CN102432974B - 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
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- CN102432974B CN102432974B CN201110259432.0A CN201110259432A CN102432974B CN 102432974 B CN102432974 B CN 102432974B CN 201110259432 A CN201110259432 A CN 201110259432A CN 102432974 B CN102432974 B CN 102432974B
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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 macromolecular nano biological medicine Material Field, be specifically related to polymer vesicle of a kind of surface deposition antimicrobial nano silver and preparation method thereof.
Background technology
The concern that polymer vesicle is more and more subject to various countries scientist is prepared in recent years by self-assembling technique, the change on corresponding form, structure or composition to be there is along with the change of the condition of the pH, temperature, electric field, light etc. in the external world due to the polymer molecule forming vesica, therefore the performance of the many excellences of polymer vesicle is also just imparted, all there is the application prospect of very wide model, as drug delivery, genophore, biomineralization template, microreactor, biological support etc. in a lot of field based on this polymer vesicle.
Amphipathilic block polymer can carry out self-assembly formation and have lipid bilayer vesicle in water, and polymer vesicle has significant improvement at mechanical properties tool compared with liposome vesicle.Specific surface area due to vesica is very large and have a cavity structure, and be desirable pharmaceutical carrier, with micellar phase ratio, its drug loading wants large many.
Health is one of topic of paying close attention to the most of people, but bacterium is ubiquitous, all-pervasive, their propagation and spread the health that the mankind in serious threat.Utilization is killed, anti-biotic material is killed and suppress the growth of unwanted bacteria, breeding is the important means improving level of human health.
The order that metal ion is killed, the activity of anti-bacteria is descending is: Hg, Ag, Cu, Cd, Cr, Ni, Pd, Co, Zn, Fe.And the toxicity such as Hg, Cd, Pb and Cr are wherein comparatively large, the metal being in fact used as metal sterilant only has Ag, Cu and Zn.Wherein the sterilizing ability of silver is the strongest, and its sterilizing ability is thousands of times of zinc, thus at present most study be the antiseptic-germicide of silver ion, 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 becoming anti-biotic material.
The preparation method of nano silver particles has many kinds, comprising: oxidation reduction process, mechanical milling method, chemical deposition, electrochemical plating, vapour deposition method and plasma oxidation-reduction circulation method etc.Chinese patent (patent No. CN1843134A, publication date on October 11st, 2006) discloses a kind of preparation method of nano silver coating agent, and the translucent yellow viscous liquid that this patent system is standby, is applied to effect that wound can play antibiotic and sterilizing.Chinese patent (patent No. CN101171929A, publication date on May 7th, 2008) has prepared a kind of nanometer silver antimicrobial preparation, and nanometer silver particle diameter is less, not easily reunites, 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 film complicated component, use inconvenience, uses face also narrower.
In sum, the research of the polymer vesicle of surface deposition nanometer silver is significant, has obvious advantage in the pharmaceutical carrier of particularly and vesica antibacterial at nanometer silver antimicrobial, and domesticly does not also have Patents to invent 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 preparation nanometer silver both can play the effect of nanometer silver in antibacterial bacteriostatic with vesica, the application of polymer vesicle in pharmaceutical carrier simultaneously also can be embodied.
For solving the aforementioned problems in the prior, technical scheme provided by the invention is:
A polymer vesicle for surface deposition nanometer silver, the polymkeric substance used is Amphipathilic block polymer PEO-
b-P (DMA-
stat-
tbA), nanometer silver with Silver Nitrate for silver-colored source, at P (DMA-
stat-
tbA) Ag on the polymeric film formed
+adsorb with the nitrogen element generation coordination on PDMA and diffusion, then be reductive agent in-situ preparation nanometer silver on vesica film with sodium borohydride, the particle diameter of described 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 as follows:
(1) synthesis of macromole evocating agent PEO-Br
Polyoxyethylene (PEO) and 2-bromine isobutyl acylbromide are with 1:(1 ~ 3) mol ratio join in flask, add the solvent of 100 ~ 250mL, add triethylamine, 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:(1 ~ 2) mol ratio join in round-bottomed flask, add monomer methacrylic acid dimethylin ethyl ester (DMA) and tert-butyl acrylate (
tbA), the mol ratio of PEO-Br, Dimethylaminoethyl Methacrylate and tert-butyl acrylate is 1:(20 ~ 30): (60 ~ 120), add appropriate solvent subsequently, under the anhydrous condition of anaerobic, reaction carries out 8 ~ 36h, synthetic polymer PEO-P (DMA-
stat-
tbA).
(3) self-assembly forms polymer vesicle
With the concentration of 1 ~ 20mg/mL by polymer P EO-P (DMA-
stat-
tbA) be dissolved in dimethyl formamide (DMF), under agitation, drip the distilled water doubling DMF volume with the speed of 10 ~ 50d/min, dialysis removing organic solvent, obtains vesicle solution.
(4) polymer vesicle surface deposition nanometer silver
PEO-P (the DMA-obtained after self-assembly
stat-
tbA) the surface deposition nanometer silver of vesica, with Silver Nitrate for silver-colored source, sodium borohydride is reductive agent, and the mol ratio of Silver Nitrate and sodium borohydride is 1:(1 ~ 30), obtain light yellow to brown solution after reduction, be desired product.
In the present invention, the molecular weight of the polyoxyethylene PEO described in step (1) is 1900 ~ 5000, segmented copolymer PEO-described in step (2)
b-P (DMA-
stat-
tbA) molecular weight is 8000 ~ 25000.
In the present invention, the solvent used in step (1), (2), (3) is one in toluene, methylene dichloride, tetrahydrofuran (THF), methyl alcohol, acetone, methyl-sulphoxide, dimethyl formamide to several.
Relative to scheme of the prior art, advantage of the present invention is:
(1) block polymer synthesized is biocompatibility, and the vesica that its self-assembly is formed can be applied to human body and can't produce toxic action, and this polymer vesicle has temperature-and pH-sensitivity.
(2) the generated in-situ nanometer silver of vesicle surface can not be reunited, can stable existence.
(3) preparation method is simple, and the scope of application is wider.
Accompanying drawing explanation
Fig. 1 is embodiment 1 polymer P EO-
b-P (DMA-
stat-
tbA)
1h NMR spectrogram.
Fig. 2 is the vesica change of size diagram in embodiment 1 step (4) before and after depositing nano silver.
Fig. 3 is the vesica uv-absorbing situation before and after embodiment 1 depositing nano silver.
Fig. 4 is the picture of embodiment 1 nanometer silver vesicle solution.
Fig. 5 is the transmission electron microscope photo of the polymer vesicle of loaded with nano Argent grain.Wherein: (a) is the vesica of diameter about 130nm, can be clearly seen that the hollow structure of vesica, stain on vesica film is nanometer silver, b () is the vesica of depositing nano silver, c (), for diameter is at the vesica of about 120nm, the stain on film is nanometer silver, (d) is for diameter is at the vesica of about 120nm, stain on film is nanometer silver, can be clearly seen that the cavity structure of vesica.
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1
(1) macromole evocating agent PEO
43the synthesis of-Br
By moisture wherein unnecessary for PEO and the 250mL methylbenzene azeotropic of 10g sheet distillation removing, the temperature of system drops to room temperature, changes ice-water bath into, can add 2mL triethylamine, the toluene solution 20mL of 1.9mL2-bromine isobutyl acylbromide, 40h is carried out in reaction, filter, extraction, collect organic phase, dry, filter, precipitation, suction filtration, vacuum-drying, obtains white powder macromole evocating agent PEO
43-Br.
(2) ATRP synthetic polymer
The macromole evocating agent PEO of 0.5g
43the catalyzer cuprous bromide (CuBr) of-Br, 0.035g, the monomer methacrylic acid dimethylin ethyl ester (DMA) of the part PMDETA of 0.040g, 1.16g, 3.16g tert-butyl acrylate (
tbA) and 2mL methanol solvate join in the round-bottomed flask of 50mL, anhydrous and oxygen-free, under the protective condition of nitrogen or argon gas, carries out atom transfer radical polymerization (ATRP), temperature 60
oc, carries out 48h.The polymkeric substance obtained revolves steaming, mistake silicon gel column, repeatedly dissolving revolve steaming, pump is taken out, and finally puts vacuum drying oven 24h, obtains block polymer PEO-
b-P (DMA-
stat-
tbA), this polymkeric substance is light yellow solid.
Fig. 1 is polymer P EO-
b-P (DMA-
stat-
tbA)
1h NMR spectrogram.
(3) polymer self assembles forms vesica
Polymer dissolution is in dimethyl formamide (DMF), and the solution of preparation 20mg/mL, drips with the speed of 10d/min the deionized water doubling DMF volume under the condition stirred 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, adds AgNO under stirring state
3solution, the mol ratio of silver ions and DMA is 1:5, stirs 30min under lucifuge condition, add 1.0mg sodium borohydride solids subsequently, lucifuge stirs, reaction 18h, and solution is that brown color is constant, without significantly reuniting and deposited phenomenon, solution is put into dialysis tubing to dialyse 48h, obtain the vesicle solution of surface deposition nanometer silver, the vesicle solution after this dialysis presents light yellow, solution is clarified, long-time soilless sticking phenomenon.DLS(dynamic light scattering) and TEM test result display vesica particle diameter at about 120nm.
Fig. 3 is the vesica uv-absorbing situation before and after depositing nano silver, and after can finding depositing nano silver, vesicle solution has absorption peak clearly at 400 nm wavelength places, proves the existence of nanometer silver.
Fig. 4 is the picture of nanometer silver vesicle solution.
Embodiment 2
(1) macromole evocating agent PEO
43the synthesis of-Br
By moisture wherein unnecessary for PEO and the 250mL methylbenzene azeotropic of 10g sheet distillation removing, the temperature of system drops to room temperature, changes ice-water bath into, can add 2mL triethylamine, the toluene solution 20mL of 1.9mL2-bromine isobutyl acylbromide, 40h is carried out in reaction, filter, extraction, collect organic phase, dry, filter, precipitation, suction filtration, vacuum-drying, obtains white powder macromole evocating agent PEO
43-Br.
(2) ATRP synthetic polymer
The macromole evocating agent PEO of 0.5g
43the catalyzer cuprous bromide (CuBr) of-Br, 0.035g, the monomer methacrylic acid dimethylin ethyl ester (DMA) of the part PMDETA of 0.040g, 1.16g, 2.06g tert-butyl acrylate (
tbA) and 2mL methanol solvate join in the round-bottomed flask of 50mL, anhydrous and oxygen-free, under the protective condition of nitrogen or argon gas, carries out atom transfer radical polymerization (ATRP), temperature 60
oc, carries out 48h.The polymkeric substance obtained revolves steaming, mistake silicon gel column, repeatedly dissolving revolve steaming, pump is taken out, and finally puts vacuum drying oven 24h, obtains block polymer PEO-
b-P (DMA-
stat-
tbA), this polymkeric substance is light yellow solid, more sticky at ambient temperature.
(3) polymer self assembles forms vesica
Polymer dissolution is in dimethyl formamide (DMF), and the solution of preparation 10mg/mL, drips with the speed of 10d/min the deionized water doubling DMF volume under the condition stirred 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, adds AgNO under stirring state
3solution, the mol ratio of silver ions and DMA is 1:10, stir 30min under lucifuge condition, add 2.0mg sodium borohydride solids subsequently, lucifuge stirs, reaction 18h, solution is that brown color is constant, without significantly reuniting and deposited phenomenon, solution being put into dialysis tubing and to dialyse 48h, obtain the vesicle solution of surface deposition nanometer silver, the vesicle solution after this dialysis presents light yellow.DLS(dynamic light scattering) and TEM test result display vesica particle diameter at about 120nm.
Embodiment 3
(1) macromole evocating agent PEO
45the synthesis of-Br
By moisture wherein unnecessary for PEO and the 250mL methylbenzene azeotropic of 10g sheet distillation removing, the temperature of system drops to room temperature, changes ice-water bath into, can add 2mL triethylamine, the toluene solution 20mL of 1.0mL2-bromine isobutyl acylbromide, 40h is carried out in reaction, filter, extraction, collect organic phase, dry, filter, precipitation, suction filtration, vacuum-drying, obtains white powder macromole evocating agent PEO
43-Br.
(2) ATRP synthetic polymer
The macromole evocating agent PEO of 0.5g
43the catalyzer cuprous bromide (CuBr) of-Br, 0.035g, the monomer methacrylic acid dimethylin ethyl ester (DMA) of the part PMDETA of 0.040g, 0.86g, 3.56g tert-butyl acrylate (
tbA) and 2mL methanol solvate join in the round-bottomed flask of 50mL, anhydrous and oxygen-free, under the protective condition of nitrogen or argon gas, carries out atom transfer radical polymerization (ATRP), temperature 60
oc, carries out 48h.The polymkeric substance obtained revolves steaming, mistake silicon gel column, repeatedly dissolving revolve steaming, pump is taken out, and finally puts vacuum drying oven 24h, obtains block polymer PEO
43-
b-P (DMA-
stat-
tbA), this yellow polymer is more sticky.
(3) polymer self assembles forms vesica
Polymer dissolution is in dimethyl formamide (DMF), and the solution of preparation 8mg/mL, drips with the speed of 5d/min the deionized water doubling DMF volume under the condition stirred 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, adds AgNO under stirring state
3solution, the mol ratio of silver ions and DMA is 1:20, stirs 30min, add 3.0mg sodium borohydride solids subsequently under lucifuge condition, lucifuge stirs, reaction 18h, solution is that brown color is constant, without significantly reuniting and deposited phenomenon, solution is put into dialysis tubing to dialyse 48h, obtain the vesicle solution of surface deposition nanometer silver, this vesica presents light yellow, soilless sticking.DLS(dynamic light scattering) and TEM test result display vesica particle diameter at about 120nm.
Embodiment 4
(1) macromole evocating agent PEO
45the synthesis of-Br
By moisture wherein unnecessary for PEO and the 250mL methylbenzene azeotropic of 10g sheet distillation removing, the temperature of system drops to room temperature, changes ice-water bath into, can add 2mL triethylamine, the toluene solution 20mL of 1.0mL2-bromine isobutyl acylbromide, 40h is carried out in reaction, filter, extraction, collect organic phase, dry, filter, precipitation, suction filtration, vacuum-drying, obtains white powder macromole evocating agent PEO
43-Br.
(2) ATRP synthetic polymer
The macromole evocating agent PEO of 1.0g
43the catalyzer cuprous bromide (CuBr) of-Br, 0.70g, the monomer methacrylic acid dimethylin ethyl ester (DMA) of the part PMDETA of 0.080g, 2.32g, 6.32g tert-butyl acrylate (
tbA) and 4mL methanol solvate join in the round-bottomed flask of 50mL, anhydrous and oxygen-free, under the protective condition of nitrogen or argon gas, carries out atom transfer radical polymerization (ATRP), temperature 60
oc, carries out 48h.The polymkeric substance obtained revolves steaming, mistake silicon gel column, repeatedly dissolving revolve steaming, pump is taken out, and finally puts vacuum drying oven 24h, obtains block polymer PEO
43-
b-P (DMA-
stat-
tbA).
(3) polymer self assembles forms vesica
Polymer dissolution is in dimethyl formamide (DMF), and the solution of preparation 20mg/mL, drips with the speed of 10d/min the deionized water doubling DMF volume under the condition stirred 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, adds AgNO under stirring state
3solution, the mol ratio of silver ions and DMA is 1:15,30min is stirred under lucifuge condition, add 1.5mg sodium borohydride solids subsequently, lucifuge stirs, reaction 18h, solution is that brown color is constant, without significantly reuniting and deposited phenomenon, solution being put into dialysis tubing and to dialyse 48h, obtaining the vesicle solution of surface deposition nanometer silver.DLS(dynamic light scattering) and TEM test result display vesica particle diameter at about 120nm.
The polymer vesicle obtained in embodiment 2-4 and embodiment 1 have similar performance.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to spirit of the present invention or modification, all should be encompassed within protection scope of the present invention.
Claims (3)
1. a polymer vesicle for surface deposition nanometer silver, is characterized in that: the polymkeric substance used is amphipathic nature block polymer PEO-P (DMA-
stat-
tbA) i.e. polyoxyethylene blocks poly-(dimethylaminoethyl methacrylate-random copolymerization-tert-butyl acrylate), nanometer silver with Silver Nitrate for silver-colored source, at P (DMA-
stat-
tbA) Ag on the polymeric film formed
+adsorbing with the nitrogen element generation coordination on PDMA and diffusion, is then reductive agent in-situ preparation nanometer silver on vesica film with sodium borohydride; Before depositing silver, the particle diameter of vesica is at 70 ~ 150nm, 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: amphipathic nature block polymer PEO-P (DMA-
stat-
tbA) with the mass ratio of nano silver particles be: (24 ~ 97) ︰ 1; The molecular weight of polyoxyethylene PEO is 1900 ~ 5000, described amphipathic nature block polymer PEO-P (DMA-
stat-
tbA) molecular weight is 8000 ~ 25000.
2. a preparation method for the polymer vesicle of surface deposition nanometer silver as claimed in claim 1, is characterized in that concrete steps are as follows:
(1) synthesis of macromole evocating agent PEO-Br
Polyoxyethylene and 2-bromine isobutyl acylbromide are with 1:(1 ~ 3) mol ratio join in flask, add the solvent of 100 ~ 250mL, add triethylamine, 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 N, N, N', N, ' N''-five methyl diethylentriamine, catalyzer cuprous bromide is with 1:1:(1 ~ 2) and mol ratio join in round-bottomed flask, add monomer methacrylic acid dimethylin ethyl ester and tert-butyl acrylate, the mol ratio of PEO-Br, Dimethylaminoethyl Methacrylate and tert-butyl acrylate is 1:(20 ~ 30): (60 ~ 120), add appropriate solvent subsequently, under the anhydrous condition of anaerobic, reaction carries out 8 ~ 36h, synthesizing amphipathic segmented copolymer PEO-P (DMA-
stat-
tbA);
(3) self-assembly forms polymer vesicle
With the concentration of 1 ~ 20mg/mL by amphipathic nature block polymer PEO-P (DMA-
stat-
tbA) be dissolved in dimethyl formamide, under agitation, drip the distilled water doubling DMF volume with the speed of 10 ~ 50d/min, dialysis removing organic solvent, obtains vesicle solution;
(4) polymer vesicle surface deposition nanometer silver
PEO-P (the DMA-obtained after self-assembly
stat-
tbA) the surface deposition nanometer silver of vesica, with Silver Nitrate for silver-colored source, sodium borohydride is reductive agent, and the mol ratio of Silver Nitrate and sodium borohydride is 1:(1 ~ 30), obtain light yellow to brown solution after reduction, be desired product.
3. preparation method according to claim 2, is characterized in that the molecular weight of the polyoxyethylene PEO described in step (1) is 1900 ~ 5000, the segmented copolymer PEO-P (DMA-described in step (2)
stat-
tbA) molecular weight is 8000 ~ 25000.
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| 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 |
| 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 |
| CN104551006A (en) * | 2015-01-12 | 2015-04-29 | 山东理工大学 | New method for preparing high thermal stability nanometer silver particles |
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| 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 |
| 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 |
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Cited By (1)
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| ITUB20152019A1 (en) * | 2015-07-08 | 2017-01-16 | Fabrizio Quadrini | METHOD OF MANUFACTURE OF ADDITIVES FOR NANOCOMPOSITE PLASTICS WITH ANTIMICROBIAL AND ANTIBACTERIAL PROPERTIES |
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