CN109535354A - A kind of nano-cluster and its preparation method and application with bactericidal effect - Google Patents
A kind of nano-cluster and its preparation method and application with bactericidal effect Download PDFInfo
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- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a kind of nano-cluster and its preparation method and application with bactericidal effect, wherein the structural formula of the nano-cluster with bactericidal effect is as follows:Wherein the numerical intervals of x, y, z are respectively 1-100, and m is 4 or 5, and n is 5 or 6.There is the present invention nano-cluster of bactericidal effect can be configured to certain density solution direct spraying in wound surface, for treating and preventing the infection of various bacteriums.The present invention has good water solubility with the nano-cluster of bactericidal effect, and the concentration of the solution is calculated as that 5-30 μ g/mL effect is best, and general 6-8 days mouse wound heals completely with the concentration of contained Argent grain.
Description
Technical field
The present invention relates to a kind of water-soluble cross-linked nanometer polymer, specifically a kind of nano-cluster with bactericidal effect
And its preparation method and application.
Background technique
Staphylococcus aureus is a kind of Gram-positive spherical bacterial, is arranged in thyrsiform under microscope, is
The common pathogenic bacteria for causing food poisoning.It is common in skin surface and upper respiratory tract mucosa.The Center for Disease Control report,
The infection as caused by S. aureus L-forms accounts for second, is only second to Escherichia coli.S. aureus L-forms are a kind of pathogenic bacteria for causing severe infections, can
Cause in human body different loci and infect, from the mild infection of epidermis to depth, fatefulue infection, such as pneumonia, endocarditis, loses
Blood disease, osteomyelitis and other metastatic complication etc..
Nano particle is the nano particle between 1-200nm.Mainly in biotechnology, bioengineering, Textile Engineering etc.
As antibacterial.Nano particle diameter is small, and specific surface area is high, can quickly adsorb in cell membrane surface, significant change bacterium
The physiological functions such as permeability and respiratory function lead to bacterial death, however pure inorganic nano (by taking silver nanoparticle as an example) has
Higher germicidal efficiency and the wide advantage of bactericidal range, but its bio-toxicity is big, pure nano-cluster, has preferable physics
And chemical stability, toxicity is low, but germicidal efficiency is low, and bactericidal range is narrow and is also easy to produce drug resistance, polymer and nano-cluster knot
It closes, effectively can avoid disadvantage in conjunction with the two advantage, have broad application prospects.
Summary of the invention
Based on the above technology and background, the present invention is directed to the deficiency of existing anti-biotic material, provides a kind of with sterilization work
Nano-cluster and its preparation method and application, by MOLECULE DESIGN means, screening obtains a kind of nanometer with bactericidal effect
Cluster.
The present invention has the nano-cluster of bactericidal effect, and structural formula is as follows:
Wherein the numerical intervals of x, y, z are respectively 1-100, and m is 4 or 5, and n is 5 or 6.
The present invention has the preparation method of the nano-cluster of bactericidal effect, is with 4- cyano -4- (phenyl formyl sulfenyl)
Valeric acid is chain-transferring agent, with azodiisobutyronitrile (AIBN) for initiator, with polyethylene glycol monomethyl ethermethacrylic acid esters and is gathered
Glycolmethacrylate is raw material, has synthesized the nano-cluster containing hydroxyl first；Again with the nano-cluster containing hydroxyl, bromine oneself
Acyl chlorides and triethylamine are raw material, and synthesis obtains the nano-cluster containing bromo；Then with nano-cluster and thioacetic acid containing bromo
Potassium raw material, synthesis obtain the nano-cluster containing thioester substrate, then cut off under conditions of piperidines and N, N'- dimethylformamide,
The nano-cluster containing sulfydryl is obtained, obtains target product finally by in-situ polymerization.
The present invention has the preparation method of the nano-cluster of bactericidal effect, includes the following steps:
Step 1: the synthesis of nano-cluster
Under nitrogen protection, chain-transferring agent 4- cyano -4- (phenyl formyl sulfenyl) valeric acid, initiator azo two is different
Butyronitrile (AIBN), polyethylene glycol monomethyl ethermethacrylic acid esters (300), polyethylene glycol methacrylate-styrene polymer (360) and second two
Alcohol dimethylacrylate (EGDMA) is added in Shrek pipe, and oil pump pumping-liquid nitrogen frozen-nitrogen inflates three circulations, each
Circulation is 8-12 times, after circulation terminates, is warming up to 60-100 DEG C, is stirred to react 8-24 hours, after reaction ice just oneself
It is settled in alkane, the nano-cluster containing hydroxyl is obtained after vacuum drying；
Wherein, chain-transferring agent 4- cyano -4- (phenyl formyl sulfenyl) valeric acid, initiator azodiisobutyronitrile
(AIBN), polyethylene glycol monomethyl ethermethacrylic acid esters (300), polyethylene glycol methacrylate-styrene polymer (360) and ethylene glycol two
The molar ratio of methacrylate (EGDMA) is 0.1-10:0.01-1:1-100:1-100:0.1-1.
Step 2: esterification
The nano-cluster containing hydroxyl, bromine caproyl chloride and the triethylamine that step 1 is obtained are according to 0.1-1:0.1-5:0.1-6's
Molar ratio is added equipped with biexhaust pipe, stirs in the two-mouth bottle of magneton, normal-temperature reaction 8-24 hours, synthesizes the nanometer containing bromo
Cluster；
Step 3: substitution reaction
The nano-cluster containing bromo and thioacetic acid potassium obtained with step 2 is added according to the molar ratio of 0.1-2:0.2-5
It equipped with biexhaust pipe, stirs in the two-mouth bottle of magneton, normal-temperature reaction 8-24 hours, synthesis obtains the nano-cluster containing thioester substrate；
Step 4: cutting reaction
The nano-cluster containing thioester substrate that step 3 is obtained is added in piperidines and N, N'- dimethylformamide mixed solution,
Normal-temperature reaction 3-10 hours, obtain the nano-cluster containing sulfydryl；
Piperidines and N in mixed solution, the volume ratio of N'- dimethylformamide are 0.1-10:0.2-20.
Step 5: in-situ polymerization
The nano-cluster 20-80mg containing sulfydryl that step 4 is obtained is dissolved in 5-50mL deionized water, is added 1-30mg's
NaBH4, the AgNO that concentration is 0.01-20mg/mL is added dropwise3Solution 1-100mL, can be obtained target product.
On the one hand, available size is less than the water-soluble polymer of 200nm, on the other hand, silver nanoparticle in polymer
The introducing of grain has good bactericidal property.
In step 1, the synthesis process of nano-cluster is as follows:
The organic solvent is selected from tetrahydrofuran, N, six alkane of N'- dimethylformamide, chloroform or dioxy etc..
In step 2, the esterification reaction process of hydroxyl and bromine caproyl chloride is as follows:
The organic solvent is selected from tetrahydrofuran, N, six alkane of N'- dimethylformamide, chloroform or dioxy etc..
In step 3, the substitution reaction process of bromo and thioacetic acid potassium is as follows:
The organic solvent is selected from tetrahydrofuran, N, six alkane of N'- dimethylformamide, chloroform or dioxy etc..
In step 4, the cutting reaction process of sulfydryl is as follows:
The organic solvent is selected from tetrahydrofuran, N, six alkane of N'- dimethylformamide, chloroform or dioxy etc..
In step 5, the process that in-situ polymerization synthesizes silver nanoparticle is as follows:
The solvent is selected from water.
The present invention has the application of the nano-cluster of bactericidal effect, is to be configured to certain density solution direct spraying in wound
Surface, for treating and preventing the infection of various bacteriums.
The present invention has good water solubility with the nano-cluster of bactericidal effect, and the concentration of the solution is with contained Argent grain
Concentration be calculated as that 5-30 μ g/mL effect is best, and general 6-8 days mouse wound heals completely.
The present invention has the nano-cluster preparation of bactericidal effect simple, and material therefor environmental protection has in biologic medical field
Very big potential using value.
Compared with the prior art, the beneficial effects of the present invention are embodied in:
1, nanometer is prepared by the method design of reversible addion-fragmentation chain transfer polymerization (RAFT polymerization) in the present invention
Cluster, not only molecular weight is controllable for the nano-cluster that this method is prepared, but also inherits the excellent water of polyethylene glycol methacrylate-styrene polymer
Dissolubility performance.
2, the present invention uses polymerization reaction, and application is simple and quick, and post-processing is easy, and reaction condition is controllable, reproducible, holds
It is easy to realize industrial production.
3, the present invention uses fabricated in situ nano-cluster technology, effectively reduces the use of organic solvent, operating method is simple
Easy, obtained nano-cluster size stable uniform, being capable of Stable distritation and presence in water.Compared to simple Argent grain or
Person's polymer, nano-cluster prepared by the present invention have lower toxicity, are expected to be widely used in terms of bacterium infection.
It should be noted that on the basis of common knowledge of the art, above-mentioned each condition can be in any combination up to this hair
Bright preferred embodiment.
Detailed description of the invention
Fig. 1 is infared spectrum before and after nano-cluster is changed by thioester substrate to sulfydryl, as seen from Figure 1, the nanometer containing sulfydryl
Cluster is in 2500cm-1There is sulfydryl characteristic absorption peak in place, and does not occur in the nano-cluster containing thioester substrate, it can be seen that sulphur
Ester group nano-cluster is cut off, and products therefrom is nano-cluster containing sulfydryl.
Grain size distribution of the nano-cluster that Fig. 2 is in dynamic light scattering (DLS).As seen from Figure 2, water-soluble
The particle diameter distribution of crosslinking nano polymer is preferable, and size is about 200nm.
Transmission electron microscope picture of the water-soluble nano cluster that Fig. 3 is at transmission electron microscope (TEM), scale are
200nm, as seen from Figure 3, the Argent grain on the nano-cluster surface with bactericidal effect are evenly distributed, and size is more regular, ruler
Very little size is about 15nm.
Fig. 4 is common Argent grain bactericidal effect figure.
Fig. 5 is the bactericidal effect figure for the nano-cluster that the present invention synthesizes.
Specific embodiment
It is further details of to illustrate the present invention below with reference to specific implementation example.It should be understood that following example only illustrates this
Invention rather than the limitation scope of the invention.
Embodiment 1:
1, under nitrogen protection, by 0.028g (0.0001mol) 4- cyano -4- (phenyl formyl sulfenyl) valeric acid,
0.0016g (0.00001mol) azodiisobutyronitrile (AIBN), 2.7g (0.009mol) poly glycol monomethyl ether methacrylic acid
Ester (OEGMA-300), 0.36g (0.001mol) polyethylene glycol methacrylate-styrene polymer (OEGMA-360), 0.007928g
(0.00004mol) ethylene glycol dimethacrylate (EGDMA) is added in Shrek pipe, and 10mlN, N'- dimethyl formyl is added
Amine makees solvent, the pumping-circulation of freezing-inflation three, and each circulation is done 10 times.After circulation terminates, 70 DEG C are warming up to, is stirred to react
12h is settled in n-hexane, is then dried in vacuo.The hydrophilic nano cluster containing hydroxyl, yield 98% are obtained；
2, the hydrophilic nano cluster 2.98g containing hydroxyl prepared using step 1 is raw material, equipped with biexhaust pipe, stirring magnetic
Middle addition 0.85g (0.004mol) bromine caproyl chloride in the two-mouth bottle of son, 0.606g (0.006mol) triethylamine (TEA) are added
10mlN, N'- dimethylformamide make solvent.After reacting 12h, filtering settles in n-hexane.It settles in triplicate, then very
Sky is dry.The hydrophilic nano cluster containing bromo, yield 90% are obtained；
3, the hydrophilic nano cluster 2.8g containing bromo prepared using step 2 is raw material, equipped with biexhaust pipe, stirring magneton
Two-mouth bottle in middle addition 0.68g (0.002mol) thioacetic acid potassium (KsAc), be added 10mlN, N'- dimethylformamide is made molten
Agent.After reacting 12h, filtering settles in n-hexane, has obtained the hydrophilic nano cluster containing thioester substrate, yield 95%；
4, the hydrophilic nano cluster 2.7g raw material containing thioester substrate prepared with step 3, equipped with biexhaust pipe, stirring magneton
Two-mouth bottle in it is middle be added molar ratio be 3mL piperidines and 6mLN, N'- dimethylformamide be solvent, react 12h after, filtering,
It is settled in n-hexane, has obtained the hydrophilic nano cluster containing sulfydryl, yield 86%；
5, the hydrophilic nano cluster 2.55g raw material containing sulfydryl prepared with step 4, in the single port bottle equipped with stirring magneton
In it is middle be added 50mg sodium borohydride, the silver nitrate (AgNO of 10mg/mL is added dropwise3) solution, after reacting 5h, centrifugation, weight is molten,
Obtain the nano-cluster with bactericidal effect.
Embodiment 2:
1, under nitrogen protection, by 0.014g (0.00005mol) 4- cyano -4- (phenyl formyl sulfenyl) valeric acid,
0.0032g (0.00002mol) azodiisobutyronitrile (AIBN), 2.4g (0.008mol) poly glycol monomethyl ether methacrylic acid
Ester (OEGMA-300), 0.72g (0.002mol) polyethylene glycol methacrylate-styrene polymer (OEGMA-360), 0.003964g
(0.00002mol) ethylene glycol dimethacrylate (EGDMA) is added in Shrek pipe, and 20ml dioxane is added and makees solvent,
Pumping-the circulation of freezing-inflation three, each circulation are done 15 times.After circulation terminates, 80 DEG C are warming up to, 10h is stirred to react, just
It settles in hexane, is then dried in vacuo.The hydrophilic nano cluster containing hydroxyl, yield 90% are obtained；
2, the hydrophilic nano cluster 2.81g containing hydroxyl prepared using step 1 is raw material, equipped with biexhaust pipe, stirring magnetic
Middle addition 0.64g (0.003mol) bromine caproyl chloride in the two-mouth bottle of son, 0.505g (0.005mol) triethylamine (TEA) are added
20ml dioxane makees solvent.After reacting 10h, filtering settles in n-hexane.Sedimentation in triplicate, is then dried in vacuo.?
The hydrophilic nano cluster containing bromo, yield 91% are arrived；
3, the hydrophilic nano cluster 2.5g containing bromo prepared using step 2 is raw material, equipped with biexhaust pipe, stirring magneton
Two-mouth bottle in middle addition 0.34g (0.003mol) thioacetic acid potassium (KsAc), be added 20ml dioxane make solvent.Reaction
After 10h, filtering settles in n-hexane, has obtained the hydrophilic nano cluster containing thioester substrate, yield 87%；
4, the hydrophilic nano cluster 2.1g raw material containing thioester substrate prepared with step 3, equipped with biexhaust pipe, stirring magneton
Two-mouth bottle in it is middle be added molar ratio be 5mL piperidines and 5mLN, N'- dimethylformamide be solvent, react 10h after, filtering,
It is settled in n-hexane, has obtained the hydrophilic nano cluster containing sulfydryl, yield 89%；
5, the hydrophilic nano cluster 1.8g raw material containing sulfydryl prepared with step 4, in the single port bottle equipped with stirring magneton
In it is middle be added 10mg sodium borohydride, the silver nitrate (AgNO of 1mg/mL is added dropwise3) solution, after reacting 8h, centrifugation is heavy molten.
Obtain the nano-cluster with bactericidal effect.
Embodiment 3:
1, under nitrogen protection, by 0.028g (0.0001mol) 4- cyano -4- (phenyl formyl sulfenyl) valeric acid,
0.0016g (0.00001mol) azodiisobutyronitrile (AIBN), 2.7g (0.009mol) poly glycol monomethyl ether methacrylic acid
Ester (OEGMA-300), 0.36g (0.001mol) polyethylene glycol methacrylate-styrene polymer (OEGMA-360), 0.007928g
(0.00004mol) ethylene glycol dimethacrylate (EGDMA) is added in Shrek pipe, and 15mlN, N'- dimethyl formyl is added
Amine makees solvent, the pumping-circulation of freezing-inflation three, and each circulation is done 10 times.After circulation terminates, 70 DEG C are warming up to, is stirred to react
16h is settled in n-hexane, is then dried in vacuo.The hydrophilic nano cluster containing hydroxyl, yield 89% are obtained；
2, the hydrophilic nano cluster 2.65g containing hydroxyl prepared using step 1 is raw material, equipped with biexhaust pipe, stirring magnetic
Middle addition 0.64g (0.003mol) bromine caproyl chloride in the two-mouth bottle of son, 0.505g (0.005mol) triethylamine (TEA) are added
15mlN, N'- dimethylformamide make solvent.After reacting 16h, filtering settles in n-hexane.It settles in triplicate, then very
Sky is dry.The hydrophilic nano cluster containing bromo, yield 96% are obtained；
3, the hydrophilic nano cluster 2.41g containing bromo prepared using step 2 is raw material, equipped with biexhaust pipe, stirring magnetic
15mlN, N'- dimethylformamide is added in middle addition 0.3426g (0.003mol) thioacetic acid potassium (KsAc) in the two-mouth bottle of son
Make solvent.After reacting 16h, filtering settles in n-hexane, has obtained the hydrophilic nano cluster containing thioester substrate, yield is
88%.
4, the hydrophilic nano cluster 2.1g raw material containing thioester substrate prepared with step 3, equipped with biexhaust pipe, stirring magneton
Two-mouth bottle in it is middle be added molar ratio be 3mL piperidines and 6mLN, N'- dimethylformamide be solvent, react 16h after, filtering,
It is settled in n-hexane, has obtained the hydrophilic nano cluster containing sulfydryl, yield 88%；
5, the hydrophilic nano cluster 1.75g raw material containing sulfydryl prepared with step 4, in the single port bottle equipped with stirring magneton
In it is middle be added 50mg sodium borohydride, the silver nitrate (AgNO of 1mg/mL is added dropwise3) solution, after reacting 5h, centrifugation is heavy molten.
Obtain the nano-cluster with bactericidal effect.
Embodiment 4: the measurement of minimal inhibitory concentration (MIC)
The nano-cluster with bactericidal effect of various concentration is dissolved in nutrient broth medium, then inoculated bacteria,
Whether by the growth of bacterium, determine that nano-cluster inhibits the minimum concentration of staphylococcus aureus growth, i.e. MIC.Operating procedure
It is as follows: (1) preparation of containing nano-cluster culture medium: nano-cluster with sterile water do to be serially diluted into again various concentration by liquid
(231,115.5,57.7,28.8,14.4,7.2 μ g/mL) takes each dilution to be added to the liquid containing 1mL bacterium solution by liquid 1mL and trains
It supports in base, measures the MIC value of nano-cluster, if its value very little, then the concentration of nano silver is slowly reduced, as make MIC accurate as possible；
(2) taking 100 μ L bacteria containing amounts is about 108Cfu/mL bacterial suspension inoculation is in the nutrient broth medium containing nano-cluster, as test
Group sample；(3) take the bacterial suspension inoculation of same concentration into the test tube of nutrient broth, as positive controls sample；(4) two are taken
The test tube of Zhi Hanyou nutrient broth, as negative control group sample；(5) by test group sample, positive controls sample and feminine gender
Control group sample is placed in 37 DEG C of incubators, and culture for 24 hours, observes result；Fungistatic effect evaluation: when positive control pipe has bacterium raw
Long, negative control pipe does not have bacterial growth, and the concentration of experiment bacteria suspension is 5 × 105Cfu/mL~5 × 106Cfu/mL, test
Mlc corresponding to the highest dilution of group asepsis growth is minimal inhibitory concentration MIC；
Embodiment 5: measurement minimum bactericidal concentration (MBC)
Experimental group is taken, 100 μ L of sample corresponding to the highest dilution of asepsis growth after cultivating according to the above method for 24 hours, into
The culture of row viable bacteria counts, while the viable count of positive controls of the test without nano silver polymer in the same way.
In formula, N0: the clump count of positive controls after culture for 24 hours；N: the clump count of experimental group after culture for 24 hours.
The foregoing is merely section Example of the invention, it is not meant to that the present invention must rely on above-mentioned process flow
It can implement.Any improvement in the present invention, the addition of equivalence replacement and auxiliary element to each raw material of the present invention, concrete mode
Selection etc., all of which fall within the scope of protection and disclosure of the present invention.
Table 1 is that general silver particles are dense to the minimal inhibitory concentration of staphylococcus aureus and Escherichia coli and minimum sterilization
Degree；Table 2 is minimal inhibitory concentration and minimum sterilization of the present invention synthesis nano-cluster for staphylococcus aureus and Escherichia coli
Concentration.By being compared with table 2, it can be seen that the present invention has 3-4 times of general silver particles with the nano-cluster of bactericidal effect
Bactericidal effect；
Table 1
Table 2
Claims (3)
1. a kind of nano-cluster with bactericidal effect, it is characterised in that its structural formula is as follows:
Wherein the numerical intervals of x, y, z are respectively 1-100, and m is 4 or 5, and n is 5 or 6.
2. a kind of preparation method of the nano-cluster described in claim 1 with bactericidal effect, it is characterised in that: be with 4- cyanogen
Base -4- (phenyl formyl sulfenyl) valeric acid is chain-transferring agent, using azodiisobutyronitrile as initiator, with poly glycol monomethyl ether
Methacrylate and polyethylene glycol methacrylate-styrene polymer are raw material, have synthesized the nano-cluster containing hydroxyl first；Again to contain
Nano-cluster, bromine caproyl chloride and the triethylamine of hydroxyl are raw material, and synthesis obtains the nano-cluster containing bromo；Then to contain bromo
Nano-cluster and thioacetic acid potassium raw material, synthesis obtains the nano-cluster containing thioester substrate, then in piperidines and N, N'- dimethyl formyl
It is cut off under conditions of amine, obtains the nano-cluster containing sulfydryl, obtain target product finally by in-situ polymerization.
3. a kind of application of the nano-cluster described in claim 1 with bactericidal effect, it is characterised in that: be configured to it is centainly dense
The solution direct spraying of degree is in wound surface, for treating and preventing the infection of various bacteriums.
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|---|---|---|---|---|
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