CN102431997B - 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 preparation method of modified graphene oxide and make, particularly a kind of graphene oxide with antibiotic, anticoagulant functions and preparation method thereof.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 again biomaterial have Long-term Anti blood coagulation, antibacterial.
Background technology
The two dimension Carbon Materials has caused researchist's extensive concern since being found, New Two Dimensional Carbon Materials graphene oxide has become study hotspot.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 after delamination has very large 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 peeled off by mechanical ultrasonic by graphite oxide and make.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 and produce the effect of mutually repelling 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 if these graphene oxides to be dissociated out from the constraint of oxidized graphite flake interlayer Van der Waals force, need certain external force (ultrasonic).Simultaneously, introduce as far as possible functional functional group in the lattice of the contiguous carbon-coating of graphite oxide, be more conducive to realize that the monolithic of graphene oxide peels off.In addition, the graphene oxide surface functional group is abundanter, may more be conducive to it and matrix is compound or self-assembly.
The preparation of graphite oxide is the key factor that determines the 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, all there is a large amount of spent acid in preparation process, and it is wayward further to prepare on this basis its dissociation degree of graphene oxide, a little less than biological function.Document shows, nitrating has considerable influence to the performance of Carbon Materials.Recklessly the levy six-ring growth mechanism of carbon nanotube when having showed take benzene as raw material, realized the Effective Regulation of the synthetic and composition and structure of the nitrogen-doped carbon based nanotube (CNx) take pyridine etc. as raw material, thereby only exist pyridine nitrogen and nitrogen species evenly to distribute in its structure and more be conducive to surface modification (W Hummers, 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), the people such as Li Xuefei (W Hummers, R Offeman. Preparation of graphite oxide [J]. J Am Chem Soc, 1958, 80:1339) studied respectively the three dimensional carbon nanotubes of nitrogen doping, Fe/MgO catalyzes and synthesizes nitrogen-doped carbon nanometer pipe and graphite-phase carbonitride.
Graphene oxide generally can be made through ultrasonic dissociating by the graphite oxide of above-mentioned three large chemical method preparations.But prepared graphite oxide exists problem, the problem how the graphite oxide dissociation degree is controlled and the graphene oxide lamella that obtains that dissociates how a large amount of spent acid are processed whether to have the 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 Application and preparation is worth the focus that higher graphene oxide has become concern, is also one of most important and tool work of challenging at present.Therefore study that spent acid, accelerating oxidation graphite in treatment preparation method thereof how dissociates and the graphene oxide of introducing the biological function such as antibiotic, anticoagulation has very important theory significance and practice significance, will the functional nano matrix material that further preparation functionalization graphene oxide and preparation graphene oxide are matrix be laid a good foundation.
Summary of the invention
In order to overcome the problem that exists in prior art, the invention provides and a kind ofly utilize aminated compounds as the acid binding agent in reaction solution and accelerating oxidation graphite is controlled dissociates, introduce simultaneously the preparation method of the graphene oxide of antibiotic, anticoagulant functions.
Another object of the present invention also is to provide the stannic oxide/graphene nano material of described 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, anticoagulant functions.
In order to complete described invention task, the invention provides a kind of method that controlledly synthesis has the graphene oxide of antibiotic, anticoagulant functions, it is characterized in that: utilize the standby graphite oxide of Brodie method, Hummers method or Staudenmaier legal system, reaction solution does not carry out aftertreatment, add aminated compounds to react in reaction solution, make the graphite oxide intermediate product of amine activation, the intermediate product of gained ultra-sonic dispersion in basic solution obtains having graphene oxide antibiotic, anticoagulant functions.
The present invention introduces oxidized graphite flake layer with aminated compounds, and this class aminated compounds both can be used as the acid binding agent in reaction solution, also as the controlled promotor of dissociating of oxidized graphite flake layer, also can make simultaneously graphene oxide have antibiotic, anticoagulant functions.The graphene oxide of this modification can effectively be avoided the congregation of graphene oxide lamella, forms water-soluble, dispersed better graphene oxide, is conducive to further modification and the application of various macromolecular materials.
More optimizes and in more detail, describedly utilize controlled the dissociating of aminated compounds accelerating oxidation graphite, and the method for introducing the graphene oxide of antibiotic, anticoagulant functions comprises the following steps:
A) utilize the standby graphite oxide of Brodie method or Hummers method or Staudenmaier legal system, reaction solution does not carry out aftertreatment;
B) add mass concentration 5 ~ 50% aminated compoundss in the reaction solution of the graphite oxide for preparing, after 0 ~ 30 ℃ of stirring reaction 1 ~ 5h, form uniform dispersion liquid;
C) with the dispersion liquid suction filtration, washing, neutral to filtrate, the oven dry filter cake makes the graphite oxide intermediate product that amine activates;
D) the graphite oxide intermediate product of amine activation is used the alkaline solution dissolving of mass concentration 0.1 ~ 5%, ultra-sonic dispersion 0.5h ~ 5h obtains homogeneous phase solution;
E) with the solution suction filtration, washing, neutral to filtrate, 30 ~ 100 ℃ of vacuum-dryings of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Aminated compounds commonly used includes but not limited to ammoniacal liquor, aliphatic amide, aromatic amine, quaternary amine alkali, pyridine, pyrroles, porphyrin etc., most preferably dimethylamine, 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 potassium 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, by activated carboxylic in organic synthesis, hydroxyl, the reaction of the classics such as carboxyl esterification is anchored on a series of aminated compoundss of different nature surface (Fig. 2 of graphite oxide, Fig. 3), can make the interlamellar spacing of graphite oxide become large, under the ultrasonic External Force Acting of peeling off, the promotion that aminated compounds is good to dissociating of graphite oxide, can effectively strengthen the degree that graphite oxide is peeled off, thereby be more conducive to graphene oxide (Fig. 2 of preparation size less (monolithic layer), Fig. 4).The graphene oxide lamella is introduced aminated compounds, also can strengthen biology performance, especially germ resistance and the anticoagulant property (Fig. 5, table 1) of graphene oxide.
Table 1 is the aminated graphene oxide (note is done the GeneO-amine) and the hemolysis rate of ordinary oxygen functionalized graphene (GeneO) when different concns that the present invention synthesizes.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 is still lower than 5% during 100 μ g/mL, but GeneO has exceeded the normal hemolysis rate scope that material allows.The graphene oxide of process amine activation is abundant because of its functional group, and when it is contacted with blood in wider concentration range, hemolysis rate is lower.
Table 1
In the present invention, the nature difference of different aminated compoundss has determined the extent of exfoliation of biological functionality graphene oxide in preparation process, has determined the difference of graphene oxide on the biological functionalitys such as antibiotic and anticoagulation.
That uses the present invention's preparation of different naturely has a graphene oxide antibiotic, anticoagulant functions, 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 greatly 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 that directly washes reaction product with water, saved water resources.
(2) the present invention introduces oxidized graphite flake layer with aminated compounds, can make the graphite oxide interlamellar spacing become large, is easy to the controlled graphene oxide that is dissociated into monolithic/multi-disc layer in the preparation process of graphene oxide.
(3) the present invention introduces oxidized graphite flake layer with aminated compounds, can make prepared graphene oxide with biological function, as antibiotic, anticoagulant functions.
(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 again graphene oxide have long-term anticoagulation, antibacterial.
In a word, the technique of controlledly synthesis amino modified stannic oxide/graphene nano material of the present invention, its synthetic 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 the modification of various macromolecular materials and application and have antibiotic, anticoagulation biological function, has good application prospect and economic benefit.
Description of drawings
Fig. 1 is that the present invention utilizes aminated compounds accelerating oxidation graphite to dissociate and introduces the reaction process schematic diagram antibiotic, that anticoagulant functions prepares graphene oxide.
Fig. 2 is the Raman figure of the representative graphene oxide (note is done the GeneO-amine) that synthesizes of the present invention.The GeneO(graphene oxide) at 1350 cm-1(D peaks) and 1580 cm-1(G peaks) there is apparent in view absorption peak two positions.Compare with GeneO, the 2D peak-to-peak type of GeneO-amine is symmetrical, acromion do not occur, can judge the graphene oxide of peeling off into monolithic layer through the graphite oxide of amine activation fully.Again because functional group has been introduced in amine activation, make characteristic peak positions that slightly skew be arranged.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 (note is done the GeneO-amine) that synthesizes of the present invention.Have in GeneO, 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 that the AFM of the representative graphene oxide (Fig. 4 b, note is done the GeneO-amine) that synthesizes of Brodie method (Fig. 4 a, note be GeneO) and the present invention schemes.AFM observes the thick size of GeneO length and width and differs, and the structure of monolithic layer exists but distributes even not.And the lamella major part of GeneO-amine is about 1.5 μ m, wide approximately 0.5 μ m, lamellar spacing is 1 ~ 1.2 nm, lamella is even, and the large or little lamella appearance of incomparable 1 nm, and the graphite oxide of amine activation is peeled off into the graphene oxide of the amine activation 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 colibacillary SEM figure of representative graphene oxide (Fig. 5 b, note is done the GeneO-amine) surface adhesion that Brodie method (Fig. 5 a, note is GeneO) and the present invention synthesize.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, is mainly 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.The intestinal bacteria size that adheres to 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
Below by embodiment, the present invention is specifically described, be necessary to be pointed out that at this, following examples only are used for the present invention is further illustrated, and can not be interpreted as limiting the scope of the invention.
Utilize the standby graphite oxide of Brodie legal system, reaction solution does not carry out aftertreatment; Add 5% pyridine compounds in the reaction solution of the graphite oxide for preparing, wherein, the quality of graphite oxide and the volume ratio of pyridine compounds are 1:10, regulate pH to neutral, after 0 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrate, the filter cake oven dry obtains the graphite oxide intermediate product that pyridine activates.The graphite oxide intermediate product of pyridyl amine activation 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 filtrate, 30 ℃ of vacuum-drying 3d of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Embodiment 2
Utilize the standby graphite oxide of Brodie legal system, reaction solution does not carry out aftertreatment; Add 50% ammoniacal liquor in the reaction solution of the graphite oxide for preparing, wherein, the quality of graphite oxide and the volume ratio of pyridine compounds are 1:100, regulate pH to neutral, after 30 ℃ of stirring reaction 5h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrate, the filter cake oven dry obtains the graphite oxide intermediate product that ammonia activates.The graphite oxide intermediate product of ammonia activation 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 filtrate, 100 ℃ of vacuum-drying 3h of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Embodiment 3
Utilize the standby graphite oxide of Brodie legal system, reaction solution does not carry out aftertreatment; Add 10% dimethylamine in the reaction solution of the graphite oxide for preparing, wherein, the quality of graphite oxide and the volume ratio of dimethylamine are 1:20, regulate pH to neutral, after 10 ℃ of stirring reaction 2h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrate, the filter cake oven dry obtains the graphite oxide intermediate product that dimethylamine activates.The graphite oxide intermediate product of dimethylamine activation 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 filtrate, 30 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Embodiment 4
Utilize the standby graphite oxide of Brodie legal system, reaction solution does not carry out aftertreatment; Add 20% methylamine in the reaction solution of the graphite oxide for preparing, wherein, the quality of graphite oxide and the volume ratio of methylamine are 1:30, regulate pH to neutral, after 20 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrate, the filter cake oven dry obtains the graphite oxide intermediate product that methylamine activates.The graphite oxide intermediate product of methylamine activation 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 filtrate, 40 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Embodiment 5
Utilize the standby graphite oxide of Brodie legal system, reaction solution does not carry out aftertreatment; Add 30% Trimethylamine 99 in the reaction solution of the graphite oxide for preparing, wherein, the quality of graphite oxide and the volume ratio of Trimethylamine 99 are 1:40, regulate pH to neutral, after 30 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrate, the filter cake oven dry obtains the graphite oxide intermediate product that Trimethylamine 99 activates.The graphite oxide intermediate product of Trimethylamine 99 activation 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 filtrate, 50 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Embodiment 6
Utilize the standby graphite oxide of Brodie legal system, reaction solution does not carry out aftertreatment; Add 30% quadrol in the reaction solution of the graphite oxide for preparing, wherein, the quality of graphite oxide and the volume ratio of quadrol are 1:40, regulate pH to neutral, after 40 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrate, the filter cake oven dry obtains the graphite oxide intermediate product that ammonia activates.The graphite oxide intermediate product of quadrol activation 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 filtrate, 50 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Embodiment 7
Utilize the standby graphite oxide of Brodie legal system, reaction solution does not carry out aftertreatment; Add 30% amino dodecane in the reaction solution of the graphite oxide for preparing, wherein, the quality of graphite oxide and the volume ratio of amino dodecane are 1:50, regulate pH to neutral, after 40 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrate, the filter cake oven dry obtains the graphite oxide intermediate product that amino dodecane activates.The graphite oxide intermediate product of amino dodecane activation 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 filtrate, 60 ℃ of vacuum-drying 1d of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Utilize the standby graphite oxide of Brodie legal system, reaction solution does not carry out aftertreatment; Add 40% cetylamine in the reaction solution of the graphite oxide for preparing, wherein, the quality of graphite oxide and the volume ratio of cetylamine are 1:40, regulate pH to neutral, after 50 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrate, the filter cake oven dry obtains the graphite oxide intermediate product that cetylamine activates.The graphite oxide intermediate product of cetylamine activation 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 filtrate, 50 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Embodiment 9
Utilize the standby graphite oxide of Brodie legal system, reaction solution does not carry out aftertreatment; Add 30% stearylamine in the reaction solution of the graphite oxide for preparing, wherein, the quality of graphite oxide and the volume ratio of stearylamine are 1:40, regulate pH to neutral, after 40 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrate, the filter cake oven dry obtains the graphite oxide intermediate product that stearylamine activates.The graphite oxide intermediate product of stearylamine activation 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 filtrate, 50 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Embodiment 10
Utilize the standby graphite oxide of Brodie legal system, reaction solution does not carry out aftertreatment; Add 30% stearylamine in the reaction solution of the graphite oxide for preparing, wherein, the quality of graphite oxide and the volume ratio of stearylamine are 1:40, regulate pH to neutral, after 40 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrate, the filter cake oven dry obtains the graphite oxide intermediate product that stearylamine activates.The graphite oxide intermediate product of stearylamine activation is dissolved with 5% potassium hydroxide solution, and ultra-sonic dispersion 2h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrate, 50 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Embodiment 11
Utilize the standby graphite oxide of Brodie legal system, reaction solution does not carry out aftertreatment; Add 40% aniline in the reaction solution of the graphite oxide for preparing, wherein, the quality of graphite oxide and the volume ratio of aniline are 1:40, regulate pH to neutral, after 40 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrate, the filter cake oven dry obtains the graphite oxide intermediate product that aniline activates.The graphite oxide intermediate product of aniline activation is dissolved with 1% sodium hydroxide solution, and ultra-sonic dispersion 2h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrate, 80 ℃ of vacuum-drying 2h of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Embodiment 12
Utilize the standby graphite oxide of Brodie legal system, reaction solution does not carry out aftertreatment; Add 30% tetramethylammonium hydroxide in the reaction solution of the graphite oxide for preparing, wherein, the quality of graphite oxide and the volume ratio of tetramethylammonium hydroxide are 1:40, regulate pH to neutral, after 40 ℃ of stirring reaction 1h, form uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrate, the filter cake oven dry obtains the graphite oxide intermediate product that tetramethylammonium hydroxide activates.The graphite oxide intermediate product of tetramethylammonium hydroxide activation is dissolved with 3% potassium hydroxide solution, and ultra-sonic dispersion 1h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrate, 50 ℃ of vacuum-drying 2d of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Embodiment 13
Utilize the standby graphite oxide of Brodie legal system, reaction solution does not carry out aftertreatment; Add 40% hydroxide (2-hydroxyethyl) in the reaction solution of the graphite oxide for preparing, wherein, the volume ratio of the quality of graphite oxide and hydroxide (2-hydroxyethyl) is 1:20, regulates pH to neutral, after 20 ℃ of stirring reaction 1h, forms uniform dispersion liquid; With the dispersion liquid suction filtration, washing, neutral to filtrate, the filter cake oven dry obtains the graphite oxide intermediate product that hydroxide (2-hydroxyethyl) activates.The graphite oxide intermediate product of hydroxide (2-hydroxyethyl) activation is dissolved with 3% potassium hydroxide solution, and ultra-sonic dispersion 1h obtains homogeneous phase solution; With the solution suction filtration, washing, neutral to filtrate, 90 ℃ of vacuum-drying 2h of filter cake obtain having graphene oxide antibiotic, anticoagulant functions.
Above-described embodiment 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, within all dropping on protection scope of the present invention.
Claims (7)
1. a controlledly synthesis has the method for the graphene oxide of antibiotic, anticoagulant functions, it is characterized in that, utilize the standby graphite oxide of Brodie method, Hummers method or Staudenmaier legal system, reaction solution does not carry out aftertreatment, add aminated compounds to react in reaction solution, make the graphite oxide intermediate product of amine activation, the intermediate product of gained ultra-sonic dispersion in basic solution obtains described graphene oxide.
2. controlledly synthesis according to claim 1 has the method for the graphene oxide of antibiotic, anticoagulant functions, it is characterized in that described method comprises the following steps:
A) utilize the standby graphite oxide of Brodie method, Hummers method or Staudenmaier legal system, reaction solution does not carry out aftertreatment;
B) add mass concentration 5 ~ 50% aminated compoundss in the reaction solution of the graphite oxide for preparing, after 0 ~ 30 ℃ of lower stirring reaction 1 ~ 5h, form uniform dispersion liquid;
C) with dispersion liquid suction filtration, washing, neutral to filtrate, the oven dry filter cake makes the graphite oxide intermediate product that amine activates;
D) the graphite oxide intermediate product with the amine activation dissolves with mass concentration 0.1 ~ 5% alkaline solution, and ultra-sonic dispersion 0.5h ~ 5h obtains homogeneous phase solution;
E) with the solution suction filtration, the washing screening is to neutral, and 30 ~ 100 ℃ of vacuum-dryings obtain described graphene oxide.
3. controlledly synthesis according to claim 1 and 2 has the method for the graphene oxide of antibiotic, anticoagulant functions, and it is characterized in that: described aminated compounds is ammoniacal liquor, aliphatic amide, aromatic amine, quaternary amine alkali, pyridine, pyrroles or porphyrin.
4. controlledly synthesis according to claim 3 has the method for the graphene oxide of antibiotic, anticoagulant functions, and it is characterized in that: described aliphatic amide is dimethylamine, methylamine, Trimethylamine 99, quadrol, amino dodecane, cetylamine or stearylamine; Described aromatic amine is aniline; Described quaternary amine alkali is tetramethylammonium hydroxide.
5. controlledly synthesis according to claim 1 and 2 has the method for the graphene oxide of antibiotic, anticoagulant functions, 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. controlledly synthesis according to claim 2 has the method for the graphene oxide of antibiotic, anticoagulant functions, and it is characterized in that: in step d), described alkali is sodium hydroxide or potassium hydroxide.
7. has a stannic oxide/graphene nano material antibiotic, anticoagulant functions to what 6 described either method made according to claim 1.
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