CN102432974A - Polymer vesica with antibacterial nano silver deposited on surface and preparation method thereof - Google Patents
Polymer vesica with antibacterial nano silver deposited on surface and preparation method thereof Download PDFInfo
- Publication number
- CN102432974A CN102432974A CN2011102594320A CN201110259432A CN102432974A CN 102432974 A CN102432974 A CN 102432974A CN 2011102594320 A CN2011102594320 A CN 2011102594320A CN 201110259432 A CN201110259432 A CN 201110259432A CN 102432974 A CN102432974 A CN 102432974A
- Authority
- CN
- China
- Prior art keywords
- vesica
- silver
- peo
- polymer
- dma
- 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.)
- Granted
Links
Images
Landscapes
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention belongs to the field of nano biological medical materials and particularly relates to polymer vesica with the surface deposited with antibacterial nano silver and a preparation method thereof. Amphipathic block polymers are self-assembled by a cosolvent method to form the vesica, and then the nano silver is generated in situ on the surface of the vesica. The polymer vesica has biocompatibility and has certain temperature and pH sensitivity; a cavity structure of the vesica can wrap various medicines; and simultaneously, due to the existence of the nano silver, the vesica also has the curative effects of sterilization and bactriostasis.
Description
Technical field
The invention belongs to high molecular nanometer biological medicine field of materials, be specifically related to polymer vesicle of a kind of surface deposition antimicrobial nano silver and preparation method thereof.
Background technology
Prepare the concern that polymer vesicle more and more receives the various countries scientist through self-assembling technique in recent years; Owing to form the variation that the polymer molecule of vesica corresponding form, structure can take place or form along with the variation of the condition of the pH in the external world, temperature, electric field, light etc.; Therefore also just given the performance of the many excellences of polymer vesicle; All has the application prospect of very wide model based on this polymer vesicle in a lot of fields, like medicine medicine carrying, genophore, biomineralization template, microreactor, biological support etc.
Amphipathilic block polymer can carry out self-assembly formation and have the duplicature vesica in water, compare polymer vesicle with liposome vesicle and have raising significantly in mechanical properties.Because the specific surface area of vesica is very big and have a cavity structure, is the ideal pharmaceutical carrier, with the micellar phase ratio, what its drug loading will be big is many.
Health is one of topic of paying close attention to the most of people, yet bacterium is ubiquitous, all-pervasive, their propagation and spread serious threat and human beings'health.Utilize to kill, anti-biotic material is killed and the growth, the breeding that suppress unwanted bacteria is an important means that improves level of human health.
The active descending order that bacterium was killed, suppressed to metals ion is: Hg, Ag, Cu, Cd, Cr, Ni, Pd, Co, Zn, Fe.And toxicity such as Hg wherein, Cd, Pb and Cr are bigger, and in fact the metal as the metal sterilant has only Ag, Cu and Zn.Wherein the sterilizing ability of silver is the strongest, and its sterilizing ability is thousands of times of zinc, thereby to study maximum at present be argentiferous ionic antiseptic-germicide, and silver ions has and destroys bacterium, the respiratory function of virus and the function of somatoblast.The excellent anti-bacterium capability of silver makes it have the potentiality that become anti-biotic material.
The preparation method of nano silver particles has many kinds, comprising: oxidation reduction process, mechanical milling method, chemical deposition, plating method, vapour deposition method and plasma oxidation-reduction circulation method etc.Chinese patent discloses a kind of preparation method of nano silver coating agent in (patent No. CN1843134A, open day on October 11st, 2006), and the translucent yellow thick liquid of this patent preparation is applied to the effect that wound can play antibiotic and sterilizing.Chinese patent (patent No. CN101171929A, open day on May 7th, 2008) has prepared a kind of nanometer silver antimicrobial preparation, and the nanometer silver particle diameter is less, is difficult for reuniting, and antibacterial effect is better.
Though the nanometer silver of above-mentioned preparation has certain antibacterial bacteriostatic usefulness, its preparation method is comparatively complicated, and the nanometer silver reagent of preparation and the complicated component of filming use inconvenience, and use face is also narrower.
In sum, the research of the polymer vesicle of surface deposition nanometer silver is significant, has remarkable advantages aspect the pharmaceutical carrier of particularly antibacterial at nanometer silver antimicrobial and vesica, and does not domesticly also have the related patent U.S. Patent No. invention to occur.
Summary of the invention
The object of the present invention is to provide polymer vesicle of a kind of surface deposition nanometer silver and preparation method thereof; Be that template prepares nanometer silver and both can bring into play the effect of nanometer silver aspect antibacterial bacteriostatic with the vesica, the application of polymer vesicle aspect pharmaceutical carrier simultaneously also can be able to embody.
For solving the aforementioned problems in the prior, technical scheme provided by the invention is:
A kind of polymer vesicle of surface deposition nanometer silver, employed polymkeric substance are Amphipathilic block polymer PEO-
b-P (DMA-
Stat-
tBA), nanometer silver is silver-colored source with Silver Nitrate, at P (DMA-
Stat-
tBA) Ag on the formed polymeric film
+With nitrogen element generation coordination and the diffusion absorption on the PDMA; Be that reductive agent original position on the vesica film generates nanometer silver then with the Peng Qinghuana; The particle diameter of said polymer vesicle is at 70～150nm, and the particle diameter of nanometer silver is 2～8nm, and the particle diameter of the vesica of depositing nano silver is at 80～160nm; Wherein: the mass ratio of amphipathic nature block polymer and nano silver particles is: (24～97) ︰ 1.
The preparation method of the polymer vesicle of a kind of surface deposition nanometer silver provided by the invention, concrete steps are following:
(1) macromole evocating agent PEO-Br's is synthetic
T 46155 (PEO) and 2-bromine isobutyl acylbromide are with 1: the mol ratio of (1～3) joins in the flask, adds the solvent of 100～250mL, adds triethylamine, and the mol ratio of triethylamine and 2-bromine isobutyl acylbromide is 1: (1～2), 12～40h is carried out in reaction.Filter, extract, wash, dissolve, precipitate last vacuum-drying and obtain macromole evocating agent PEO-Br.
(2) ATRP synthetic polymer
Macromole evocating agent PEO-Br, part PMDETA, catalyzer cuprous bromide are with 1:1: the mol ratio of (1～2) joins in the round-bottomed flask, add monomer Dimethylaminoethyl Methacrylate (DMA) and tert-butyl acrylate (
tBA), the mol ratio of PEO-Br, Dimethylaminoethyl Methacrylate and tert-butyl acrylate is 1: (20～30): (60～120), adding an amount of solvent subsequently, 8～36h, synthetic polymer PEO-P (DMA-are carried out in reaction under the anhydrous condition of anaerobic
Stat-
tBA).
(3) self-assembly forms polymer vesicle
With the concentration of 1～20mg/mL with polymer P EO-P (DMA-
Stat-
tBA) be dissolved in the N (DMF), under agitation condition, drip the zero(ppm) water that doubles the DMF volume with the speed of 10～50d/min, organic solvent is removed in dialysis, obtains vesica solution.
(4) polymer vesicle surface deposition nanometer silver
PEO-P (the DMA-that obtains after the self-assembly
Stat-
tBA) the surface deposition nanometer silver of vesica is silver-colored source with Silver Nitrate, and Peng Qinghuana is a reductive agent, and the mol ratio of Silver Nitrate and Peng Qinghuana is 1: (1～30), obtain the light yellow brown solution that arrives after the reduction, be desired product.
Among the present invention, the molecular weight of the T 46155 PEO described in the step (1) is 1900～5000, segmented copolymer PEO-described in the step (2)
b-P (DMA-
Stat-
tBA) molecular weight is 8000～25000.
Among the present invention, the solvent that uses in step (1), (2), (3) is to several kinds in toluene, methylene dichloride, THF, methyl alcohol, acetone, methyl-sulphoxide, the N.
With respect to scheme of the prior art, advantage of the present invention is:
(1) the synthetic block polymer is a biocompatibility, and the vesica that its self-assembly forms can be applied to human body and can't produce toxic action, and this polymer vesicle has temperature and the dual susceptibility of pH.
(2) nanometer silver of vesica surface in situ generation can not reunited, can stable existence.
(3) preparation method is simple, and the scope of application is wider.
Description of drawings
Fig. 1 is embodiment 1 polymer P EO-
b-P (DMA-
Stat-
tBA)
1H NMR spectrogram.
Fig. 2 is the diagram of the vesica change of size before and after the depositing nano silver in embodiment 1 step (4).
Fig. 3 is the vesica uv-absorbing situation before and after the embodiment 1 depositing nano silver.
Fig. 4 is the picture of embodiment 1 nanometer silver vesica solution.
Fig. 5 is the transmission electron microscope photo of loading nano silvery particulate polymer vesicle.Wherein: (a) be vesica about diameter 130nm, can be clearly seen that the hollow structure of vesica, the stain on the vesica film is a nanometer silver; (b) be the vesica of depositing nano silver; (c) be the vesica of diameter about 120nm, the stain on the film is a nanometer silver, (d) is the vesica of diameter about 120nm; Stain on the film is a nanometer silver, can be clearly seen that the cavity structure of vesica.
Embodiment
Further specify the present invention through embodiment below.
Embodiment 1
(1) macromole evocating agent PEO
43-Br's is synthetic
Flaky PEO of 10g and the distillation of 250mL methylbenzene azeotropic are removed wherein redundant moisture, and the temperature of system drops to room temperature, changes ice-water bath into, can add the 2mL triethylamine; 1.9mL2-the toluene solution 20mL of bromine isobutyl acylbromide, 40h is carried out in reaction, filters extraction; Collect organic phase, drying is filtered, deposition; Suction filtration, vacuum-drying obtains white powder macromole evocating agent PEO
43-Br.
(2) ATRP synthetic polymer
0.5g macromole evocating agent PEO
43-Br, the catalyzer cuprous bromide (CuBr) of 0.035g, the part PMDETA of 0.040g, the monomer Dimethylaminoethyl Methacrylate (DMA) of 1.16g, the 3.16g tert-butyl acrylate (
tBA) and the 2mL methanol solvate join in the round-bottomed flask of 50mL, anhydrous and oxygen-free carries out ATRP (ATRP), temperature 60 under the protective condition of nitrogen or argon gas
oC carries out 48h.The polymkeric substance that obtains revolves steaming, mistake silica gel pillar, steaming is revolved in dissolving repeatedly, pump is taken out, and puts vacuum drying oven 24h at last, obtains block polymer PEO-
b-P (DMA-
Stat-
tBA), this polymkeric substance is a light yellow solid.
Fig. 1 is polymer P EO-
b-P (DMA-
Stat-
tBA)
1H NMR spectrogram.
(3) the polymkeric substance self-assembly forms vesica
Polymer dissolution is prepared the solution of 20mg/mL in N (DMF), the speed with 10d/min under stirring condition drips the deionized water that doubles the DMF volume in DMF solution, and dialysis 48h removes organic solvent DMF, obtains light blue solution.
(4) polymer vesicle surface deposition nanometer silver
The concentration of polymer vesicle solution is 1.6mg/mL, and stirring state adds AgNO down
3Solution, the mol ratio of silver ions and DMA are 1:5, stir 30min under the lucifuge condition, add the 1.0mg sodium borohydride solids subsequently; Lucifuge stirs, reaction 18h, and solution is pale brown look constant; Do not have and significantly to reunite and deposited phenomenon, solution is put into the dialysis tubing 48h that dialyses, obtain the vesica solution of surface deposition nanometer silver; Vesica solution after this dialysis appears light yellow, and the solution clarification does not have agglomeration for a long time.DLS (dynamic light scattering) and TEM test result show that the particle diameter of vesica is about 120nm.
Fig. 3 is the vesica uv-absorbing situation before and after the depositing nano silver, can find depositing nano silver after vesica solution in 400 nm wavelength absorption peak is clearly arranged, prove the existence of nanometer silver.
Fig. 4 is the picture of nanometer silver vesica solution.
Embodiment 2
(1) macromole evocating agent PEO
43-Br's is synthetic
Flaky PEO of 10g and the distillation of 250mL methylbenzene azeotropic are removed wherein redundant moisture, and the temperature of system drops to room temperature, changes ice-water bath into, can add the 2mL triethylamine; 1.9mL2-the toluene solution 20mL of bromine isobutyl acylbromide, 40h is carried out in reaction, filters extraction; Collect organic phase, drying is filtered, deposition; Suction filtration, vacuum-drying obtains white powder macromole evocating agent PEO
43-Br.
(2) ATRP synthetic polymer
0.5g macromole evocating agent PEO
43-Br, the catalyzer cuprous bromide (CuBr) of 0.035g, the part PMDETA of 0.040g, the monomer Dimethylaminoethyl Methacrylate (DMA) of 1.16g, the 2.06g tert-butyl acrylate (
tBA) and the 2mL methanol solvate join in the round-bottomed flask of 50mL, anhydrous and oxygen-free carries out ATRP (ATRP), temperature 60 under the protective condition of nitrogen or argon gas
oC carries out 48h.The polymkeric substance that obtains revolves steaming, mistake silica gel pillar, steaming is revolved in dissolving repeatedly, pump is taken out, and puts vacuum drying oven 24h at last, obtains block polymer PEO-
b-P (DMA-
Stat-
tBA), this polymkeric substance is a light yellow solid, and is more sticking at ambient temperature.
(3) the polymkeric substance self-assembly forms vesica
Polymer dissolution is prepared the solution of 10mg/mL in N (DMF), the speed with 10d/min under stirring condition drips the deionized water that doubles the DMF volume in DMF solution, and dialysis 48h removes organic solvent DMF, obtains light blue solution.
(4) polymer vesicle surface deposition nanometer silver
The concentration of polymer vesicle solution is 1.6mg/mL, and stirring state adds AgNO down
3Solution, the mol ratio of silver ions and DMA are 1:10, stir 30min under the lucifuge condition; Add the 2.0mg sodium borohydride solids subsequently, lucifuge stirs, reaction 18h; Solution is pale brown look constant, do not have and significantly to reunite and deposited phenomenon, and solution is put into the dialysis tubing 48h that dialyses; Obtain the vesica solution of surface deposition nanometer silver, the vesica solution after this dialysis appears light yellow.DLS (dynamic light scattering) and TEM test result show that the particle diameter of vesica is about 120nm.
Embodiment 3
(1) macromole evocating agent PEO
45-Br's is synthetic
Flaky PEO of 10g and the distillation of 250mL methylbenzene azeotropic are removed wherein redundant moisture, and the temperature of system drops to room temperature, changes ice-water bath into, can add the 2mL triethylamine; 1.0mL2-the toluene solution 20mL of bromine isobutyl acylbromide, 40h is carried out in reaction, filters extraction; Collect organic phase, drying is filtered, deposition; Suction filtration, vacuum-drying obtains white powder macromole evocating agent PEO
43-Br.
(2) ATRP synthetic polymer
0.5g macromole evocating agent PEO
43-Br, the catalyzer cuprous bromide (CuBr) of 0.035g, the part PMDETA of 0.040g, the monomer Dimethylaminoethyl Methacrylate (DMA) of 0.86g, the 3.56g tert-butyl acrylate (
tBA) and the 2mL methanol solvate join in the round-bottomed flask of 50mL, anhydrous and oxygen-free carries out ATRP (ATRP), temperature 60 under the protective condition of nitrogen or argon gas
oC carries out 48h.The polymkeric substance that obtains revolves steaming, mistake silica gel pillar, steaming is revolved in dissolving repeatedly, pump is taken out, and puts vacuum drying oven 24h at last, obtains block polymer PEO
43-
b-P (DMA-
Stat-
tBA), this light yellow polymkeric substance is more sticking.
(3) the polymkeric substance self-assembly forms vesica
Polymer dissolution is prepared the solution of 8mg/mL in N (DMF), the speed with 5d/min under stirring condition drips the deionized water that doubles the DMF volume in DMF solution, and dialysis 48h removes organic solvent DMF, obtains light blue solution.
(4) polymer vesicle surface deposition nanometer silver
The concentration of polymer vesicle solution is 1.0mg/mL, and stirring state adds AgNO down
3Solution, the mol ratio of silver ions and DMA are 1:20, stir 30min under the lucifuge condition; Add the 3.0mg sodium borohydride solids subsequently, lucifuge stirs, reaction 18h; Solution is pale brown look constant, do not have and significantly to reunite and deposited phenomenon, and solution is put into the dialysis tubing 48h that dialyses; Obtain the vesica solution of surface deposition nanometer silver, this vesica appears light yellow, does not have and reunites.DLS (dynamic light scattering) and TEM test result show that the particle diameter of vesica is about 120nm.
Embodiment 4
(1) macromole evocating agent PEO
45-Br's is synthetic
Flaky PEO of 10g and the distillation of 250mL methylbenzene azeotropic are removed wherein redundant moisture, and the temperature of system drops to room temperature, changes ice-water bath into, can add the 2mL triethylamine; 1.0mL2-the toluene solution 20mL of bromine isobutyl acylbromide, 40h is carried out in reaction, filters extraction; Collect organic phase, drying is filtered, deposition; Suction filtration, vacuum-drying obtains white powder macromole evocating agent PEO
43-Br.
(2) ATRP synthetic polymer
1.0g macromole evocating agent PEO
43-Br, the catalyzer cuprous bromide (CuBr) of 0.70g, the part PMDETA of 0.080g, the monomer Dimethylaminoethyl Methacrylate (DMA) of 2.32g, the 6.32g tert-butyl acrylate (
tBA) and the 4mL methanol solvate join in the round-bottomed flask of 50mL, anhydrous and oxygen-free carries out ATRP (ATRP), temperature 60 under the protective condition of nitrogen or argon gas
oC carries out 48h.The polymkeric substance that obtains revolves steaming, mistake silica gel pillar, steaming is revolved in dissolving repeatedly, pump is taken out, and puts vacuum drying oven 24h at last, obtains block polymer PEO
43-
b-P (DMA-
Stat-
tBA).
(3) the polymkeric substance self-assembly forms vesica
Polymer dissolution is prepared the solution of 20mg/mL in N (DMF), the speed with 10d/min under stirring condition drips the deionized water that doubles the DMF volume in DMF solution, and dialysis 48h removes organic solvent DMF, obtains light blue solution.
(4) polymer vesicle surface deposition nanometer silver
The concentration of polymer vesicle solution is 1.8mg/mL, and stirring state adds AgNO down
3Solution, the mol ratio of silver ions and DMA are 1:15, stir 30min under the lucifuge condition; Add the 1.5mg sodium borohydride solids subsequently, lucifuge stirs, reaction 18h; Solution is pale brown look constant; Do not have and significantly to reunite and deposited phenomenon, solution is put into the dialysis tubing 48h that dialyses, obtain the vesica solution of surface deposition nanometer silver.DLS (dynamic light scattering) and TEM test result show that the particle diameter of vesica is about 120nm.
Polymer vesicle that obtains among the embodiment 2-4 and embodiment 1 have similar performance.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to let the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (4)
1. the polymer vesicle of a surface deposition nanometer silver, it is characterized in that: employed polymkeric substance is Amphipathilic block polymer PEO-P (DMA-
Stat-
tBA), nanometer silver is silver-colored source with Silver Nitrate, at P (DMA-
Stat-
tBA) Ag on the formed polymeric film
+With nitrogen element generation coordination and the diffusion absorption on the PDMA, be that reductive agent original position on the vesica film generates nanometer silver then with the Peng Qinghuana; The particle diameter of vesica is at 70～150nm before the depositing silver, and the particle diameter of the vesica of depositing nano silver is at 80～160nm, and the particle diameter of nanometer silver is 2～8nm; Wherein: the mass ratio of amphipathic nature block polymer and nano silver particles is: (24～97) ︰ 1.
2. the preparation method of the polymer vesicle of a surface deposition nanometer silver as claimed in claim 1 is characterized in that concrete steps are following:
(1) macromole evocating agent PEO-Br's is synthetic
T 46155 and 2-bromine isobutyl acylbromide are with 1: the mol ratio of (1～3) joins in the flask, adds the solvent of 100～250mL, adds triethylamine, and the mol ratio of triethylamine and 2-bromine isobutyl acylbromide is 1: (1～2), and 12～40h is carried out in reaction; Filter, extract, wash, dissolve, precipitate last vacuum-drying and obtain macromole evocating agent PEO-Br;
(2) ATRP synthetic polymer
Macromole evocating agent PEO-Br, part PMDETA, catalyzer cuprous bromide are with 1:1: the mol ratio of (1～2) joins in the round-bottomed flask; Add monomer Dimethylaminoethyl Methacrylate and tert-butyl acrylate; The mol ratio of PEO-Br, Dimethylaminoethyl Methacrylate and tert-butyl acrylate is 1: (20～30): (60～120); Add an amount of solvent subsequently, 8～36h, synthetic polymer PEO-P (DMA-are carried out in reaction under the anhydrous condition of anaerobic
Stat-
tBA);
(3) self-assembly forms polymer vesicle
With the concentration of 1～20mg/mL with polymer P EO-P (DMA-
Stat-
tBA) be dissolved in the N, under agitation condition, drip the zero(ppm) water that doubles the DMF volume with the speed of 10～50d/min, organic solvent is removed in dialysis, obtains vesica solution;
(4) polymer vesicle surface deposition nanometer silver
PEO-P (the DMA-that obtains after the self-assembly
Stat-
tBA) the surface deposition nanometer silver of vesica is silver-colored source with Silver Nitrate, and Peng Qinghuana is a reductive agent, and the mol ratio of Silver Nitrate and Peng Qinghuana is 1: (1～30), obtain the light yellow brown solution that arrives after the reduction, be desired product.
3. preparation method according to claim 2, the molecular weight that it is characterized in that the T 46155 PEO described in the step (1) is 1900～5000, the segmented copolymer PEO-P (DMA-described in the step (2)
Stat-
tBA) molecular weight is 8000～25000.
4. preparation method according to claim 2 is characterized in that the solvent that uses in step (1), (2), (3) is the one to multiple kind in toluene, methylene dichloride, THF, methyl alcohol, acetone, methyl-sulphoxide or the N.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110259432.0A CN102432974B (en) | 2011-09-05 | 2011-09-05 | Polymer vesica with antibacterial nano silver deposited on surface and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110259432.0A CN102432974B (en) | 2011-09-05 | 2011-09-05 | Polymer vesica with antibacterial nano silver deposited on surface and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102432974A true CN102432974A (en) | 2012-05-02 |
| CN102432974B CN102432974B (en) | 2015-02-18 |
Family
ID=45981335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110259432.0A Expired - Fee Related CN102432974B (en) | 2011-09-05 | 2011-09-05 | Polymer vesica with antibacterial nano silver deposited on surface and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102432974B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977293A (en) * | 2012-11-26 | 2013-03-20 | 同济大学 | Polymersome with dual response to ultrasound and pH and method for preparing same |
| CN103588931A (en) * | 2013-11-04 | 2014-02-19 | 安徽理工大学 | Double in-situ synthesis method of temperature-responsive nano silver composite hydrogel |
| CN104551006A (en) * | 2015-01-12 | 2015-04-29 | 山东理工大学 | New method for preparing high thermal stability nanometer silver particles |
| CN105412924A (en) * | 2014-08-22 | 2016-03-23 | 苏州大学 | Sugar-containing photodynamic therapy nano particles with blood stability and target ability and preparing method of sugar-containing photodynamic therapy nano particles |
| CN106632919A (en) * | 2016-09-30 | 2017-05-10 | 东莞理工学院 | Redox response type block copolymer vesica and preparation method thereof |
| CN106632920A (en) * | 2016-09-30 | 2017-05-10 | 东莞理工学院 | Ferrocenyl-contained amphipathy triblock copolymer and detecting and preparing method thereof |
| CN107474119A (en) * | 2017-06-28 | 2017-12-15 | 宁波日新恒力科技有限公司 | Antibacterial aquaporin vesica and its preparation method and application |
| CN107698969A (en) * | 2017-09-12 | 2018-02-16 | 滁州远方车船装备工程有限公司 | A kind of track traffic retardant-rubber tenacity increased nylon bellows material and preparation method thereof |
| CN111450058A (en) * | 2020-04-17 | 2020-07-28 | 于力 | Preparation of nano zero-valent silver spray for sterilizing and healing animal wound and preparation method thereof |
| CN115197347A (en) * | 2021-04-13 | 2022-10-18 | 中国石油化工股份有限公司 | Preparation method of bacteriostatic chromium-polyethylene catalyst |
| CN115486444A (en) * | 2022-09-21 | 2022-12-20 | 河北省科学院能源研究所 | Preparation method of silver-loaded polymer vesicle |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITUB20152019A1 (en) * | 2015-07-08 | 2017-01-16 | Fabrizio Quadrini | METHOD OF MANUFACTURE OF ADDITIVES FOR NANOCOMPOSITE PLASTICS WITH ANTIMICROBIAL AND ANTIBACTERIAL PROPERTIES |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772706A (en) * | 2005-10-24 | 2006-05-17 | 天津大学 | Prepn process of nanometer tin oxide material with surface decorating silver |
-
2011
- 2011-09-05 CN CN201110259432.0A patent/CN102432974B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772706A (en) * | 2005-10-24 | 2006-05-17 | 天津大学 | Prepn process of nanometer tin oxide material with surface decorating silver |
Non-Patent Citations (1)
| Title |
|---|
| UMA CHATTERJEE ET AL.: "Dispersion of Functionalized Silver Nanoparticles in Polymer Matrices: Stability, Characterization, and Physical Properties", 《POLYMER COMPOSITES》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977293B (en) * | 2012-11-26 | 2014-07-16 | 同济大学 | Polymersome with dual response to ultrasound and pH and method for preparing same |
| CN102977293A (en) * | 2012-11-26 | 2013-03-20 | 同济大学 | Polymersome with dual response to ultrasound and pH and method for preparing same |
| CN103588931A (en) * | 2013-11-04 | 2014-02-19 | 安徽理工大学 | Double in-situ synthesis method of temperature-responsive nano silver composite hydrogel |
| CN103588931B (en) * | 2013-11-04 | 2015-08-19 | 安徽理工大学 | Two in-situ synthetic methods of temperature-responsive nano silver composite hydrogel |
| CN105412924B (en) * | 2014-08-22 | 2018-10-16 | 苏州大学 | Nano-particle of the photodynamic therapy containing sugar and preparation method thereof with blood stability and targeting |
| CN105412924A (en) * | 2014-08-22 | 2016-03-23 | 苏州大学 | Sugar-containing photodynamic therapy nano particles with blood stability and target ability and preparing method of sugar-containing photodynamic therapy nano particles |
| CN104551006A (en) * | 2015-01-12 | 2015-04-29 | 山东理工大学 | New method for preparing high thermal stability nanometer silver particles |
| CN106632919B (en) * | 2016-09-30 | 2019-04-30 | 东莞理工学院 | A kind of redox response type block copolymer vesicles and preparation method thereof |
| CN106632920A (en) * | 2016-09-30 | 2017-05-10 | 东莞理工学院 | Ferrocenyl-contained amphipathy triblock copolymer and detecting and preparing method thereof |
| CN106632920B (en) * | 2016-09-30 | 2019-03-01 | 东莞理工学院 | One kind amphipathic three block copolymer containing ferrocenyl and its detection, preparation method |
| CN106632919A (en) * | 2016-09-30 | 2017-05-10 | 东莞理工学院 | Redox response type block copolymer vesica and preparation method thereof |
| CN107474119A (en) * | 2017-06-28 | 2017-12-15 | 宁波日新恒力科技有限公司 | Antibacterial aquaporin vesica and its preparation method and application |
| CN107474119B (en) * | 2017-06-28 | 2020-07-10 | 宁波日新恒力科技有限公司 | Antibacterial aquaporin vesicles and preparation method and application thereof |
| CN107698969A (en) * | 2017-09-12 | 2018-02-16 | 滁州远方车船装备工程有限公司 | A kind of track traffic retardant-rubber tenacity increased nylon bellows material and preparation method thereof |
| CN111450058A (en) * | 2020-04-17 | 2020-07-28 | 于力 | Preparation of nano zero-valent silver spray for sterilizing and healing animal wound and preparation method thereof |
| CN115197347A (en) * | 2021-04-13 | 2022-10-18 | 中国石油化工股份有限公司 | Preparation method of bacteriostatic chromium-polyethylene catalyst |
| CN115197347B (en) * | 2021-04-13 | 2023-08-11 | 中国石油化工股份有限公司 | Preparation method of antibacterial polyethylene chromium catalyst |
| CN115486444A (en) * | 2022-09-21 | 2022-12-20 | 河北省科学院能源研究所 | Preparation method of silver-loaded polymer vesicle |
| CN115486444B (en) * | 2022-09-21 | 2024-01-30 | 河北省科学院能源研究所 | Preparation method of silver-loaded polymer vesicle |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102432974B (en) | 2015-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102432974A (en) | Polymer vesica with antibacterial nano silver deposited on surface and preparation method thereof | |
| CN102671201A (en) | Antibacterial nano silver modified polymeric micelle and preparation method thereof | |
| Li et al. | Metal–organic-framework-based materials for antimicrobial applications | |
| Shalaby et al. | Electrospun nanofibers hybrid composites membranes for highly efficient antibacterial activity | |
| Islam et al. | Mussel-inspired immobilization of silver nanoparticles toward antimicrobial cellulose paper | |
| Abdelgawad et al. | Antimicrobial wound dressing nanofiber mats from multicomponent (chitosan/silver-NPs/polyvinyl alcohol) systems | |
| Soumia et al. | Fe3O4-alginate nanocomposite hydrogel beads material: One-pot preparation, release kinetics and antibacterial activity | |
| Kong et al. | Antibacterial properties of novel poly (methyl methacrylate) nanofiber containing silver nanoparticles | |
| Prabhu et al. | Silver nanoparticles: mechanism of antimicrobial action, synthesis, medical applications, and toxicity effects | |
| CN104174074B (en) | A kind of medication coat composition that is applicable to be coated in implantation or interventional medical device surface | |
| CN104353127A (en) | Composite antibacterial material of graphene quantum dot and fibroin, preparation and application | |
| Elbarbary et al. | Radiation synthesis and characterization of polyvinyl alcohol/chitosan/silver nanocomposite membranes: antimicrobial and blood compatibility studies | |
| Xiao et al. | Polyelectrolyte multilayer-assisted immobilization of zero-valent iron nanoparticles onto polymer nanofibers for potential environmental applications | |
| Du et al. | An injectable multifunctional hydrogel for eradication of bacterial biofilms and wound healing | |
| Li et al. | How effective are metal nanotherapeutic platforms against bacterial infections? A comprehensive review of literature | |
| CN101934202B (en) | Method for preparing antimicrobial polymer separation membrane | |
| Shahini et al. | Recent innovations in synthesis/characterization of advanced nano-porous metal-organic frameworks (MOFs); current/future trends with a focus on the smart anti-corrosion features | |
| CN102702451B (en) | High-efficiency and antibacterial polymeric micelle with high pH sensibility and biocompatibility and preparation method thereof | |
| CN113751079B (en) | Perovskite-titanium dioxide nano composite photocatalyst loaded by biological material and construction method and application thereof | |
| Zhang et al. | Ionic liquid assisted electrospun cellulose acetate fibers for aqueous removal of triclosan | |
| CN104177628A (en) | Composite nano sliver polymer antibacterial micelle and preparation method thereof | |
| Phan et al. | The mechanistic actions of different silver species at the surfaces of polyacrylonitrile nanofibers regarding antibacterial activities | |
| CN101927006A (en) | Preparation method of pH-responded metal organic coordination polymer based on medicament | |
| Sobhani et al. | Graft hyper-branched dendrimer onto WS2 nanosheets modified Poly (N-Vinylcaprolactam) as a thermosensitive nanocarrier for Pioglitazone delivery using near-infrared radiation | |
| Li et al. | Hybridization of carboxymethyl chitosan with bimetallic MOFs to construct renewable metal ion “warehouses” with rapid sterilization and long-term antibacterial effects |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150218 Termination date: 20170905 |