CN102431997A - Graphene oxide with antibacterial and anticoagulant functions and preparation method thereof - Google Patents
Graphene oxide with antibacterial and anticoagulant functions and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a method for modifying graphene oxide by controllable synthetic amination with amine based compounds and prepared graphene oxide nano material with antibacterial and anticoagulant functions. The method utilizes Brodie method, Hummers method, or Staudenmaier method to prepare graphene oxide, does not conduct post-treatment to reaction liquid, adds amine based compounds into the reaction liquid for reaction, prepares amine activated graphene oxide intermediate product, and disperses by ultrasonic the intermediate product in alkaline solution to obtain graphene oxide with antibacterial and anticoagulant functions. The invention introduces amine based compounds into graphite oxide laminate. The amine based compounds can be acid-capturer in the reaction liquid of the synthesis process and promoter in controllable decomposition of graphite oxide laminate, and can make the prepared graphene oxide have antibacterial and anticoagulant functions.
Description
Technical field
The stannic oxide/graphene nano material that the present invention relates to a kind of modified oxidized preparation method of graphene and make, particularly a kind of graphene oxide and preparation method thereof with antibiotic, anticoagulation function.The graphene oxide of this modification can be used as the base mateiral of functionalization graphene oxide or novel functional stuffing, can satisfy the mechanical property requirements of biomaterial, can make biomaterial have long-term anticoagulation, antibacterial again.
Background technology
Two dimension raw material of wood-charcoal material has caused researchist's extensive concern since coming to light, novel two-dimentional raw material of wood-charcoal material graphene oxide has become the research focus.Compare with carbon nanotube with the soccerballene of costliness, graphene oxide is cheap, and raw material is easy to get.A large amount of oxygen base functional groups is rich on the surface of graphite oxide, and the oxidized graphite flake layer behind the stripping layer has very big specific surface area, and using value surpasses graphite oxide.Therefore, graphene oxide is expected to become the high quality filler of polymer nanocomposites.
Graphene oxide can be made through ultrasonic the peeling off of machinery by graphite oxide.A large amount of functional groups are contained on the graphene oxide surface; As-OH ,-COOH ,-O-, C=O etc.; The existence of these functional groups; Make to produce the effect of repelling each other between the functional group of different lamellas, can make graphite flake that peeling off to a certain degree arranged, and give graphene oxide some new characteristics.But, need certain external force (ultrasonic) from the constraint of oxidized graphite flake interlayer Van der Waals force if will these graphene oxides dissociated out.Simultaneously, in the lattice of the contiguous carbon-coating of graphite oxide, introduce functional functional group as far as possible, be more conducive to realize that the monolithic of graphene oxide peels off.In addition, the graphene oxide surface functional group is abundant more, possibly more help it and matrix is compound or self-assembly.
The preparation of graphite oxide is the key factor of decision graphene oxide preparation.Graphite oxide generally can pass through chemical method (Brodie method, Hummers method, Staudenmaier method) and make.The Brodie method (Brodie B.C..On the atomic weight of graphite [J]. Phil.Trans. Roy. Soc, 1859,149:249-59.), Hummers method (W Hummers; R Offeman. Preparation of graphite oxide [J]. J Am Chem Soc, 1958,80:1339), Staudenmaier method (Y Matsuo; K Watanabe; T Fukutsuka, et al. Charaterization of n-hexadecy-lakylamine-intercalated graphite oxide as sorbents [J]. Carbon, 2003; 41 (8): 1545-1550) all belong to the liquid phase chemical oxidation style; In the preparation process, all have a large amount of spent acid, and it is wayward further to prepare its dissociation degree of graphene oxide on this basis, a little less than the biological function.Document shows that nitrating has considerable influence to the performance of raw material of wood-charcoal material.Levy recklessly and showed the six-ring growth mechanism of carbon nanotube when being raw material with benzene; Realized with pyridine etc. being effective regulation and control of synthetic and composition and structure of the nitrogen-doped carbon based nanotube (CNx) of raw material; Thereby only exist pyridine nitrogen and nitrogen species uniform distribution more to help surface-treated (W Hummers in its structure; R Offeman. Preparation of graphite oxide [J]. J Am Chem Soc, 1958,80:1339).Wang Zhiyong (W Hummers; R Offeman. Preparation of graphite oxide [J]. J Am Chem Soc, 1958,80:1339), Cao Yong (W Hummers; R Offeman. Preparation of graphite oxide [J]. J Am Chem Soc; 1958,80:133), people such as Li Xuefei (W Hummers, R Offeman. Preparation of graphite oxide [J]. J Am Chem Soc; 1958,80:1339) studied the adulterated three dimensional carbon nanotubes of nitrogen, Fe/MgO catalysis synthetic nitrogen doped carbon nanometer pipe and graphite phase carbon nitride respectively.
Graphene oxide generally can be made through ultrasonic dissociating by the graphite oxide of above-mentioned three big chemical method preparations.But whether problem, the problem how the graphite oxide dissociation degree is controlled and the graphene oxide lamella that obtains that dissociates that prepared graphite oxide exists a large amount of spent acid how to handle have problems such as biological functionality, and these problems have directly restricted the application of graphene oxide in the biological medicine material matrix.
For overcoming the above problems, give full play to the advantageous property of graphene oxide, how to prepare the focus that the higher graphene oxide of using value has become concern, also be one of at present most important and tool work of challenging.Therefore studying that spent acid, promotes oxidn graphite in the treatment preparation method thereof how dissociates and the graphene oxide of introducing biological function such as antibiotic, anticoagulation has very important significance for theories and practice significance, will be that the functional nano matrix material of matrix lays a good foundation to further preparation functionalization graphene oxide and preparation graphene oxide.
Summary of the invention
In order to overcome the problem that exists in the prior art, the invention provides a kind of aminated compounds that utilizes as the acid binding agent in the reaction solution and promotes oxidn graphite is controlled dissociates, introduce the preparation method of the graphene oxide of antibiotic, anticoagulation function simultaneously.
Another object of the present invention also is to provide the stannic oxide/graphene nano material of said method preparation.
The present invention as a kind of functional modifier, carries out aminated modification to graphite oxide with aminated compounds, and the further ultrasonic preparation graphene oxide that dissociates, and makes to have aminated stannic oxide/graphene nano material antibiotic, the anticoagulation function.
In order to accomplish described invention task; The present invention provides a kind of controlledly synthesis to have the method for the graphene oxide of antibiotic, anticoagulation function; It is characterized in that: utilize Brodie method, Hummers method or Staudenmaier legal system to be equipped with graphite oxide; Reaction solution does not carry out aftertreatment, in reaction solution, adds aminated compounds and reacts, and makes amine activatory graphite oxide intermediate product; The intermediate product of gained ultra-sonic dispersion in basic soln obtains having graphene oxide antibiotic, the anticoagulation function.
The present invention introduces oxidized graphite flake layer with aminated compounds, and this type aminated compounds both can be used as the acid binding agent in the reaction solution, also as the controlled dissociated promotor of oxidized graphite flake layer, also can make graphene oxide have antibiotic, anticoagulation function simultaneously.The graphene oxide of this modification can effectively be avoided the congregation of graphene oxide lamella, forms water-soluble, dispersed better graphene oxide, helps the further modification and the application of various macromolecular materials.
More optimize with in more detail, describedly utilize controlled the dissociating of aminated compounds promotes oxidn graphite, and the method for introducing the graphene oxide of antibiotic, anticoagulation function may further comprise the steps:
A) utilize Brodie method or Hummers method or Staudenmaier legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment;
B) in the reaction solution of the graphite oxide for preparing, add mass concentration 5 ~ 50% aminated compoundss, behind 0 ~ 30 ℃ of stirring reaction 1 ~ 5h, form uniform dispersion liquid;
C) with the dispersion liquid suction filtration, washing, neutral to filtrating, the oven dry filter cake makes amine activatory graphite oxide intermediate product;
D) with the alkaline solution dissolving of amine activatory graphite oxide intermediate product with mass concentration 0.1 ~ 5%, ultra-sonic dispersion 0.5h ~ 5h obtains homogeneous phase solution;
E) with the solution suction filtration, washing, neutral to filtrating, 30 ~ 100 ℃ of vacuum-dryings of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
Aminated compounds commonly used includes but not limited to ammoniacal liquor, aliphatic amide, aromatic amine, quaternary amine alkali, pyridine, pyrroles, porphyrin etc., most preferably n n dimetylaniline, methylamine, Trimethylamine 99, quadrol, amino dodecane, cetylamine, stearylamine, aniline, tetramethylammonium hydroxide, hydroxide (2-hydroxyethyl).
The quality of described graphite oxide is preferably 1:10 ~ 1:100 with the ratio of the volume of aminated compounds, and wherein the consumption of graphite oxide is in gram, and aminated compounds is in milliliter.
Described alkali is sodium hydroxide or Pottasium Hydroxide.
The invention still further relates to the aminated stannic oxide/graphene nano material that described method makes.
Aminated stannic oxide/graphene nano material of the present invention; Utilize the oxygen-containing functional group on graphite oxide surface to be avtive spot; A series of aminated compoundss of different nature are anchored on the surface (Fig. 2, Fig. 3) of graphite oxide through the reaction of classics such as activated carboxylic, hydroxyl, carboxyl esterification in the organic synthesis; Can make the interlamellar spacing of graphite oxide become big, under ultrasonic external force effect of peeling off, the promotion property that aminated compounds is good to dissociating of graphite oxide; The effective degree peeled off of enhanced oxidation graphite, thus be more conducive to the graphene oxide (Fig. 2, Fig. 4) of preparation size littler (monolithic layer).The graphene oxide lamella is introduced aminated compounds, but the also biology performance of enhanced oxidation Graphene, especially bacterinertness and anticoagulant property (Fig. 5, table 1).
Table 1 is aminated graphene oxide of synthetic of the present invention (note is done the GeneO-amine) and the hemolysis rate of common graphene oxide (GeneO) when different concns.GeneO, GeneO-amine in 0.5 ~ 2.5 μ g/mL concentration range hemolysis rate all 5%, very little to erythrocytic destructiveness, can be further used in the preparation of bio-medical material.And the hemolysis rate of GeneO-amine still is lower than 5% during 100 μ g/mL, but GeneO has exceeded the normal hemolysis rate scope that material allows.Through amine activatory graphene oxide abundant because of its functional group, hemolysis rate was lower when it was contacted with blood in wider concentration range.
Table 1
The nature difference of different aminated compoundss has determined the extent of exfoliation of biological functionality graphene oxide in the preparation process among the present invention, has determined the difference of graphene oxide on biological functionalitys such as antibiotic and anticoagulation.
That uses the present invention's preparation of different naturely has a graphene oxide antibiotic, the anticoagulation function, can prepare the nano composite material of different purposes.
The invention has the beneficial effects as follows:
(1) the present invention introduces oxidized graphite flake layer with aminated compounds, can significantly reduce there are a large amount of spent acid in Brodie method, Hummers method or Staudenmaier method in last handling process problem.Reduce the cost of direct water washing reaction product, practiced thrift water resources.
(2) the present invention introduces oxidized graphite flake layer with aminated compounds, can make the graphite oxide interlamellar spacing become big, in the preparation process of graphene oxide, is easy to the controlled graphene oxide that is dissociated into monolithic/multi-disc layer.
(3) the present invention introduces oxidized graphite flake layer with aminated compounds, can make prepared graphene oxide have biological function, like antibiotic, anticoagulation function.
(4) graphene oxide that makes of the Brodie method of this improvement, Hummers method or Staudenmaier method; Not only can be used as the base mateiral of functionalization graphene oxide; Also can be used as novel functional stuffing; Can satisfy the mechanical property requirements of biomaterial, can make graphene oxide have secular anticoagulation, antibacterial again.
In a word, the technology of the modified oxidized graphene nano material of controlledly synthesis amido of the present invention, its compound method is controlled, simple, and preparation cycle is short, is easy to suitability for industrialized production.The nano material of the present invention preparation can be widely used in modification and the application of various macromolecular materials and have antibiotic, anticoagulation biological function, has good application prospects and economic benefit.
Description of drawings
Fig. 1 is that the present invention utilizes aminated compounds promotes oxidn graphite to dissociate and introduces reaction process synoptic diagram antibiotic, that the anticoagulation function prepares graphene oxide.
Fig. 2 is the Raman figure of the representative graphene oxide of synthetic of the present invention (note is done the GeneO-amine).GeneO (graphene oxide) has apparent in view absorption peak at 1350 cm-1 (D peak) and two positions of 1580 cm-1 (G peak).Compare with GeneO, acromion does not appear in the 2D peak-to-peak type symmetry of GeneO-amine, can judge the graphene oxide of peeling off into monolithic layer through amine activatory graphite oxide fully.Because functional group has been introduced in the amine activation, make characteristic peak positions that skew slightly arranged again.Flexible and the formation vibration except C=O, other peaks also appear in the GeneO-amine in the Raman collection of illustrative plates.A bands of a spectrum at 3300 cm-1 places are N-H stretching vibrations; B bands of a spectrum (N-H) at 3360 cm-1 places are the frequencys multiplication of II bands of a spectrum; I bands of a spectrum at 1595 cm-1 places are C=O stretching vibration, N-H formation vibration, C-N stretching vibration.
Fig. 3 is the FTIR figure of the representative graphene oxide of synthetic of the present invention (note is done the GeneO-amine).Have in GeneO, the GeneO-amine structure-OH and-existence of C=O, and the GeneO-amine is at 1650 cm
-1The place O-N stretching vibration occurred than GeneO.
Fig. 4 a and Fig. 4 b are the AFM figure of the representative graphene oxide (Fig. 4 b, note is done the GeneO-amine) of Brodie method (Fig. 4 a, note is GeneO) and synthetic of the present invention.AFM observes the thick size of GeneO length and width and differs, and the structure of monolithic layer exists but distributes even inadequately.And the lamella major part of GeneO-amine is about 1.5 μ m, wide about 0.5 μ m; Lamellar spacing is 1 ~ 1.2 nm; Lamella is even, and the big or little lamella appearance of incomparable 1 nm, and amine activatory graphite oxide is peeled off into the amine activatory graphene oxide of single lamella fully.Thickness obviously greater than single-sheet thickness 0.34 nm of graphite, mainly cause because oxy radical and amine activating group stretch out graphite flake by the outside.
Fig. 5 a and Fig. 5 b are the representative colibacillary SEM figure of graphene oxide (Fig. 5 b, note is done the GeneO-amine) surface adhesion of Brodie method (Fig. 5 a, note is GeneO) and synthetic of the present invention.Normal Bacillus coli cells smooth surface, thalline is full, is the shaft-like of the blunt circle in two ends, and thalline is grown up and is about 1 ~ 2 μ m.On the GeneO surface, intestinal bacteria distribute more, and major part presents dead state, mainly is the effect that dimensional effect has been brought into play anti-bacterial attachment.And on GeneO-amine surface, intestinal bacteria adhere to comparatively small amt, all present dead state.Adherent intestinal bacteria size is 2 μ m ~ 3 μ m by common 1 μ m variation, and is a bunch existence, and dead bacterial structure is fuzzy gradually, and it is flat that rod-like structure becomes gradually.
Embodiment
Through embodiment the present invention is specifically described below, be necessary to be pointed out that at this, following examples only are used for the present invention is further specified, and can not be interpreted as the restriction to protection domain of the present invention.
Utilize the Brodie legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In the reaction solution of the graphite oxide for preparing, add 5% pyridine compounds, wherein, the quality of graphite oxide and the volume ratio of pyridine compounds are 1:10, regulate pH to neutral, behind 0 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrating, the filter cake oven dry obtains pyridine activatory graphite oxide intermediate product.Pyridyl amine activatory graphite oxide intermediate product is dissolved with 0.1% sodium hydroxide solution, and ultra-sonic dispersion 5h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrating, 30 ℃ of vacuum-drying 3d of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
Embodiment 2
Utilize the Brodie legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In the reaction solution of the graphite oxide for preparing, add 50% ammoniacal liquor, wherein, the quality of graphite oxide and the volume ratio of pyridine compounds are 1:100, regulate pH to neutral, behind 30 ℃ of stirring reaction 5h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrating, the filter cake oven dry obtains ammonia activatory graphite oxide intermediate product.Ammonia activatory graphite oxide intermediate product is dissolved with 5% potassium hydroxide solution, and ultra-sonic dispersion 0.5h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrating, 100 ℃ of vacuum-drying 3h of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
Embodiment 3
Utilize the Brodie legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In the reaction solution of the graphite oxide for preparing, add 10% n n dimetylaniline, wherein, the quality of graphite oxide and the volume ratio of n n dimetylaniline are 1:20, regulate pH to neutral, behind 10 ℃ of stirring reaction 2h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrating, the filter cake oven dry obtains n n dimetylaniline activatory graphite oxide intermediate product.N n dimetylaniline activatory graphite oxide intermediate product is dissolved with 0.2% sodium hydroxide solution, and ultra-sonic dispersion 2h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrating, 30 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
Embodiment 4
Utilize the Brodie legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In the reaction solution of the graphite oxide for preparing, add 20% methylamine, wherein, the quality of graphite oxide and the volume ratio of methylamine are 1:30, regulate pH to neutral, behind 20 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrating, the filter cake oven dry obtains methylamine activatory graphite oxide intermediate product.Methylamine activatory graphite oxide intermediate product is dissolved with 0.3% sodium hydroxide solution, and ultra-sonic dispersion 2h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrating, 40 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
Embodiment 5
Utilize the Brodie legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In the reaction solution of the graphite oxide for preparing, add 30% Trimethylamine 99, wherein, the quality of graphite oxide and the volume ratio of Trimethylamine 99 are 1:40, regulate pH to neutral, behind 30 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrating, the filter cake oven dry obtains Trimethylamine 99 activatory graphite oxide intermediate product.Trimethylamine 99 activatory graphite oxide intermediate product is dissolved with 0.3% potassium hydroxide solution, and ultra-sonic dispersion 2h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrating, 50 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
Embodiment 6
Utilize the Brodie legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In the reaction solution of the graphite oxide for preparing, add 30% quadrol, wherein, the quality of graphite oxide and the volume ratio of quadrol are 1:40, regulate pH to neutral, behind 40 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrating, the filter cake oven dry obtains ammonia activatory graphite oxide intermediate product.Quadrol activatory graphite oxide intermediate product is dissolved with 0.5% potassium hydroxide solution, and ultra-sonic dispersion 2h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrating, 50 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
Embodiment 7
Utilize the Brodie legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In the reaction solution of the graphite oxide for preparing, add 30% amino dodecane, wherein, the quality of graphite oxide and the volume ratio of amino dodecane are 1:50, regulate pH to neutral, behind 40 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrating, the filter cake oven dry obtains amino dodecane activatory graphite oxide intermediate product.Amino dodecane activatory graphite oxide intermediate product is dissolved with 0.6% sodium hydroxide solution, and ultra-sonic dispersion 2h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrating, 60 ℃ of vacuum-drying 1d of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
Embodiment 8
Utilize the Brodie legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In the reaction solution of the graphite oxide for preparing, add 40% cetylamine, wherein, the quality of graphite oxide and the volume ratio of cetylamine are 1:40, regulate pH to neutral, behind 50 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrating, the filter cake oven dry obtains cetylamine activatory graphite oxide intermediate product.Cetylamine activatory graphite oxide intermediate product is dissolved with 0.5% potassium hydroxide solution, and ultra-sonic dispersion 2h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrating, 50 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
Embodiment 9
Utilize the Brodie legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In the reaction solution of the graphite oxide for preparing, add 30% stearylamine, wherein, the quality of graphite oxide and the volume ratio of stearylamine are 1:40, regulate pH to neutral, behind 40 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrating, the filter cake oven dry obtains stearylamine activatory graphite oxide intermediate product.Stearylamine activatory graphite oxide intermediate product is dissolved with 0.7% potassium hydroxide solution, and ultra-sonic dispersion 2h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrating, 50 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
Embodiment 10
Utilize the Brodie legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In the reaction solution of the graphite oxide for preparing, add 30% stearylamine, wherein, the quality of graphite oxide and the volume ratio of stearylamine are 1:40, regulate pH to neutral, behind 40 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrating, the filter cake oven dry obtains stearylamine activatory graphite oxide intermediate product.Stearylamine activatory graphite oxide intermediate product is dissolved with 5% potassium hydroxide solution, and ultra-sonic dispersion 2h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrating, 50 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
Embodiment 11
Utilize the Brodie legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In the reaction solution of the graphite oxide for preparing, add 40% aniline, wherein, the quality of graphite oxide and the volume ratio of aniline are 1:40, regulate pH to neutral, behind 40 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrating, the filter cake oven dry obtains aniline activatory graphite oxide intermediate product.Aniline activatory graphite oxide intermediate product is dissolved with 1% sodium hydroxide solution, and ultra-sonic dispersion 2h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrating, 80 ℃ of vacuum-drying 2h of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
Embodiment 12
Utilize the Brodie legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In the reaction solution of the graphite oxide for preparing, add 30% tetramethylammonium hydroxide, wherein, the quality of graphite oxide and the volume ratio of tetramethylammonium hydroxide are 1:40, regulate pH to neutral, behind 40 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrating, the filter cake oven dry obtains tetramethylammonium hydroxide activatory graphite oxide intermediate product.Tetramethylammonium hydroxide activatory graphite oxide intermediate product is dissolved with 3% potassium hydroxide solution, and ultra-sonic dispersion 1h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrating, 50 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
Embodiment 13
Utilize the Brodie legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In the reaction solution of the graphite oxide for preparing, add 40% hydroxide (2-hydroxyethyl), wherein, the volume ratio of the quality of graphite oxide and hydroxide (2-hydroxyethyl) is 1:20, regulates pH to neutral, behind 20 ℃ of stirring reaction 1h, forms uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrating, the filter cake oven dry obtains hydroxide (2-hydroxyethyl) activatory graphite oxide intermediate product.Hydroxide (2-hydroxyethyl) activatory graphite oxide intermediate product is dissolved with 3% potassium hydroxide solution, and ultra-sonic dispersion 1h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrating, 90 ℃ of vacuum-drying 2h of filter cake obtain having graphene oxide antibiotic, the anticoagulation function.
The foregoing description limits the present invention never in any form, and all employings are equal to the technical scheme of the form acquisition of replacement or equivalent transformation, all drop within protection scope of the present invention.
Claims (7)
1. a controlledly synthesis has the method for the graphene oxide of antibiotic, anticoagulation function; It is characterized in that utilize Brodie method, Hummers method or Staudenmaier legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment; In reaction solution, adding aminated compounds reacts; Make amine activatory graphite oxide intermediate product, the intermediate product of gained ultra-sonic dispersion in basic soln obtains described graphene oxide.
2. that controlledly synthesis according to claim 1 has is antibiotic, the method for the graphene oxide of anticoagulation function, it is characterized in that described method may further comprise the steps:
A) utilize Brodie method, Hummers method or Staudenmaier legal system to be equipped with graphite oxide, reaction solution does not carry out aftertreatment;
B) in the reaction solution of the graphite oxide for preparing, add mass concentration 5 ~ 50% aminated compoundss, behind 0 ~ 30 ℃ of following stirring reaction 1 ~ 5h, form uniform dispersion liquid;
C) with dispersion liquid suction filtration, washing, neutral to filtrating, the oven dry filter cake makes amine activatory graphite oxide intermediate product;
D) amine activatory graphite oxide intermediate product is dissolved with mass concentration 0.1 ~ 5% alkaline solution, ultra-sonic dispersion 0.5h ~ 5h obtains homogeneous phase solution;
E) with the solution suction filtration, washing filter thing is to neutral, and 30 ~ 100 ℃ of vacuum-dryings obtain described graphene oxide.
3. that controlledly synthesis according to claim 1 and 2 has is antibiotic, the method for the graphene oxide of anticoagulation function, and it is characterized in that: described aminated compounds is ammoniacal liquor, aliphatic amide, aromatic amine, quaternary amine alkali, pyridine, pyrroles or porphyrin.
4. that controlledly synthesis according to claim 3 has is antibiotic, the method for the graphene oxide of anticoagulation function, and it is characterized in that: described aliphatic amide is n n dimetylaniline, methylamine, Trimethylamine 99, quadrol, amino dodecane, cetylamine or stearylamine; Described aromatic amine is an aniline; Described quaternary amine alkali is tetramethylammonium hydroxide or hydroxide (2-hydroxyethyl).
5. that controlledly synthesis according to claim 1 and 2 has is antibiotic, the method for the graphene oxide of anticoagulation function; It is characterized in that: the quality of described graphite oxide and the volume ratio of aminated compounds are 1:10 ~ 1:100; Wherein the consumption of graphite oxide is in gram, and aminated compounds is in milliliter.
6. that controlledly synthesis according to claim 2 has is antibiotic, the method for the graphene oxide of anticoagulation function, and it is characterized in that: in the step c), described alkali is sodium hydroxide or Pottasium Hydroxide.
7. has a stannic oxide/graphene nano material antibiotic, the anticoagulation function according to what the described arbitrary method of claim 1 to 6 made.
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