CN104472538A - Functional graphene oxide loaded nano-silver antibacterial material as well as preparation method and application thereof - Google Patents
Functional graphene oxide loaded nano-silver antibacterial material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nano-silver antibacterial materials and discloses an aminated polyethylene glycol functional graphene oxide loaded nano-silver antibacterial material, a preparation method of the antibacterial material and an application of the antibacterial material in the fields of bacteriostasis and sterilization. The method comprises the following steps: adding aminated polyethylene glycol into an aqueous solution of graphene oxide, adding 1-ethyl-(3-dimethylaminopropyl) carbonyldiimine hydrochloride and N-hydroxy succinimide, regulating the pH value, stirring, and reacting, thereby obtaining the aminated polyethylene glycol modified graphene oxide; preparing the aqueous solution of the graphene oxide, adding silver nitrate, heating until the solution is boiled after dissolving, adding sodium citrate or NaBH4 aqueous solution, reacting, and cooling, thereby obtaining the aminated polyethylene glycol functional graphene oxide loaded nano-silver antibacterial material. The antibacterial material prepared by the invention has good water solubility and stability, the loading efficiency and antibacterial activity are obviously improved, and the antibacterial material has obvious antibacterial activity and can be widely applied to the fields of bacteriostasis and sterilization.
Description
Technical field
The invention belongs to nano silver antibacterial material technical field, particularly a kind of amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material and preparation method thereof and the application in the fields such as antibacterial, sterilization.
Background technology
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.Utilize anti-biotic material to kill and suppress the growth of noxious bacteria, breed to be the important means improving level of human health.
The drug resistance that directed toward bacteria produces antibiotic, develop more efficient antibacterials especially medicines for inhibiting drug-resistant bacteria be the Critical policies of current field of medicaments.In numerous anti-biotic materials, the advantages such as inorganic antiseptic has the toxic and side effect of human body lower, and environmental pollution is little, cause the great attention of people.Inorganic antiseptic mainly comprises the metals such as Ag, Cu, Zn, Ti and ion thereof, and they have kill bacteria or reduce the breeding of bacterium, the characteristic of growing ability.In inorganic antiseptic, current most study, development and application are very fast, commercial applications is maximum is Ag based inorganic antibacterial agent.Because the sterilizing ability of Ag is the strongest, its sterilization intensity is about Zn
2+1000 times.Because the toxicity of other metal such as Hg, Cd, Pb and Cr is comparatively large, what current inorganic antiseptic used is mainly Ag, Cu and Zn.Good heat resistance, has a broad antifungal spectrum, effective antibacterial phase is long, toxicity is lower, can not produce drug resistance etc. is the remarkable advantage that Ag based inorganic antibacterial agent has.But meanwhile, Ag based inorganic antibacterial agent also has shortcoming that is easy to change, that prepare relative difficulty etc.
The shortcoming of high for Nano Silver price, difficult dispersion and easy oxidation discoloration, Recent study finds carrier nanorize, and anti-biotic material can be made to have larger specific surface area, and load efficiency is high, stronger suction-operated is produced to microorganism, thus shows better antibacterial effect.Graphene is the Two-dimensional Carbon material of monoatomic thickness, there is a series of excellent properties such as high-specific surface area, outstanding heat conductivility and mechanical property, outstanding electron transmission performance, it is the ideal carrier of functional material, its derivative graphene oxide is possessing outside the above character of Graphene, also with abundant functional group, as hydroxyl (-OH), carboxyl (-COOH), carbonyl (-C=O), the existence of these groups can carry out functional modification to graphene oxide.The pattern of nano material and particle diameter more and more receive the concern of people to the research of antibacterial performance impact in recent years, people wish to search out efficiently and do not produce the anti-biotic material of resistance, namely by preparing the nano material of different-shape or different-grain diameter as anti-biotic material, thus best antimicrobial nano pattern and particle diameter is found.Nowadays the nanometer of different-shape and particle diameter has become a main direction of new fabrication, wishes that this research provides new therapy approach and active drug for clinical, antibacterial research realizes important breakthrough.
So far the nano silver antibacterial material that closes amination polyethylene glycol functional graphene oxide load different-grain diameter is found no and for report that is antibacterial, sterilization.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is the preparation method providing a kind of amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material.The present invention utilizes amination polyethylene glycol to carry out functionalization to carrier graphene oxide, improve the stability of graphene oxide-loaded nano silver and the biologically active in antibacterial, sterilization process, increase the validity of nanometer silver antimicrobial activity and the continuation of anti-biotic material.
Another object of the present invention is the amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material providing said method to prepare.In nano silver antibacterial material of the present invention, Nano Silver can have different particle diameters, and within the scope of specified particle diameter, have significantly excellent antibacterial effect.
Still a further object of the present invention is to provide the application of above-mentioned amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material in the fields such as antibacterial, sterilization.Wherein, the Nano Silver of load is main active, has the function of bacteria growing inhibiting and sterilization.
Object of the present invention is realized by following proposal:
A preparation method for amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material, comprises the following steps:
(1) under water bath sonicator condition, amination polyethylene glycol is added in the aqueous solution of graphene oxide, add 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) and N-hydroxy-succinamide (NHS) again, stirring reaction after adjustment pH, obtains the polyethyleneglycol modified graphene oxide of amination (GO@PEG);
(2) the polyethyleneglycol modified graphene oxide of amination step (1) prepared is made into the aqueous solution, adds silver nitrate, is heated to boiling, adds sodium citrate or NaBH after to be dissolved
4the aqueous solution, reaction, cooling, obtains amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material (GO@PEG@AgNps).
In step (1), the mass ratio of graphene oxide used and amination polyethylene glycol is preferably 1:1 ~ 1:2.
The mass ratio of step (1) graphene oxide used and 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) is preferably 1:2 ~ 1:2.5.
The mass ratio of step (1) graphene oxide used and N-hydroxy-succinamide (NHS) is preferably 1:4 ~ 1:5.
The graphene oxide that in step (2), amination used is polyethyleneglycol modified and the mass ratio of silver nitrate are preferably 1:1 ~ 1:2.
In step (2), the mass ratio of silver nitrate used and sodium citrate is preferably 1:1 ~ 1:2.
Silver nitrate used and NaBH in step (2)
4consumption mol ratio be preferably 6:1 ~ 1:1.
Mainly through adding sodium citrate or NaBH in the present invention
4realize the preparation of Nano Silver and the control to its particle size, and by regulating sodium citrate or NaBH
4the large I of consumption prepare the Nano Silver of different-grain diameter.
Described in step (1), the concentration of the aqueous solution of graphene oxide is preferably 1 ~ 5mg/mL.Regulate pH to refer to regulate pH to faintly acid described in step (1), be preferably 5 ~ 6.
The preferred ultrasonic power of water bath sonicator described in step (1) is 60W.
The time of stirring reaction described in step (1) is preferably 10 ~ 12h.
Graphene oxide used in step (1) is the graphene oxide using conventional H ummers method oxidation processes Graphene to obtain.
React described in step (1) and at room temperature carry out.
Be separated by centrifugal or filtration after having reacted in step (1), the solid obtained is the polyethyleneglycol modified graphene oxide of amination.For subsequent use after the graphene oxide preferably freeze drying that the amination that separation obtains is polyethyleneglycol modified.
Described in step (2), the concentration of aqueous solution of the graphene oxide that amination is polyethyleneglycol modified is preferably 1 ~ 5mg/mL.
NaBH used in step (2)
4the concentration of the aqueous solution is preferably 10 ~ 50mMol/L.
The time of reaction described in step (2) is preferably 0.5 ~ 1h.
The amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material (GO@PEG@AgNps) that the invention described above method prepares, wherein graphene oxide is by amination polyethylene glycol functionalization, loading nano silvery again, the graphene oxide of functionalization enhances the stable and dispersed of the Nano Silver of its load, and improve load efficiency, and the Nano Silver particle size range of load is adjustable.The present invention's research shows, the antibacterial activity of the anti-biotic material that the present invention prepares is relevant to the particle diameter of the Nano Silver of load, is preferably 10 ~ 80nm, most preferably is 10nm, and now, the antibacterial effect of the anti-biotic material prepared is best.
The amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material (GO@PEG@AgNps) that the inventive method prepares adopts amination polyethylene glycol functional graphene oxide, improve the stability of its loading nano silvery, and the biologically active of Nano Silver, add the validity of nano material antibacterial activity, can be widely used in various antibacterial, sterilization field.
Mechanism of the present invention is:
Water-soluble and the biocompatibility that the graphene oxide that the present invention utilizes the material of the good water solubility such as amidized polyethylene glycol (PEG) to modify has had, can stable existence.Simultaneously, amidized polyethylene glycol is positively charged, can induce more electronegative nano-silver loaded on graphene oxide, not only increase the load efficiency of graphene oxide, the biologically active of Nano Silver, add the validity of nano material antibacterial activity, and stable composite antibacterial nano material can be formed.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) the present invention prepares the functional graphene oxide loading nano silvery anti-biotic material of multiple grain diameter nano silver;
(2) the functional graphene oxide loading nano silvery anti-biotic material that the present invention prepares has good water-soluble and stability, and its load efficiency, antibacterial activity are significantly improved.
(3) preparation method's step of the present invention is simple, is directly coupled under reductant effect with silver nitrate by the graphene oxide of functionalization, and preparation process is without the need to adding other auxiliary reagent, product system simply, and product can directly be preserved and use.
Accompanying drawing explanation
Fig. 1 is the graphene oxide shape appearance figure that in embodiment 1, amination is polyethyleneglycol modified.
Fig. 2 is functional graphene oxide load different-grain diameter nanoscale silver figure.
Fig. 3 is the MTT antibacterial experiment figure of the Nano Silver of functional graphene oxide load different-grain diameter.
Fig. 4 is the dull and stereotyped bacteria growing inhibiting lab diagram of different-grain diameter functional graphene oxide loading nano silvery anti-biotic material.
Fig. 5 is the lab diagram that different-grain diameter functional graphene oxide loading nano silvery anti-biotic material destroys bacterial cell membrane.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
As long as the raw materials used purity of the present invention reaches more than chemical pure, source all can be buied from market.
Embodiment 1: the preparation of amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) preparation of graphene oxide, adopt conventional H ummers method, concrete steps are as follows: take 1g graphite powder and be placed in round-bottomed flask, then add 6g potassium permanganate and mix, and then add the 131mL concentrated sulfuric acid and SPA mixed acid (volume ratio 9:1).First above-mentioned reactant is heated to 35 ~ 40 DEG C stir, is then heated to 50 DEG C and stirs 12h.After having reacted, reactant be cooled to room temperature and pour in 100mL frozen water, dripping the 30%H of 3mL
2o
2.By mixture by metal master test screen sieve (W.S.Tyler, 300 μm), then by filtrate centrifugation 1h under 6000rpm, give up supernatant, lower floor's solid matter uses 200mL water successively, the each centrifuge washing of HCl and 200mL ethanol of 200mL 30% 2 times, solution is again centrifugal, give up supernatant.By the dry 12h of lower floor's material freeze obtained, obtain graphene oxide (GO).
(2) graphene oxide that step (1) obtains is mixed with the solution that concentration is 1mg/mL.Get this solution of 50mL ultrasonic in a water bath, then, the amination polyethylene glycol (PEG) taking 50mg joins in above-mentioned GO solution, add 100mg EDC.HCl and 200mg NHS again, (adopting HCl to regulate) pH value of this mixture is regulated to be 5 ~ 6, stirring reaction 12h at 25 DEG C, by solution centrifugal 1h under 6000rpm after having reacted, supernatant liquor is given up, the dry 12h of lower floor's material freeze, namely obtains the polyethyleneglycol modified graphene oxide of amination (GO@PEG).Observed by TEANAI-10 type transmission electron microscope (TEM), as shown in Figure 1.Be scattered in the aqueous solution, obtain the dispersion of nano particle, its particle diameter is at 400 ~ 500nm.This nano particle can at room temperature stable existence, easily preserves.
(3) the above-mentioned GO@PEG distilled water prepared is mixed with the solution that concentration is 1mg/mL, get 10mL and add 10mg silver nitrate powder, after silver nitrate dissolves, solution being heated to boiling, add the powder of 20mg sodium citrate, further boiling reflux 1h.Under cool to room temperature, can prepare amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material, the particle diameter of the Nano Silver of wherein load is about 10nm.
Embodiment 2: the preparation of amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) preparation of graphene oxide is with embodiment 1
(2) preparation of the graphene oxide (GO@PEG) that amination is polyethyleneglycol modified is with embodiment 1.
(3) by the solution of the above-mentioned GO@PEG distilled water preparation 1mg/mL prepared, get 10mL and add 10mg silver nitrate powder, after silver nitrate dissolves, solution is heated to boiling, add the powder of 15mg sodium citrate, further boiling reflux 1h, under cool to room temperature, can prepare amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material, the particle diameter of the Nano Silver of wherein load is about 30nm.
Embodiment 3: the preparation of amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) preparation of graphene oxide is with embodiment 1
(2) preparation of the graphene oxide (GO@PEG) that amination is polyethyleneglycol modified is with embodiment 1.
(3) by the solution of the above-mentioned GO@PEG distilled water preparation 1mg/mL prepared, get 10mL and add 10mg silver nitrate powder, after silver nitrate dissolves, solution being heated to boiling, adding the powder of 10mg sodium citrate, further boiling reflux 1h.Under cool to room temperature, can prepare amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material, the particle diameter of the Nano Silver of wherein load is about 50nm.
Embodiment 4: the preparation of amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) preparation of graphene oxide is with embodiment 1.
(2) solution of graphene oxide preparation 5mg/mL step (1) obtained.Get this solution of 10mL ultrasonic 1h in a water bath, then, the amination polyethylene glycol (PEG) taking 75mg joins in above-mentioned GO solution, add 125mg EDC.HCl and 250mg NHS again, (regulating with HCl) pH value of this mixture is regulated to be 5 ~ 6, stirring reaction 12h at 25 DEG C, by solution centrifugal 1h under 6000rpm after having reacted, supernatant liquor is given up, the dry 12h of lower floor's material freeze, namely obtains the polyethyleneglycol modified graphene oxide of amination (GO@PEG).Be scattered in the aqueous solution, obtain the dispersion of nano particle, its particle diameter is at 400 ~ 500nm.This nano particle can at room temperature stable existence, easily preserves.
(3) by the solution of the above-mentioned GO@PEG distilled water preparation 1mg/mL prepared, get 10mL and add 10mg silver nitrate powder, after silver nitrate dissolves, solution being heated to boiling, adding the powder of 20mg sodium citrate, further boiling reflux 1h.Under cool to room temperature, can prepare amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material, the particle diameter of the Nano Silver of wherein load is about 10nm.
Embodiment 5: the preparation of amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) preparation of graphene oxide is with embodiment 1.
(2) solution of graphene oxide preparation 2mg/mL step (1) obtained.Get this solution of 25mL ultrasonic in a water bath, then, the amination polyethylene glycol (PEG) taking 100mg joins in above-mentioned GO solution, add 100mg EDC.HCl and 200mg NHS again, (regulating with HCl) pH value of this mixture is regulated to be 5 ~ 6, stirring reaction 12h at 25 DEG C, by solution centrifugal 1h under 6000rpm after having reacted, supernatant liquor is given up, the dry 12h of lower floor's material freeze, namely obtains the polyethyleneglycol modified graphene oxide of amination (GO@PEG).Be scattered in the aqueous solution, obtain the dispersion of nano particle, its particle diameter is at 400 ~ 500nm.This nano particle can at room temperature stable existence, easily preserves.
(3) by the solution of the above-mentioned GO@PEG distilled water preparation 1mg/mL prepared, get 10mL and add 15mg silver nitrate powder, after silver nitrate dissolves, solution being heated to boiling, adding the powder of 10mg sodium citrate, further boiling reflux 1h.Under cool to room temperature, can prepare amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material, the particle diameter of the Nano Silver of wherein load is about 50nm.
Embodiment 6: the preparation of amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) preparation of graphene oxide is with embodiment 1.
(2) preparation of the graphene oxide (GO@PEG) that amination is polyethyleneglycol modified is with embodiment 1.
(3) by the solution of the above-mentioned GO@PEG distilled water preparation 1mg/mL prepared, get 10mL and add 10mg silver nitrate powder, after silver nitrate dissolves, solution being heated to boiling, adding the NaBH that 1mL concentration is 10mMol/L
4solution, stir 30min, under cool to room temperature, can prepare amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material, the particle diameter of the Nano Silver of wherein load is about 80nm.
Embodiment 7: the performance measurement of amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) observed the particle diameter of the amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material that embodiment 1 ~ 3 and embodiment 6 prepare by TEANAI-10 type transmission electron microscope (TEM), the results are shown in Figure 2.As seen from the figure, the present invention prepares the Nano Silver that domain size distribution is 10 ~ 80nm, and successful load is in amination polyethylene glycol functional graphene oxide, and above-mentioned four kinds of particles all can at room temperature stable existence, easily preserves.
(2) the amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material for preparing of embodiment 1 ~ 3 and embodiment 6 as anti-biotic material bacteriostatic experiment:
The multiple bacterial strain purchased from DSMZ of Guangdong Province of this experimental selection, comprises Escherichia coli, staphylococcus aureus, bacillus subtilis, Pseudomonas aeruginosa, antibiotic-resistance E. coli, resistant Staphylococcus aureus, resistance bacillus subtilis, drug-resistant pseudomonas aeruginosa.Tested sample number into spectrum is: the Nano Silver particle diameter of a, embodiment 1 is the functional graphene oxide loading nano silvery anti-biotic material of 10nm; The Nano Silver particle diameter of b, embodiment 2 is the functional graphene oxide loading nano silvery anti-biotic material of 30nm; The Nano Silver particle diameter of c, embodiment 3 is the functional graphene oxide loading nano silvery anti-biotic material of 50nm; The Nano Silver particle diameter of d, embodiment 6 is the functional graphene oxide loading nano silvery anti-biotic material of 80nm.
1. MTT method of testing
Get the bacterium being in exponential phase, adjustment viable cell concentrations is 1 × 10
6cFU/mL is added on 96 well culture plates, every hole 9 μ L, then add the above-mentioned four kinds of sample solutions of variable concentrations 10 μ L respectively, negative control is equal-volume PBS buffer solution, application of sample group and control group all establish 4 multiple holes to be placed in 37 DEG C, cultivate 24h, then add MTT (5mg/mL) 20 μ L/ hole, continue to cultivate 4h in air surge incubator, then three solution 100 μ L holes are added, adopt oscillator to make it mix, then continue to cultivate at 37 DEG C, placement is spent the night.Under 570nm wavelength, OD value is measured by microplate reader.Calculate cell survival rate, the results are shown in Figure 3.
The OD value of the actual OD value/negative control hole of Survival probability of bacteria (%)=medicine feeding hole;
Bacteria suppression rate (%)=100%-cell survival rate;
2. plate dilution method bacteria growing inhibiting experiment
Bacterial culture to be spent the night at 37 DEG C at medium and obtains the bacterium of logarithmic phase.Adjustment bacterial suspension makes its concentration close to 1 × 10
6cFU/mL.Subsequently, the inoculation of the bacterial suspension of 50 μ L is equably on LB agar plate.Then, be that the above-mentioned four kinds of samples of 15 μ g/mL join LB agar plate respectively by 20 μ L concentration and coating evenly, and at 37 DEG C incubated overnight.Observe the stand density of bacterium, the results are shown in Figure 4.
3. minimum antimicrobial concentration (MIC) experiment
Get the bacterium reaching logarithmic phase vegetative period, by bacterium diluted concentration about 1 × 10
6cFU/mL.Then become a series of concentration to join respectively containing in bacterium culture medium above-mentioned four kinds of Sample Dilutions, put 37 DEG C and jointly hatch 8h.The optical density value being measured 600nm place by microplate reader carries out assessing (OD
600).In given the test agent, turbidity is minimal inhibitory concentration closest to the least concentration of control group turbidity, and parallel three of each experiment, the results are shown in Table 1 ~ 2.
The minimum antimicrobial concentration of table 1 functional graphene oxide loading nano silvery anti-biotic material
Note: the strain number of use, e. coli k12, staphylococcus aureus ATCC25213, Pseudomonas aeruginosa GF31, bacillus subtilis ATCC6633.
Table 2 functional graphene oxide loading nano silvery anti-biotic material is to the minimum antimicrobial concentration of drug-resistant bacteria
Note: the strain number of use, antibiotic-resistance E. coli CICC10662, resistant Staphylococcus aureus S4050, drug-resistant pseudomonas aeruginosa ATCC9027, resistance bacillus subtilis ATCC9327.
4. functional graphene oxide loading nano silvery anti-biotic material destroys bacterial cell membrane experiment
Collect bacterial cell, and to wash twice with PBS, adding 20 μ L concentration is that above-mentioned four kinds of samples of 15 μ g/mL add and at 37 DEG C, jointly hatch 2h containing in bacterium liquid, then fixes 2h with 2.5% glutaraldehyde solution.Then sample is used according to the order of sequence respectively the ethanol dehydration 10min of 50,70,85,90 and 100%, then gold-plated film, observes the change of ne ar, the results are shown in Figure 5 by SEM (SEM).
From Fig. 1 ~ 5 and table 1 ~ 2, the present invention has prepared the amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material that load has different-grain diameter Nano Silver, and the equal Absorbable organic halogens of above-mentioned system, long-term preservation and use.And anti-biotic material of the present invention has significant antibacterial activity for various bacteria and drug-resistant bacteria thereof, and antibacterial activity changes with the Nano Silver change of size prepared, and has optimum antibacterial effect when Nano Silver particle diameter is 10nm.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for functional graphene oxide loading nano silvery anti-biotic material, is characterized in that comprising the following steps:
(1) under water bath sonicator condition, amination polyethylene glycol is added in the aqueous solution of graphene oxide, add 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate and N-hydroxy-succinamide again, stirring reaction after adjustment pH, obtains the graphene oxide that amination is polyethyleneglycol modified;
(2) the polyethyleneglycol modified graphene oxide of amination step (1) prepared is made into the aqueous solution, adds silver nitrate, is heated to boiling, adds sodium citrate or NaBH after to be dissolved
4the aqueous solution, reaction, cooling, obtains amination polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material.
2. the preparation method of functional graphene oxide loading nano silvery anti-biotic material according to claim 1, is characterized in that: in step (1), the mass ratio of graphene oxide used and amination polyethylene glycol is 1:1 ~ 1:2; The mass ratio of graphene oxide used and 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate is 1:2 ~ 1:2.5; The mass ratio of graphene oxide used and N-hydroxy-succinamide is 1:4 ~ 1:5.
3. the preparation method of functional graphene oxide loading nano silvery anti-biotic material according to claim 1, is characterized in that: the graphene oxide that in step (2), amination used is polyethyleneglycol modified and the mass ratio of silver nitrate are 1:1 ~ 1:2.
4. the preparation method of functional graphene oxide loading nano silvery anti-biotic material according to claim 1, is characterized in that: in step (2), the mass ratio of silver nitrate used and sodium citrate is 1:1 ~ 1:2; Silver nitrate used and NaBH
4consumption mol ratio be 6:1 ~ 1:1.
5. the preparation method of functional graphene oxide loading nano silvery anti-biotic material according to claim 1, is characterized in that: described in step (1), the concentration of the aqueous solution of graphene oxide is 1 ~ 5mg/mL.
6. the preparation method of functional graphene oxide loading nano silvery anti-biotic material according to claim 1, is characterized in that: described in step (2), the concentration of aqueous solution of the graphene oxide that amination is polyethyleneglycol modified is 1 ~ 5mg/mL.
7. the preparation method of functional graphene oxide loading nano silvery anti-biotic material according to claim 1, is characterized in that: NaBH used in step (2)
4the concentration of the aqueous solution is 10 ~ 50mMol/L.
8. the preparation method of functional graphene oxide loading nano silvery anti-biotic material according to claim 1, is characterized in that: regulate pH to refer to regulate pH to faintly acid described in step (1); The ultrasonic power of described water bath sonicator is 60W; Described in step (2), the time of reaction is 0.5 ~ 1h.
9. a functional graphene oxide loading nano silvery anti-biotic material, is characterized in that the preparation method of the functional graphene oxide loading nano silvery anti-biotic material according to any one of claim 1 ~ 8 obtains.
10. the application of functional graphene oxide loading nano silvery anti-biotic material according to claim 9 in antibacterial, sterilization field.
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