CN103642070A - Antibiotic composite membrane of nano-silk fibroin-chitosan-nano-silver - Google Patents
Antibiotic composite membrane of nano-silk fibroin-chitosan-nano-silver Download PDFInfo
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- CN103642070A CN103642070A CN201310555491.1A CN201310555491A CN103642070A CN 103642070 A CN103642070 A CN 103642070A CN 201310555491 A CN201310555491 A CN 201310555491A CN 103642070 A CN103642070 A CN 103642070A
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- nanometer
- fibroin
- chitosan
- silver
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- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000012528 membrane Substances 0.000 title claims abstract description 22
- 230000003115 biocidal effect Effects 0.000 title abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 40
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 108010022355 Fibroins Proteins 0.000 claims abstract description 28
- 229920001661 Chitosan Polymers 0.000 claims abstract description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 235000013305 food Nutrition 0.000 claims abstract description 3
- 239000012567 medical material Substances 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims description 38
- 239000004332 silver Substances 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 30
- 230000000845 anti-microbial effect Effects 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005286 illumination Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000012460 protein solution Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000003242 anti bacterial agent Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 description 16
- 230000000844 anti-bacterial effect Effects 0.000 description 10
- 229940088710 antibiotic agent Drugs 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 244000005700 microbiome Species 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 241000233866 Fungi Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention discloses an antibiotic composite membrane of nano-silk fibroin-chitosan-nano-silver and a preparation method thereof. Nano-silver is prepared by in-situ reduction of silver nitrate with nano-silk fibroin and chitosan, and then a nano-silk fibroin-nano-silver antibiotic composite membrane is prepared further. The antibiotic composite membrane is widely applicable to food packages, hygienic products, and medical materials.
Description
Technical field
The invention belongs to nano material, anti-biotic material technical field, be specifically related to a kind of nanometer fibroin-chitosan-nanometer silver antimicrobial composite membrane.
Background technology
Bacterium is ubiquitous, all-pervasive, their propagation and spread the health that the mankind in serious threat.Along with a large amount of uses of the chemicalses such as microbiotic, sterilizing agent and sterilant, the bacterial dissociation population being caused by resistance is more and more, and the global bacterium Disaster Event causing thus occurs again and again.For suppressing the generation of this bacterioid disaster, research and development and application novel antibacterial material are imperative.Anti-biotic material is mainly divided into inorganic antibacterial material, organic anti-bacterial material, organic-inorganic composite antimicrobial material at present.
Along with people constantly increase the requirement for all kinds of anti-biotic materials, the exploitation of anti-biotic material has obtained unprecedented attention, the emphasis of paying close attention to and the main growth point of demand are organic polymer anti-biotic materials, now just at the antibiotic polymer material of extensive exploitation, adopt respectively the technological line that adds inorganic salt antiseptic-germicide and organic compound antiseptic-germicide, but organic synthesis antimicrobial additive all belongs to organic compound, its volatility, perviousness and transport property are strong, exist and easily lose efficacy and hygienic safety hidden danger.
Summary of the invention
For addressing the above problem, the object of the present invention is to provide a kind of nanometer fibroin-chitosan-nanometer silver antimicrobial composite membrane and preparation method thereof, this matrix material can be widely used in food product pack, sanitary product, field of medical materials.
Adopt nano thread fibroin, chitosan in situ reduction Silver Nitrate to prepare nanometer silver, and further prepare nano thread fibroin-nanometer silver antimicrobial composite membrane, concrete steps are as follows:
(1) the nanometer silk fibroin water solution that preparation quality concentration is 0.5 ~ 3%, the chitosan aqueous solution that mass concentration is 8.5-10%, dropwise adds sodium hydroxide, regulator solution pH to 6-8 under stirring;
(2) under stirring, in step (1) gained solution, add Silver Nitrate, obtain the mixed solution that silver nitrate concentration is 20 ~ 45 mmol/L, continue to stir 30min;
(3) mixing solutions step (2) being obtained carries out illumination, and illumination action time is 12 ~ 20 h, obtains uniform nano thread fibroin, chitosan, nanometer silver mixing solutions;
(4) mixing solutions step (3) being obtained joins in the nanometer silk fibroin protein solution that massfraction is 2%-5%, controlling silver-colored add-on is 0.08% ~ 1.5% of nano thread fibroin consumption, is then prepared into nanometer fibroin-chitosan-nanometer silver antimicrobial composite membrane;
Positively effect of the present invention is: nanometer silver is to take the novel product that nanotechnology forms as foundation development, at aspects such as electricity, optics and catalysis, has very excellent characteristic.Simultaneously due to surface effects, volume effect, quantum size effect and macro quanta tunnel effect, it is the incomparable antibacterial effect of anti-biotic material that nanometer silver has conventional silver, the nanometer silver of minute quantity can make microorganism comprise that the Growth and reproduction of bacterium, fungi, yeast etc. keeps lower level, and effect is lasting.Based on this, nano silver antibacterial material has application prospect very widely, comprises various antibacterial dress ornaments, antibacterials, toy for children, personal-care supplies etc.
Nano thread fibroin, as the reductive agent of Silver Nitrate and the stablizer of nanometer silver, without additional other chemical reagent, pollutes few.
Required illumination condition can be sunlight or simulated solar illumination, is conveniently easy to get.
Reaction conditions is gentle, without severe condition such as High Temperature High Pressure, and good energy-conserving effect.
Prepared nanometer silver particle diameter little (about 5-7 nm), size distribution are even.Little particle diameter has higher specific surface area, also just means higher anti-microbial activity and lower consumption.
Nanometer silver good stability, places and still can keep good dispersiveness, and can dissolve each other with plurality of reagents half a year, therefore has Application Areas widely.
Nano thread fibroin and chitosan are as mould material matrix, and biocompatibility and biological degradability are good.
Antibacterial high efficiency.In material 2 h that silver mass concentration is 1%, sterilizing rate can reach more than 99.9%.
Broad-spectrum antibacterial property.Prepared anti-biotic material has all shown excellent resistance for gram-positive microorganism and Gram-negative bacteria.
Embodiment
Below in conjunction with embodiment, describe technical scheme of the present invention in detail, but protection domain is not so limited.
1 one kinds of nanometer fibroin-chitosan-nanometer silver antimicrobial composite membranes of embodiment
Adopt nano thread fibroin, chitosan in situ reduction Silver Nitrate to prepare nanometer silver, and further prepare nano thread fibroin-nanometer silver antimicrobial composite membrane, concrete steps are as follows:
(1) the nanometer silk fibroin water solution that preparation quality concentration is 0.5%, the chitosan aqueous solution that mass concentration is 10%, dropwise adds sodium hydroxide, regulator solution pH to 7 under stirring;
(2) under stirring, in step (1) gained solution, add Silver Nitrate, obtain the mixed solution that silver nitrate concentration is 20 mmol/L, continue to stir 30min;
(3) mixing solutions step (2) being obtained carries out illumination, and illumination action time is 12 h, obtains uniform nano thread fibroin, chitosan, nanometer silver mixing solutions;
(4) it is in 2%% nanometer silk fibroin protein solution that mixing solutions step (3) being obtained joins massfraction, controlling silver-colored add-on is 0.08%% of nano thread fibroin consumption, then adopts supercritical carbon dioxide process to be prepared into nanometer fibroin-chitosan-nanometer silver antimicrobial composite membrane;
2 one kinds of nanometer fibroin-chitosan-nanometer silver antimicrobial composite membranes of embodiment
Adopt nano thread fibroin, chitosan in situ reduction Silver Nitrate to prepare nanometer silver, and further prepare nano thread fibroin-nanometer silver antimicrobial composite membrane, concrete steps are as follows:
(1) the nanometer silk fibroin water solution that preparation quality concentration is 3%, the chitosan aqueous solution that mass concentration is 8.5%, dropwise adds sodium hydroxide, regulator solution pH to 7 under stirring;
(2) under stirring, in step (1) gained solution, add Silver Nitrate, obtain the mixed solution that silver nitrate concentration is 45 mmol/L, continue to stir 30min;
(3) mixing solutions step (2) being obtained carries out illumination, and illumination action time is 15 h, obtains uniform nano thread fibroin, chitosan, nanometer silver mixing solutions;
(4) it is in 5% nanometer silk fibroin protein solution that mixing solutions step (3) being obtained joins massfraction, controlling silver-colored add-on is 0.08% of nano thread fibroin consumption, then use deionized water wash 5 times, room temperature is dried, and obtains nanometer fibroin-chitosan-nanometer silver antimicrobial composite membrane;
3 one kinds of nanometer fibroin-chitosan-nanometer silver antimicrobial composite membranes of embodiment
Adopt nano thread fibroin, chitosan in situ reduction Silver Nitrate to prepare nanometer silver, and further prepare nano thread fibroin-nanometer silver antimicrobial composite membrane, concrete steps are as follows:
(1) the nanometer silk fibroin water solution that preparation quality concentration is 2%, the chitosan aqueous solution that mass concentration is 9.2%, dropwise adds sodium hydroxide, regulator solution pH to 8 under stirring;
(2) under stirring, in step (1) gained solution, add Silver Nitrate, obtain the mixed solution that silver nitrate concentration is 40mmol/L, continue to stir 30min;
(3) mixing solutions step (2) being obtained carries out illumination, and illumination action time is 20h, obtains uniform nano thread fibroin, chitosan, nanometer silver mixing solutions;
(4) it is in 4% nanometer silk fibroin protein solution that mixing solutions step (3) being obtained joins massfraction, controlling silver-colored add-on is 1% of nano thread fibroin consumption, then adopts the green mode of non-organic solvent to be prepared into nanometer fibroin-chitosan-nanometer silver antimicrobial composite membrane;
Composite membrane of the present invention has antibacterial high efficiency.In material 2 h that silver mass concentration is 1%, sterilizing rate can reach more than 99.9%.Prepared anti-biotic material has all shown excellent resistance for gram-positive microorganism and Gram-negative bacteria.
Claims (2)
1. a preparation method for nanometer fibroin-chitosan-nanometer silver antimicrobial composite membrane, is characterized in that:
Nano thread fibroin, chitosan in situ reduction Silver Nitrate are prepared nanometer silver, and further prepare nano thread fibroin-nanometer silver antimicrobial composite membrane, and concrete steps are as follows:
(1) the nanometer silk fibroin water solution that preparation quality concentration is 0.5 ~ 3%, the chitosan aqueous solution that mass concentration is 8.5-10%, dropwise adds sodium hydroxide, regulator solution pH to 6-8 under stirring;
(2) under stirring, in step (1) gained solution, add Silver Nitrate, obtain the mixed solution that silver nitrate concentration is 20 ~ 45 mmol/L, continue to stir 30min;
(3) mixing solutions step (2) being obtained carries out illumination, and illumination action time is 12 ~ 20 h, obtains uniform nano thread fibroin, chitosan, nanometer silver mixing solutions;
(4) mixing solutions step (3) being obtained joins in the nanometer silk fibroin protein solution that massfraction is 2%-5%, controlling silver-colored add-on is 0.08% ~ 1.5% of nano thread fibroin consumption, is then prepared into nanometer fibroin-chitosan-nanometer silver antimicrobial composite membrane;
Nanometer fibroin-chitosan-nanometer silver antimicrobial matrix material that a kind of preparation method as described in claim 1 obtains.
2. the application of the fibroin-chitosan-nanometer silver antimicrobial of the nanometer as described in claim 2 matrix material in food product pack, sanitary product, medical material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310555491.1A CN103642070A (en) | 2013-11-11 | 2013-11-11 | Antibiotic composite membrane of nano-silk fibroin-chitosan-nano-silver |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310555491.1A CN103642070A (en) | 2013-11-11 | 2013-11-11 | Antibiotic composite membrane of nano-silk fibroin-chitosan-nano-silver |
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| CN103642070A true CN103642070A (en) | 2014-03-19 |
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| CN201310555491.1A Pending CN103642070A (en) | 2013-11-11 | 2013-11-11 | Antibiotic composite membrane of nano-silk fibroin-chitosan-nano-silver |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289727A (en) * | 2014-10-22 | 2015-01-21 | 苏州正业昌智能科技有限公司 | Method for preparing nano-silver by taking modified chitosan as reducing agent |
| CN104817706A (en) * | 2015-03-12 | 2015-08-05 | 浙江海洋学院 | Preparation method for Setipinna tenuifilis protein nano-silver antibacterial film |
| 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 |
| CN106633927A (en) * | 2016-12-30 | 2017-05-10 | 常州工程职业技术学院 | Preparation method of antibacterial composite silver nanoparticle-silk fibroin film |
| CN110204756A (en) * | 2019-06-18 | 2019-09-06 | 合肥工业大学 | High-strength anti-biotic material of a kind of chitosan-loaded silver and preparation method thereof |
| CN110790987A (en) * | 2019-10-18 | 2020-02-14 | 宿迁市江南大学产业技术研究院 | Chitosan-silk fibroin edible film and preparation method thereof |
| CN117694398A (en) * | 2023-11-10 | 2024-03-15 | 上海交通大学 | Preparation method and application of silk fibroin-containing composite edible membrane liquid |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289727A (en) * | 2014-10-22 | 2015-01-21 | 苏州正业昌智能科技有限公司 | Method for preparing nano-silver by taking modified chitosan as reducing agent |
| CN104817706A (en) * | 2015-03-12 | 2015-08-05 | 浙江海洋学院 | Preparation method for Setipinna tenuifilis protein nano-silver antibacterial film |
| 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 |
| CN106633927A (en) * | 2016-12-30 | 2017-05-10 | 常州工程职业技术学院 | Preparation method of antibacterial composite silver nanoparticle-silk fibroin film |
| CN106633927B (en) * | 2016-12-30 | 2019-02-22 | 常州工程职业技术学院 | A kind of preparation method of silver nanoparticle-silk fibroin antibacterial composite film |
| CN110204756A (en) * | 2019-06-18 | 2019-09-06 | 合肥工业大学 | High-strength anti-biotic material of a kind of chitosan-loaded silver and preparation method thereof |
| CN110204756B (en) * | 2019-06-18 | 2022-02-11 | 合肥工业大学 | A kind of chitosan silver-loaded high-strength antibacterial material and preparation method thereof |
| CN110790987A (en) * | 2019-10-18 | 2020-02-14 | 宿迁市江南大学产业技术研究院 | Chitosan-silk fibroin edible film and preparation method thereof |
| CN110790987B (en) * | 2019-10-18 | 2021-07-02 | 宿迁市江南大学产业技术研究院 | A kind of chitosan-silk fibroin edible film and preparation method thereof |
| CN117694398A (en) * | 2023-11-10 | 2024-03-15 | 上海交通大学 | Preparation method and application of silk fibroin-containing composite edible membrane liquid |
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Application publication date: 20140319 |