CN104588645B - A kind of ag nano-cluster compound with antibacterial activity and preparation method thereof - Google Patents
A kind of ag nano-cluster compound with antibacterial activity and preparation method thereof Download PDFInfo
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- CN104588645B CN104588645B CN201510059292.0A CN201510059292A CN104588645B CN 104588645 B CN104588645 B CN 104588645B CN 201510059292 A CN201510059292 A CN 201510059292A CN 104588645 B CN104588645 B CN 104588645B
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Abstract
The invention discloses a kind of nanometer silver cluster compound with antibacterial activity and preparation method thereof, nanometer silver cluster compound uses polymer and the argent ion of biocompatibility, generate the stable solution of the polymer inclusion of nanometer silver cluster compound under light illumination, nanometer silver cluster compound has the physical characteristic of argent nanoparticle, such as surface plasma, visible ray can be absorbed, thus lose the sensitivity to light, can be present in steadily in the long term in solution, and there is the reactivity of the high surface of argent nanoparticle, there is stronger antibacterial activity.Staphylococcus aureus is carried out antibacterial activity test show, minimal inhibitory concentration (MIC) 5 μ g/mL, reached the least concentration limit that current domestic and international similar best product can reach.
Description
Technical field
The present invention relates to metal nanometer cluster compound, a kind of nanometer silver cluster compound with antibacterial activity and preparation side thereof
Method.
Background technology
Known to there is the metal of antibacterial activity mainly have silver, zinc, cadmium, chromium, cobalt, nickel.But, as follows, argent
Antibacterial activity higher relative to other metals, and the toxicity of life entity compares again relatively low by it, so as far back as 1881,
Argent (the mainly positive monovalent ion Ag of silver+) be just widely used in medical science as antibacterials.Relative to biological antibiotic,
For it typically produces antibacterial action by unique binding mode, argent can have multiple binding mode, as can and albumen
The sulfydryl sulfur of the disulfide bond of matter combines, and makes protein folding misplace, and the protein that dislocation folds is translocated to epicyte and causes
Inactivation;The Fe-S cluster compound system of interference ferrum stable state, increases intracellular Fe2+Concentration, may result in activation superoxides system;
Silver ion can interact with the DNA of base pair, thus prevents DNA replication dna;Also can interrupt what TCA circulation drove
The multiple binding modes such as the generation of active oxygen (ROS) participate in antibacterial action, thus are easily widely accepted and use.
At present, the antibacterial of the argent of use is usually argent (Ag+1) aqueous solubilized compound, or the silver oxide of solid
(Ag+1).Its general character is both unstable, the most active low.Such as monovalence silver under light illumination, it is easily varied into argent, and solid
Silver oxide can only use paste, it is impossible to wiring solution-forming preparation uses.
Summary of the invention
It is an object of the invention to provide a kind of ag nano-cluster compound with antibacterial activity and preparation method thereof.
A kind of nanometer silver cluster compound with antibacterial activity that the present invention provides, is by the silver atom cluster compound of following different structure
Mixture with polymer monomer composition;
Described silver atom cluster compound has Ag2、Ag3、Ag4、Ag5、Ag6、Ag7、Ag8、Ag9、Ag11And Ag13(nanometer silver bunch closes
Fig. 1 is shown in by thing Species Structure schematic diagram);
Described polymer monomer is the mixture of polymethyl methacrylate and polyvinylpyrrolidone.
The preparation method of a kind of nanometer silver cluster compound with antibacterial activity that the present invention provides, as in figure 2 it is shown, include as follows
Step:
By silver nitrate and water miscible polymer monomer, it is dissolved in distilled water at 2: 1 in molar ratio, is stirred at room temperature at least 10
Minute, form lurid clear solution;Then this solution is transferred in transparent glass drying oven, by the monochrome of 300 nanometers
Light source radiates, radiated time 24-25 hour, until forming wine-colored solution;Finally by wine-colored solution, through entering
One step dialysis, removes the little molecule of impurity, obtains pure nanometer silver cluster compound;Described polymer monomer is polymethyl
Acid methyl ester and the mixture of polyvinylpyrrolidone, their mass ratio is 1: 1.This ag nano-cluster compound not only has very
Good antibacterial effect, and in the solution being present in various solvent that can be stable.
Above-mentioned light-catalysed extent of chemical reaction, it is also possible to detect with absorption spectrum.Along with reaction is carried out, absorbance meeting
Incrementally increasing, after waiting reaction to complete, absorbance will be invariable, as shown in Figure 4.
Described silver nitrate can use silver sulfate, silver acetate to substitute.
High molecular nanometer Silver Clusters compound of the present invention can make product such as Silver Clusters compound gel, the Silver Clusters of various antibiotic preparation
Polymer solution, Silver Clusters compound spray etc..
Beneficial effects of the present invention:
Compared with prior art, the present invention uses polymer and the argent ion of biocompatibility, generates nanometer silver under light illumination
The stable solution of the polymer inclusion of cluster compound, nanometer silver has the physical characteristic of argent nanoparticle, such as surface plasma
Property, visible ray can be absorbed, thus lose the sensitivity to light, it is possible to be present in steadily in the long term in solution, and again
There is the reactivity of the high surface of argent nanoparticle, so having stronger antibacterial activity.Staphylococcus aureus is entered
Row antibacterial activity test shows, minimal inhibitory concentration (MIC) 5 μ g/mL, has reached current domestic and international similar best product energy
The least concentration limit reached.
Accompanying drawing explanation
Fig. 1 nanometer silver cluster compound species schematic diagram
Fig. 2 nanometer silver cluster compound synthesis schematic diagram
Fig. 3 compares in the progress of same time span difference monochromater catalytic reaction.
Fig. 4 detects 300nm monochromatic light and is catalyzed the visible ray spectrogram of progress in time.
Fig. 5 300nm photocatalysis generates the mass spectrum that the Mass Spectrometer Method of solution arrives.
Species analysis result corresponding to the mass spectrum that Fig. 6 detects.
Fig. 7 is to staphylococcus aureus antibacterial activity test Comparative result.
Detailed description of the invention
The selection of embodiment 1 synthesis condition and determining
The selection of photochemical reaction light source
General photochemical reaction, uses monochromater relatively good, can produce more single product, it is to avoid other pair is anti-
Should.So monochromater is selected in this preparation.First by the monochromater of different wave numbers carry out light-catalyzed reaction (720nm, 505
Nm, 405nm, 365nm, 300nm and 254nm), it was found that the light-catalyzed reaction of 720nm and 505nm is very
Slowly, but 405nm, 365nm, 300nm and 254nm light-catalyzed reaction, relative to the light source of the first two different wave length
The fastest, although difference is not very big, but has difference between them yet, and in a word, wavelength is the shortest, and energy is the highest, and reaction is more
Hurry up (shown in Fig. 3).Illustrating to guarantee that reaction is rapidly completed, monochromater has relatively high energy it is critical that factor.No
But the light-catalyzed reaction of 300nm is second fast, and absorbing light spectral peak is also the widest.General peak width means to generate
Species number the most.It is demonstrated experimentally that the solution of the light-catalyzed reaction of 300nm is the species generating nanometer silver cluster compound
The solution that number is most.Sum it up, the monochromater of 300nm is chosen as synthetically prepared optimal light source.
Polymer and the selection of argent proportioning
By changing the ratio of silver ion and polymer monomer, selecting 300nm light to irradiate, experiment demonstrates silver ion and polymer
The ratio of monomer is 2, i.e. two silver ions, during relative to a monomer, can generate maximized nanometer silver cluster compound
Species quantity, and solution can keep stable in During Illumination.Ratio less than 2, it is also possible to generation product, but illumination
During, system is unstable, black precipitate easily occurs.More than 2, highly stable in the present During Illumination of system, but,
Can be only generated the least species, such as Ag2And Ag3.So ratio is 2 to be optimum selection.
The radiated time of light source selects
The monochromater that we use, monochromaticity is the best, but power is smaller, only 0.5mW, the solution of 10 milliliters, makes
Irradiating with this light source, use the progress of absorption spectrum detection reaction simultaneously, question response completes, and needs 24-25 hour (see Fig. 4).
Silver selects: silver nitrate, silver sulfate, silver acetate
Polymer monomer selects: polymethyl methacrylate and polyvinylpyrrolidone.Their structural formula is:
The preparation of embodiment 2 high molecular nanometer Silver Clusters compound:
1) polymethyl methacrylate and polyvinylpyrrolidone in mass ratio 1: 1 are mixed, and be configured to the polymer of 10mM
Monomer solution is standby;
2) take silver nitrate aqueous solution 10 milliliters (10mM) and 5 milliliters of polymer monomer aqueous solution, stir at least under room temperature
10 minutes, form lurid clear solution, be encapsulated in the vial of 20 milliliters, then with the monochromater spoke of 300nm
Penetrating (0.5mW), around live by metal aluminum foil paper cap, Continuous irradiation has been reacted for 24 hours;
3) reaction solution is through dialysis, removes the little molecule of impurity, obtains pure nanometer silver cluster compound.
Obtain mass spectrum with mass spectrometer mensuration end product and see Fig. 5, Fig. 6.Illustrate in product containing following silver atom cluster compound
Ag2、Ag3、Ag4、Ag5、Ag6、Ag7、Ag8、Ag9、Ag11、Ag13。
The antibacterial activity test of embodiment 3 high molecular nanometer Silver Clusters compound:
Staphylococcus aureus is carried out antibacterial activity test, minimal inhibitory concentration (MIC) 5 μ g/mL, has reached current state
The least concentration limit that outer similar best product can reach.The solution using 0.5mg/mL concentration carries out activity test, experiment knot
As shown in Figure 7, after 4 hours, laboratory observation group colony forming single-digit is relative to blank, already close to experiment for fruit
Detection bottom line, reduces 107Times.Single antibacterial antibacterial activity test result shows, our product has reached international same
The equal level of antibacterial activity of series products, and our product has more stability that other like product do not has and various informative
Property.
Claims (3)
1. the preparation method of a nanometer silver cluster compound with antibacterial activity, it is characterised in that comprise the steps:
By silver nitrate and water miscible polymer monomer, it is dissolved in distilled water at 2: 1 in molar ratio, is stirred at room temperature at least 10
Minute, form lurid clear solution;Then this solution is transferred in transparent glass drying oven, by the monochrome of 300 nanometers
Light source radiates, radiated time 24-25 hour, forms wine-colored solution;Finally by wine-colored solution, through further
Dialysis, removes the little molecule of impurity, obtains pure nanometer silver cluster compound;
Described nanometer silver cluster compound, silver atom cluster compound and polymer monomer by following different structure form:
Described silver atom cluster compound has Ag2、Ag3、Ag4、Ag5、Ag6、Ag7、Ag8、Ag9、Ag11And Ag13;
Described polymer monomer is the mixture of polymethyl methacrylate and polyvinylpyrrolidone, polymethyl methacrylate
It is 1: 1 with the mass ratio of polyvinylpyrrolidone.
2. the preparation method of nanometer silver cluster compound as claimed in claim 1, it is characterised in that described silver nitrate sulphuric acid
Silver or silver acetate substitute.
3. the nanometer silver cluster compound that as claimed in claim 1 or 2 prepared by method application in preparation antibacterials.
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