by embodiment 1,2,3,4,5 correspondences; Among the A figure of Fig. 7, C is contrast (what contrast employing is the innermost layer of pasting wound dressing), and 1,2,3 are the sample that embodiment 6 obtains.As seen from the figure, the anti-bacterial fibre material for preparing of the present invention all has good fungistatic effect to pseudomonas aeruginosa, Escherichia coli, staphylococcus aureus.
Claims (10)
1. the application of silk in preparation anti-bacterial fibre material.
2. anti-bacterial fibre material, it is characterized in that: its average pore size is 0.5~5.0 μ m, and porosity is 60~90%, and average fibre diameter is 40~100nm; The percentage by weight of its component and each component is: fibroin albumen 65~98%, silver particles 0~5%, conductive agent 1~15%, crosslinking agent 1~15%.
3. a kind of anti-bacterial fibre material according to claim 2 is characterized in that: described conductive agent is a kind of in borate, acetate, the silicate.
4. a kind of anti-bacterial fibre material according to claim 2 is characterized in that: described crosslinking agent is a kind of in tannic acid, citric acid, the boric acid.
5. one kind is the method for feedstock production anti-bacterial fibre material with silk, it is characterized in that step is as follows:
(1) silk obtains silk fibroin water solution after coming unstuck, dissolve, dialysing;
(2) liquor argenti nitratis ophthalmicus is joined in the silk fibroin water solution, form mixed liquor, adjust pH value to 6~10, reaction obtains the Nano Silver silk fibroin protein solution;
(3) in the Nano Silver silk fibroin protein solution, add conductive agent and crosslinking agent, obtain to carry the anti-bacterial fibre material of silver by method of electrostatic spinning;
Or: in silk fibroin water solution, add conductive agent and crosslinking agent, obtain not carry the anti-bacterial fibre material of silver by method of electrostatic spinning.
6. the method for preparing the anti-bacterial fibre material according to claim 5 is characterized in that: the silk in the described step (1) is one or more in domestic silkworm silk, tussah, tussah silk or the ricinus silk.
7. the method for preparing the anti-bacterial fibre material according to claim 5 is characterized in that: the used lysate of dissolving is watery hydrochloric acid, dilute sulfuric acid, CaCl in the described step (1)
2Or a kind of in the KBr aqueous solution.
8. the method for preparing the anti-bacterial fibre material according to claim 5 is characterized in that: the concentration of the silver nitrate aqueous solution in the described step (2) is 0.01~0.1mol/L; Adopt hydrochloric acid or sodium hydroxide solution to adjust the pH value; Reaction time is 4~10h, and reaction temperature is 15~40 ℃.
9. the method for preparing the anti-bacterial fibre material according to claim 5 is characterized in that: in the described step (3), the amount that adds conductive agent and crosslinking agent accounts for respectively and adds 1~5% and 1~5% of back gross mass.
10. the method for preparing the anti-bacterial fibre material according to claim 5 is characterized in that: in the described step (3), the technological parameter of method of electrostatic spinning is: voltage 15~35kV, spinning distance 7~20cm, spinning solution feed quantity 0.1~3.0ml/h.
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Cited By (10)
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CN102580554A (en) * | 2012-01-11 | 2012-07-18 | 杭州天创环境科技股份有限公司 | Antibacterial porous polymeric membrane |
CN103361885A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of antibacterial silk fibroin fibrous membrane |
CN103882718A (en) * | 2014-04-11 | 2014-06-25 | 西南大学 | Preparation method of silk modified by nano-silver as well as product and application of silk modified by nano-silver |
CN105040416A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Nano-silver antibacterial blended fabric |
CN105040415A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Nano-antibacterial fabric |
CN105088780A (en) * | 2015-08-22 | 2015-11-25 | 苏州正业昌智能科技有限公司 | Nano-silver antibacterial cotton fabric |
CN106310345A (en) * | 2016-09-21 | 2017-01-11 | 天津工业大学 | Silver-loaded multi-stage structure nanometer fiber wound antimicrobial dressing |
CN106435801A (en) * | 2016-09-21 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of regenerated silk protein fiber based on rare-earth/metal ions |
CN107641965A (en) * | 2016-07-22 | 2018-01-30 | 盐城工业职业技术学院 | A kind of preparation technology of antibiotic antistatic finishing agent and its manufactured coral fleece blanket fabrics |
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CN1904159A (en) * | 2006-07-13 | 2007-01-31 | 苏州大学 | Anti bacteria natural silk composite nano-fiber material and its preparation method |
CN101044848A (en) * | 2007-04-03 | 2007-10-03 | 山东农业大学 | Nanometer silver antibiotic powder fixed by silk fibroin and preparation method thereof |
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CN1904159A (en) * | 2006-07-13 | 2007-01-31 | 苏州大学 | Anti bacteria natural silk composite nano-fiber material and its preparation method |
CN101044848A (en) * | 2007-04-03 | 2007-10-03 | 山东农业大学 | Nanometer silver antibiotic powder fixed by silk fibroin and preparation method thereof |
Cited By (13)
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CN102580554A (en) * | 2012-01-11 | 2012-07-18 | 杭州天创环境科技股份有限公司 | Antibacterial porous polymeric membrane |
CN103361885A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of antibacterial silk fibroin fibrous membrane |
CN103361885B (en) * | 2013-06-28 | 2015-11-11 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of antibacterial fibroin fiber film |
CN103882718A (en) * | 2014-04-11 | 2014-06-25 | 西南大学 | Preparation method of silk modified by nano-silver as well as product and application of silk modified by nano-silver |
CN103882718B (en) * | 2014-04-11 | 2015-11-11 | 西南大学 | Nano Silver modifies preparation method of silk and products thereof and application |
CN105040415A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Nano-antibacterial fabric |
CN105040416A (en) * | 2015-08-22 | 2015-11-11 | 苏州正业昌智能科技有限公司 | Nano-silver antibacterial blended fabric |
CN105088780A (en) * | 2015-08-22 | 2015-11-25 | 苏州正业昌智能科技有限公司 | Nano-silver antibacterial cotton fabric |
CN107641965A (en) * | 2016-07-22 | 2018-01-30 | 盐城工业职业技术学院 | A kind of preparation technology of antibiotic antistatic finishing agent and its manufactured coral fleece blanket fabrics |
CN106310345A (en) * | 2016-09-21 | 2017-01-11 | 天津工业大学 | Silver-loaded multi-stage structure nanometer fiber wound antimicrobial dressing |
CN106435801A (en) * | 2016-09-21 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of regenerated silk protein fiber based on rare-earth/metal ions |
EP3976864A4 (en) * | 2019-05-30 | 2023-09-06 | Skinner, Jack, L. | Device for polymer materials fabrication using gas flow and electrostatic fields |
US12031236B2 (en) | 2019-05-30 | 2024-07-09 | Montana Technological University | Device for polymer materials fabrication using gas flow and electrostatic fields |
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Application publication date: 20101215 |