CN104472538B - Functional graphene oxide loading nano silvery anti-biotic material and preparation method and application - Google Patents
Functional graphene oxide loading nano silvery anti-biotic material and preparation method and application Download PDFInfo
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Abstract
The invention belongs to nano silver antibacterial material technical field, a kind of amino polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material and preparation method and the application in antibacterial, sterilized field are disclosed.The method is comprised the following steps：By in the aqueous solution of amino polyethylene glycol addition graphene oxide, add 1 ethyl (3 dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate and N HOSu NHSs, stirring reaction after regulation pH, obtains the polyethyleneglycol modified graphene oxide of amination；Be made into the aqueous solution, added silver nitrate, it is to be dissolved after be heated to boiling, add sodium citrate or NaBH4The aqueous solution, reaction, cooling obtains amino polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material.The present invention prepares anti-biotic material has good water solubility and stability, and load efficiency, antibacterial activity are significantly improved, and with significant antibacterial activity, can be widely applied to antibacterial, sterilized field.
Description
Technical field
The invention belongs to nano silver antibacterial material technical field, more particularly to a kind of amino polyethylene glycol functionalization oxidation
Graphene-supported nano silver antibacterial material and preparation method thereof and the application in the field such as antibacterial, sterilized.
Background technology
Health is one of topic that people pay close attention to the most, however, bacterium is ubiquitous, all-pervasive, their propagation and
Spread the serious health that threaten the mankind.It is to improve people that the growth of harmful bacteria, breeding are killed and suppressed using anti-biotic material
One important means of the class general level of the health.
The drug resistance that directed toward bacteria produces to antibiotic, develops more efficient antibacterials and especially suppresses drug-resistant bacteria
Medicine is the Critical policies of current field of medicaments.In numerous anti-biotic materials, inorganic antiseptic has the secondary work of poison to human body
With relatively low, the advantages of environmental pollution is small, cause the great attention of people.The main gold such as including Ag, Cu, Zn, Ti of inorganic antiseptic
Category and its ion, they have breeding, the characteristic of growth ability killed bacterium or reduce bacterium.In inorganic antiseptic, mesh
It is Ag based inorganic antibacterial agents that preceding most study, development and application are very fast, commercial applications are most.Because the sterilizing ability of Ag is most
By force, its sterilization intensity is about Zn2+1000 times.It is inorganic at present anti-because the toxicity of other metals such as Hg, Cd, Pb and Cr is larger
Predominantly Ag, Cu and Zn that microbial inoculum is used.Heat-resist, has a broad antifungal spectrum, effective antibacterial phase is long, toxicity is relatively low, it is resistance to produce
Property of medicine etc. is the remarkable advantage that Ag based inorganic antibacterial agents have.But at the same time Ag based inorganic antibacterial agents also have mutability
Color, the shortcoming for preparing relative difficulty etc..
For Nano Silver price it is high, it is difficult dispersion and easy oxidation discoloration shortcoming, Recent study find carrier nanosizing, can
Make anti-biotic material that there is bigger specific surface area, load efficiency is high, stronger suction-operated is produced to microorganism, so as to show
More preferable antibacterial effect.Graphene is the two-dimentional carbon material of monoatomic thickness, with high-specific surface area, the heat conductivility of protrusion and
A series of excellent properties such as mechanical property, outstanding electron transmission performance, are the ideal carrier of functional material, the oxidation of its derivative
Graphene outside possessing Graphene above property, also with abundant functional group, such as hydroxyl (- OH), carboxyl (- COOH), carbonyl
Base (- C=O), the presence of these groups can carry out functional modification to graphene oxide.In recent years the pattern of nano material and
Research of the particle diameter to antibacterial performance impact is increasingly paid close attention to by people, does not produce it is desirable to search out efficiently and resistance
Anti-biotic material, i.e., be used as anti-biotic material by preparing the nano material of different-shape or different-grain diameter, so as to find optimal
Antimicrobial nano pattern and particle diameter.Nowadays the nanometer of different-shape and particle diameter has become a main direction prepared by new nanometer,
Wish that this research, for clinic provides new therapy approach and active drug, realizes important breakthrough in antibacterial research.
So far find no and close the nanometer silver antimicrobial that amino polyethylene glycol functional graphene oxide loads different-grain diameter
Material and its for antibacterial, sterilized report.
The content of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide a kind of amination to gather
The preparation method of ethylene glycol functional graphene oxide loading nano silvery anti-biotic material.The present invention utilizes amino polyethylene glycol pair
Carrier graphene oxide carries out functionalization, improves the stability of graphene oxide-loaded nano silver and antibacterial, sterilized
Bioactivity in journey, increases the validity of nanometer silver antimicrobial activity and the continuation of anti-biotic material.
Another object of the present invention is that the amino polyethylene glycol functional graphene oxide for providing above method preparation is born
Carrying nano silver anti-biotic material.Nano Silver can have different particle diameters in nano silver antibacterial material of the invention, and in specified particle diameter
In the range of have significantly excellent antibacterial effect.
Still a further object of the present invention is to provide above-mentioned amino polyethylene glycol functional graphene oxide loading nano silvery to resist
Application of the bacterium material in the field such as antibacterial, sterilized.Wherein, the Nano Silver of load is main active, with suppression bacterium
Growth and sterilized function.
The purpose of the present invention is realized by following proposal：
A kind of preparation method of amino polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material, including with
Lower step：
(1) under the conditions of water bath sonicator, by the aqueous solution of amino polyethylene glycol addition graphene oxide, 1- second is added
Base-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) and N-hydroxy-succinamide (NHS), adjust pH
Stirring reaction, obtains the polyethyleneglycol modified graphene oxide of amination (GO@PEG) afterwards；
(2) the polyethyleneglycol modified graphene oxide of the amination for preparing step (1) is made into the aqueous solution, adds nitre
Sour silver, it is to be dissolved after be heated to boiling, add sodium citrate or NaBH4The aqueous solution, reaction, cooling obtains the poly- second two of amination
Alcohol functional graphene oxide loading nano silvery anti-biotic material (GO@PEG@AgNps).
Graphene oxide used is preferably 1 with the mass ratio of amino polyethylene glycol in step (1):1~1:2.
Graphene oxide used by step (1) and 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate
(EDCHCl) mass ratio is preferably 1:2~1:2.5.
Graphene oxide used by step (1) is preferably 1 with the mass ratio of N-hydroxy-succinamide (NHS):4~1:5.
The mass ratio of the polyethyleneglycol modified graphene oxide of amination used and silver nitrate is preferably 1 in step (2):1
~1:2.
The mass ratio of silver nitrate used and sodium citrate is preferably 1 in step (2):1~1:2.
Silver nitrate used and NaBH in step (2)4Consumption mol ratio be preferably 6:1~1:1.
It is main by adding sodium citrate or NaBH in the present invention4Realize the preparation and the control to its particle size of Nano Silver
System, and by adjusting sodium citrate or NaBH4The big I of consumption prepare the Nano Silver of different-grain diameter.
The concentration of the aqueous solution of graphene oxide is preferably 1~5mg/mL described in step (1).Adjusted described in step (1)
Section pH refers to regulation pH to faintly acid, 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 is the oxidation obtained using conventional H ummers method oxidation processes Graphenes in step (1)
Graphene.
Reacted described in step (1) is carried out at room temperature.
Can be separated by centrifugation or filtering after the completion of reaction in step (1), the poly- second of the solid for obtaining as amination
The graphene oxide of glycol modification.The polyethyleneglycol modified graphene oxide preferably freeze drying standby of isolated amination
With.
The concentration of aqueous solution of the polyethyleneglycol modified graphene oxide of amination described in step (2) is preferably 1~5mg/
mL。
NaBH used in step (2)4The concentration of the aqueous solution is preferably 10~50mMol/L.
The time reacted described in step (2) is preferably 0.5~1h.
The amino polyethylene glycol functional graphene oxide loading nano silvery antibacterial that the invention described above method is prepared
Material (GO PEG AgNps), wherein graphene oxide by amino polyethylene glycol functionalization, then loading nano silvery, functionalization
Graphene oxide enhances the stabilization and dispersiveness of the Nano Silver of its load, and improves load efficiency, and the Nano Silver for loading
Particle size range is adjustable.The present invention is studied and shown, antibacterial activity and the Nano Silver for loading of the anti-biotic material for preparing of the invention
Particle diameter it is related, preferably 10~80nm, most preferably 10nm, now, the antibacterial effect of the anti-biotic material for preparing is optimal.
The amino polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material that the inventive method is prepared
(GO PEG AgNps) uses amino polyethylene glycol functional graphene oxide, improves the stability of its loading nano silvery,
And the bioactivity of Nano Silver, the validity of nano material antibacterial activity is increased, can be widely applied to various antibacterial, sterilized necks
In domain.
Mechanism of the invention is：
The present invention has using the graphene oxide of the material modification of the good water solubilities such as amidized polyethylene glycol (PEG)
Water solubility and biocompatibility, can stable existence.Meanwhile, amidized polyethylene glycol is positively charged, can induce
More electronegative nano-silver loadeds not only increase load efficiency, the Nano Silver of graphene oxide on graphene oxide
Bioactivity, increased the validity of nano material antibacterial activity, and the composite antibacterial nano material of stabilization can be formed.
The present invention has the following advantages and beneficial effect relative to prior art：
(1) present invention prepares the functional graphene oxide loading nano silvery anti-biotic material of various particle size of nanometer silver；
(2) the functional graphene oxide loading nano silvery anti-biotic material that the present invention is prepared has good water solubility
And stability, and its load efficiency, antibacterial activity be significantly improved.
(3) preparation method step of the present invention is simple, directly makees the graphene oxide of functionalization and silver nitrate in reducing agent
Lower coupling is used, preparation process need not add other auxiliary reagents, product system simply, and product can directly be preserved and used.
Brief description of the drawings
Fig. 1 is the polyethyleneglycol modified graphene oxide shape appearance figure of amination in embodiment 1.
Fig. 2 is functional graphene oxide load different-grain diameter nanoscale silver figure.
Fig. 3 is the MTT antibacterial experiment figures of the Nano Silver of functional graphene oxide load different-grain diameter.
Fig. 4 is the flat board bacteria growing inhibiting experiment of different-grain diameter functional graphene oxide loading nano silvery anti-biotic material
Figure.
Fig. 5 is the experiment that different-grain diameter functional graphene oxide loading nano silvery anti-biotic material destroys bacterial cell membrane
Figure.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
As long as it is pure above that the raw materials used purity of the present invention reaches chemistry, source is commercially available.
Embodiment 1：The preparation of amino polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) preparation of graphene oxide, using conventional H ummers methods, comprises the following steps that：Weigh 1g graphite powders and be placed in circle
In the flask of bottom, add 6g potassium permanganate and be well mixed, be subsequently adding the 131mL concentrated sulfuric acids and SPA mixed acid (volume ratio 9:
1).Above-mentioned reactant first is heated into 35~40 DEG C to stir, 50 DEG C is then heated to and is stirred 12h.Will after the completion of reaction
Reactant is cooled to room temperature and pours into 100mL frozen water, and the 30%H of 3mL is added dropwise2O2.Mixture is tested by metal master and is sieved
Choosing sieve (W.S.Tyler, 300 μm), then by filtrate under 6000rpm centrifugation 1h, give up supernatant, lower floor's solid matter
Use 200mL water, each centrifuge washing of HCl and 200mL ethanol of 200mL 30% 2 times that solution is centrifuged again successively, give up supernatant
Liquid.The lower floor's material freeze that will be obtained dries 12h, obtains graphene oxide (GO).
(2) graphene oxide obtained by step (1) is configured to the solution that concentration is 1mg/mL.The 50mL solution is taken to exist
Ultrasound in water-bath, then, the amino polyethylene glycol (PEG) for weighing 50mg is added in above-mentioned GO solution, adds 100mg
EDC.HCl and 200mg NHS, are 5~6 by the pH value regulation (using HCl to adjust) of the mixture, the stirring reaction at 25 DEG C
12h, 1h is centrifuged after the completion of reaction by solution under 6000rpm, and supernatant liquor is given up, and lower floor's material freeze dries 12h, obtains final product
To the polyethyleneglycol modified graphene oxide of amination (GO@PEG).Seen by TEANAI-10 types transmission electron microscope (TEM)
Examine, as shown in Figure 1.It is scattered in the aqueous solution, is obtained the dispersion of nano-particle, its particle diameter is in 400~500nm.Should
Nano-particle can stable existence at room temperature, easily preserve.
(3) the above-mentioned GO@PEG distilled water for preparing is configured to the solution that concentration is 1mg/mL, takes 10mL and add
Enter 10mg silver nitrate powders, after after silver nitrate dissolving, solution is heated to boiling, add the powder of 20mg sodium citrates, enter one
Step boiling reflux 1h.It is cooled at room temperature, you can prepare amino polyethylene glycol functional graphene oxide load nanometer
Silver-colored anti-biotic material, wherein the particle diameter of the Nano Silver for loading about 10nm.
Embodiment 2：The preparation of amino polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) preparation of graphene oxide is with embodiment 1
(2) preparation of the polyethyleneglycol modified graphene oxide of amination (GO@PEG) is with embodiment 1.
(3) the above-mentioned GO@PEG for preparing are prepared the solution of 1mg/mL with distilled water, 10mL is taken and is added 10mg nitre
Sour silver powder, after after silver nitrate dissolving, boiling is heated to by solution, adds the powder of 15mg sodium citrates, is further seethed with excitement back
Stream 1h, is cooled at room temperature, you can prepare amino polyethylene glycol functional graphene oxide loading nano silvery antibacterial material
Material, wherein the particle diameter of the Nano Silver for loading about 30nm.
Embodiment 3：The preparation of amino polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) preparation of graphene oxide is with embodiment 1
(2) preparation of the polyethyleneglycol modified graphene oxide of amination (GO@PEG) is with embodiment 1.
(3) the above-mentioned GO@PEG for preparing are prepared the solution of 1mg/mL with distilled water, 10mL is taken and is added 10mg nitre
Sour silver powder, after after silver nitrate dissolving, boiling is heated to by solution, adds the powder of 10mg sodium citrates, is further seethed with excitement back
Stream 1h.It is cooled at room temperature, you can prepare amino polyethylene glycol functional graphene oxide loading nano silvery antibacterial material
Material, wherein the particle diameter of the Nano Silver for loading about 50nm.
Embodiment 4：The preparation of amino polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) preparation of graphene oxide is with embodiment 1.
(2) graphene oxide obtained by step (1) is prepared the solution of 5mg/mL.The 10mL solution is taken to surpass in a water bath
Sound 1h, then, the amino polyethylene glycol (PEG) for weighing 75mg is added in above-mentioned GO solution, adds 125mg EDC.HCl
It is 5~6 by pH value regulation (being adjusted with HCl) of the mixture with 250mg NHS, stirring reaction 12h, has reacted at 25 DEG C
Solution is centrifuged 1h under 6000rpm after, supernatant liquor is given up, lower floor's material freeze dries 12h, that is, obtained amination and gather
The graphene oxide (GO@PEG) of ethylene glycol modification.It is scattered in the aqueous solution, is obtained the dispersion of nano-particle, its grain
Footpath is in 400~500nm.The nano-particle can stable existence at room temperature, easily preserve.
(3) the above-mentioned GO@PEG for preparing are prepared the solution of 1mg/mL with distilled water, 10mL is taken and is added 10mg nitre
Sour silver powder, after after silver nitrate dissolving, boiling is heated to by solution, adds the powder of 20mg sodium citrates, is further seethed with excitement back
Stream 1h.It is cooled at room temperature, you can prepare amino polyethylene glycol functional graphene oxide loading nano silvery antibacterial material
Material, wherein the particle diameter of the Nano Silver for loading about 10nm.
Embodiment 5：The preparation of amino polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) preparation of graphene oxide is with embodiment 1.
(2) graphene oxide obtained by step (1) is prepared the solution of 2mg/mL.The 25mL solution is taken to surpass in a water bath
Sound, then, the amino polyethylene glycol (PEG) for weighing 100mg is added in above-mentioned GO solution, adds 100mg EDC.HCl
It is 5~6 by pH value regulation (being adjusted with HCl) of the mixture with 200mg NHS, stirring reaction 12h, has reacted at 25 DEG C
Solution is centrifuged 1h under 6000rpm after, supernatant liquor is given up, lower floor's material freeze dries 12h, that is, obtained amination and gather
The graphene oxide (GO@PEG) of ethylene glycol modification.It is scattered in the aqueous solution, is obtained the dispersion of nano-particle, its grain
Footpath is in 400~500nm.The nano-particle can stable existence at room temperature, easily preserve.
(3) the above-mentioned GO@PEG for preparing are prepared the solution of 1mg/mL with distilled water, 10mL is taken and is added 15mg nitre
Sour silver powder, after after silver nitrate dissolving, boiling is heated to by solution, adds the powder of 10mg sodium citrates, is further seethed with excitement back
Stream 1h.It is cooled at room temperature, you can prepare amino polyethylene glycol functional graphene oxide loading nano silvery antibacterial material
Material, wherein the particle diameter of the Nano Silver for loading about 50nm.
Embodiment 6：The preparation of amino polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) preparation of graphene oxide is with embodiment 1.
(2) preparation of the polyethyleneglycol modified graphene oxide of amination (GO@PEG) is with embodiment 1.
(3) the above-mentioned GO@PEG for preparing are prepared the solution of 1mg/mL with distilled water, 10mL is taken and is added 10mg nitre
Sour silver powder, after after silver nitrate dissolving, boiling is heated to by solution, and it is the NaBH of 10mMol/L to add 1mL concentration4Solution, stirs
30min is mixed, is cooled at room temperature, you can prepare amino polyethylene glycol functional graphene oxide loading nano silvery antibacterial
Material, wherein the particle diameter of the Nano Silver for loading about 80nm.
Embodiment 7：The performance measurement of amino polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material
(1) embodiment 1~3 is observed by TEANAI-10 types transmission electron microscope (TEM) and embodiment 6 is prepared
Amino polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material particle diameter, as a result see Fig. 2.As seen from the figure,
The present invention prepares the Nano Silver that particle diameter distribution is 10~80nm, and is successfully supported on the oxidation of amino polyethylene glycol functionalization
On Graphene, and above-mentioned four kinds of particles can stable existence at room temperature, easily preserve.
(2) the amino polyethylene glycol functional graphene oxide load that embodiment 1~3 and embodiment 6 are prepared is received
The silver-colored anti-biotic material of rice as anti-biotic material bacteriostatic experiment：
The various bacterial strains purchased from DSMZ of Guangdong Province of this experimental selection, including Escherichia coli, Staphylococcus aureus
It is bacterium, bacillus subtilis, Pseudomonas aeruginosa, antibiotic-resistance E. coli, resistant Staphylococcus aureus, resistance bacillus subtilis, resistance to
Medicine Pseudomonas aeruginosa.Institute's test agent is numbered：A, the Nano Silver particle diameter of embodiment 1 are received for the functional graphene oxide of 10nm is loaded
The silver-colored anti-biotic material of rice；B, the Nano Silver particle diameter of embodiment 2 are the functional graphene oxide loading nano silvery anti-biotic material of 30nm；
C, the Nano Silver particle diameter of embodiment 3 are the functional graphene oxide loading nano silvery anti-biotic material of 50nm；D, embodiment 6 are received
Rice silver granuel footpath is the functional graphene oxide loading nano silvery anti-biotic material of 80nm.
1. MTT method of testings
The bacterium in exponential phase is taken, adjustment viable cell concentrations are 1 × 106CFU/mL is added on 96 well culture plates, often
The μ L of hole 9, then the above-mentioned four kinds of sample solutions of the μ L of various concentrations 10 are separately added into, negative control is isometric PBS, sample-adding group
4 multiple holes are all provided with control group and are placed in 37 DEG C, cultivate 24h, the μ L/ holes of MTT (5mg/mL) 20 are subsequently adding, in air surge culture
Continue to cultivate 4h in case, be subsequently adding the μ L holes of three solution 100, it is well mixed using oscillator, then proceed at 37 DEG C
Lower culture, stands overnight.OD values are determined under 570nm wavelength with ELIASA.Cell survival rate is calculated, Fig. 3 is as a result seen.
The OD values of the actual OD values/negative control hole of Survival probability of bacteria (%)=medicine feeding hole；
Bacteria suppression rate (%)=100%- cell survival rates；
2. plate dilution method bacteria growing inhibiting experiment
Bacteria Culture is overnight obtained the bacterium of logarithmic phase in culture medium at 37 DEG C.Adjustment bacterial suspension connects its concentration
Nearly 1 × 106CFU/mL.Then, the inoculation of the bacterial suspension of 50 μ L is equably on LB agar plates.Then, respectively by 20 μ
L concentration is that the above-mentioned four kinds of samples of 15 μ g/mL are added to LB agar plates and is coated with uniform, and the incubated overnight at 37 DEG C.See
The stand density of bacterium is examined, Fig. 4 is as a result seen.
3. minimum antimicrobial concentration (MIC) experiment
The bacterium that growth period reaches logarithmic phase is taken, by bacterium diluted concentration about 1 × 106CFU/mL.Then by above-mentioned four kinds
Sample Dilution is added separately to common be incubated 8h containing in bacterium culture medium, putting 37 DEG C into a series of concentration.Determined by ELIASA
OD value at 600nm is estimated (OD600).Turbidity is closest to the least concentration of control group turbidity in given the test agent
It is minimal inhibitory concentration, each experiment is parallel three, the results are shown in Table 1~2.
The minimum antimicrobial concentration of the functional graphene oxide loading nano silvery anti-biotic material of table 1
Note：The strain number for using, e. coli k12, staphylococcus aureus ATCC25213, Pseudomonas aeruginosa GF31 are withered
Careless bacillus ATCC6633.
Minimum antimicrobial concentration of the functional graphene oxide loading nano silvery anti-biotic material of table 2 to drug-resistant bacteria
Note：The strain number for using, antibiotic-resistance E. coli CICC10662, resistant Staphylococcus aureus S4050, resistance
Pseudomonas aeruginosa ATCC9027, resistance bacillus subtilis ATCC9327.
4. functional graphene oxide loading nano silvery anti-biotic material destruction bacterial cell membrane experiment
Bacterial cell is collected, and is washed twice with PBS, add above-mentioned four kinds of samples that 20 μ L concentration are 15 μ g/mL to add
2h is incubated containing common at 37 DEG C in bacterium solution, then 2h is fixed with 2.5% glutaraldehyde solution.Then sample is sequentially used respectively
50th, 70,85,90 and 100% ethanol dehydration 10min, then gold-plated film, bacterium shape is observed with SEM (SEM)
The change of state, is as a result shown in Fig. 5.
From Fig. 1~5 and table 1~2, the present invention has prepared the poly- second of amination for being loaded with different-grain diameter Nano Silver
Glycol functional graphene oxide loading nano silvery anti-biotic material, and above-mentioned system can stablize, for a long time preserve and use.And this
The anti-biotic material of invention has a significant antibacterial activity for various bacteria and its drug-resistant bacteria, and antibacterial activity is with preparing
Nano Silver change of size and change, Nano Silver particle diameter be 10nm when have optimal antibacterial effect.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of functional graphene oxide loading nano silvery anti-biotic material, it is characterised in that including following step
Suddenly：
(1) under the conditions of water bath sonicator, will amino polyethylene glycol add graphene oxide the aqueous solution in, add 1- ethyls-
(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate and N-hydroxy-succinamide, stirring reaction after regulation pH, obtain ammonia
The graphene oxide of base polyethylene glycol modification；
(2) the polyethyleneglycol modified graphene oxide of the amination for preparing step (1) is made into the aqueous solution, adds nitric acid
Silver, it is to be dissolved after be heated to boiling, add sodium citrate or NaBH4The aqueous solution, reaction, cooling obtains amino polyethylene glycol
Functional graphene oxide loading nano silvery anti-biotic material；
The mass ratio of silver nitrate used and sodium citrate is 1 in step (2):1~1:2；Silver nitrate used and NaBH4Consumption rub
You are than being 6:1~1:1.
2. the preparation method of functional graphene oxide loading nano silvery anti-biotic material according to claim 1, its feature
It is：Graphene oxide used and the mass ratio of amino polyethylene glycol are 1 in step (1):1~1:2；Graphene oxide used
It is 1 with the mass ratio of 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate:2~1:2.5；Graphite oxide used
Alkene is 1 with the mass ratio of N-hydroxy-succinamide:4~1:5.
3. the preparation method of functional graphene oxide loading nano silvery anti-biotic material according to claim 1, its feature
It is：The mass ratio of the polyethyleneglycol modified graphene oxide of amination used and silver nitrate is 1 in step (2):1~1:2.
4. the preparation method of functional graphene oxide loading nano silvery anti-biotic material according to claim 1, its feature
It is：The concentration of the aqueous solution of graphene oxide described in step (1) is 1~5mg/mL.
5. the preparation method of functional graphene oxide loading nano silvery anti-biotic material according to claim 1, its feature
It is：The concentration of aqueous solution of the polyethyleneglycol modified graphene oxide of amination described in step (2) is 1~5mg/mL.
6. the preparation method of functional graphene oxide loading nano silvery anti-biotic material according to claim 1, its feature
It is：NaBH used in step (2)4The concentration of the aqueous solution is 10~50mMol/L.
7. the preparation method of functional graphene oxide loading nano silvery anti-biotic material according to claim 1, its feature
It is：PH is adjusted described in step (1) and refers to regulation pH to faintly acid；The ultrasonic power of described water bath sonicator is 60W；Step
(2) time reacted described in is 0.5~1h.
8. a kind of functional graphene oxide loading nano silvery anti-biotic material, it is characterised in that according to any one of claim 1~7
The preparation method of described functional graphene oxide loading nano silvery anti-biotic material is obtained.
9. suppression of the functional graphene oxide loading nano silvery anti-biotic material according to claim 8 for the purpose of non-treatment
Application in bacterium, sterilized field.
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