CN106115680A - A kind of curcumin derivate modifies method and the product thereof of graphene oxide - Google Patents
A kind of curcumin derivate modifies method and the product thereof of graphene oxide Download PDFInfo
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Abstract
The present invention relates to a kind of method that curcumin derivate modifies graphene oxide, concretely comprise the following steps: weigh graphene oxide 10 50 milligrams, add 30 200 milliliters of organic solvents, ultrasonic reaction 2 hours at 40 90 DEG C, dispersion forms uniform dark brown liquid；It is slowly added to alkaline reagent 0.2 1 grams, continues ultrasonic or back flow reaction 1 hour, obtain the dispersion liquid of graphene oxide；Weigh curcumin derivate 0.1 0.5 grams; add 30 200 milliliters of organic solvents to dissolve; the lysate of gained is slowly added dropwise to the dispersion liquid of graphene oxide, and adds 0.1 gram of potassium iodide, then under the protection of noble gas at 70 110 DEG C ultrasonic or back flow reaction 48 hours；After the solution of gained filters, by organic solvent washing, finally the vacuum drying oven in 50 DEG C is dried to obtain product；The graphene oxide good stability that curcumin derivate prepared by the inventive method is modified, bioavailability is high, and toxicity is little, and fluorescent optics character is remarkably reinforced, and reaction gentleness, and technique is simple, is suitable for large-scale production.
Description
Technical field
The present invention relates to new material technology field, be specifically related to one and utilize curcumin derivate to pass through physics or chemistry
Grafting mode modifies method and the product thereof of graphene oxide.
Background technology
Curcumin is a kind of natural plant polyphenol extracted from the rhizome Rhizoma Curcumae Longae of zingiberaceous plant.Curcumin and derivant thereof
Not only there is the medicine physiotherapy functions such as significant antiinflammatory, antioxidation, blood fat reducing, atherosclerosis, antitumor, anti HIV-1 virus,
The most also there is good photoluminescent property and biological cell image displaying function (K.Liu, T.L.Guo, et al., Bivalent
Ligand Containing Curcumin and Cholesterol as a Fluorescence Probe for Aβ
Plaques in Alzheimer’s Disease,ACS Chemical Neuroscience,2012,3(2):141–146；Xu
G.Y.,J.F.Wang,et al.,Two-photon absorption and cell imaging of two multi-
branched dyes based on curcumin,Dyes and Pigments,2015,123:267-273)。
Active component in natural curcumin mainly comprises: curcumin, demethoxycurcumin and double de-methoxy Rhizoma Zingiberis Recens
Flavin, an existing halogen-containing curcumin derivate of class, is by a kind of to the saturated of C1-C8 or unsaturated aliphatic hydrocarbon or or many
Kind, and F, Cl, Br or I, synthesize together with curcumin or demethoxycurcumin or bisdemethoxycurcumin and obtain.
Such as curcumin derivate [double (4-bromine butoxy-3-the methoxyphenyl)-1,6-heptadiene-3,5-diketone of 1,7-]
Delivered pertinent literature, disclose relevant preparation method and physico-chemical property (specifically refer to G.Y.Xu, J.F.Wang,
G.F.Si,S.S.Zhou,A novel highly selective chemosensor based on curcumin
fordetection of Cu2+and its application for bioimaging,Sensors and Actuators
B,2016,230:684–689).The preparation method of this thing is as follows with its major experimental analytical data and physicochemical properties:
Preparation method: be dissolved in 20mL DMF solution by 1.1g curcumin, adds 0.9g potassium carbonate, stirring reaction 30min
After, add the Isosorbide-5-Nitrae-dibromobutane and a little potassium iodide heavily steamed, back flow reaction 5h when 80 DEG C, after reaction terminates, liquid is mixed
Compound is poured in 20mL cold water, after filtration, obtains faint yellow crystallite object by silicagel column partition method.The curcumin prepared
Its Main physical chemical property of derivant is: faint yellow crystallite, and in water, dissolubility is low, is soluble in such as ethanol, chloroform, DMF,
The organic solvents such as DMSO.Optical property (such as single photon and two-photon etc.) is stronger than curcumin, and experimentation also shows this compound
To Fe3+,Ag+, especially to Cu2+Have and preferably combine and selective power.
Owing to curcumin and derivant thereof are insoluble in water, external it is oxidized easily；Bioavailability is low and biological in vivo
Activity etc. are less obvious, limit its clinical practice.
Adopt at present in many ways to improve curcumin and the bioavailability of derivant thereof.Including structural modification
Method, i.e. with curcumin as lead compound, design and synthesize a large amount of curcumin analog and derivant, to increase it
Water solublity and anti-tumor activity, or with carrier ancillary technique method, i.e. use liposome, nanoparticle, prodrug etc. novel
Carrier technique.If N.R.Jamesa etc. is in order to overcome and to improve curcumin curative effect of medication not enough, the side chain of glycosyl galactose is utilized to form sediment
Powder and curcumin react and have obtained a kind of grafting conjugated thing (LANH2-Pu Ald-Cur SA), and experiment shows this yoke thing pair
HepG2 hepatoma carcinoma cell does not only have preferable targeting, and can increase metabolic function and improve the aggregation of drug disposition
(P.R.Sarikaa,N.R.James,et al.Galactosylated pullulan–curcumin conjugate
micelles for site specificanticancer activity to hepatocarcinoma cellsP,
Colloids and Surfaces B:Biointerfaces,2015,133:347–355)。
T.S.Anirudhan etc. are grafted onto curcumin on modified chitosan nano particle, and research finds by this
Plant the curcumin medicine of systems communicate, on the one hand improve bioavailability, reduce drug toxicity；On the other hand it is greatly prolonged
Curcumin release time in different pH value (T.S.Anirudhan, P.L.Divya, et al.Synthesis and
characterization of novel drug delivery system using modified chitosan based
hydrogel grafted with cyclodextrin,Chemical Engineering Journal,2016,284:
1259–1269)。
Additionally Chinese invention patent application number be 201210013139.0 patent document disclose a kind of high drug load Rhizoma Zingiberis Recens
Flavin micelle prodrug and preparation method thereof.1,3-propanedicarboxylic acid is joined the curcumin of modification and MPEG mono-PLA of the how light base of end with vinegar
The form of key is bonded, and forms the curcumin micelle monomer of high percent grafting.The drug loading of its micellar system, particle diameter and stable
Property all significantly improves, and enhances EPR effect.Chinese invention patent application number is the patent literary composition of 201210229335.1
Part discloses the preparation method and applications of a kind of curcumin chitosan monostearate grafting micelle.It is with curcumin as raw material
Medicine, uses the graft that oligochitosan, stearic acid are formed as pharmaceutical carrier, defines CSO-A/curcumin through complex reaction and carry
Medicine nano-micelle.MCF-7, MCF-7/Adr and colorectal cancer cells are had by this micelle internal and external test display CSO-SA/curcumin
There is stronger lethal effect.Chinese invention patent application number be 201210141117.2 patent document disclose a kind of Rhizoma Curcumae Longae
Element-polysaccharide conjugate and preparation method and application.Its preparation method is: first passes through phthalein amine and reacts diamine compounds
An Amino End Group be grafted on polysaccharide, obtain the polysaccharide macro-molecular of a free Amino End Group, subsequently with schiff base reaction at polysaccharide bone
Curcumin is introduced on frame.By the graft modification to curcumin, improve its water solublity, inside and outside stability and safety.
Chinese invention patent application number be 201510216062.5 patent document disclose a kind of 1,7-bis(3,4-dimethoxyphenyl)-1,6-heptadiene-3,5-dione polymer latex
Bundle and preparation method thereof and the injection of this polymer micelle or oral administration system and medical usage.This carrier micelle is at water
Property medium in dissolubility and thermodynamic stability significantly improve, and effectively reduce its seepage, degraded and metabolism in vivo, real
Show long circulating and tumor tissues passive target, thus improve drug effect and safety.
Graphene oxide (GO) is the special derivant of Graphene, its surface contain substantial amounts of hydroxyl (-OH), epoxy radicals,
Carboxyl (-COOH), these hydrophilic radicals make GO have good water solublity.Curcumin according to currently available technology connects
In branch method, not yet relate to the method for the graphene oxide about curcumin derivate modification and prepare its light of products therefrom
The property learned Quality Research.
Summary of the invention
The technical problem to be solved in the present invention is a kind of method providing curcumin derivate to modify graphene oxide, carries
The water solublity of high hydrophobicity curcumin derivate and stability, improve the optical property of graphene oxide simultaneously.
Concrete technical scheme is as follows:
1, a kind of method that curcumin derivate modifies graphene oxide, comprises the following steps:
1) weigh graphene oxide 10-50 milligram, add 30-200 milliliter organic solvent, ultrasonic reaction 2 at 40-90 DEG C
Hour, dispersion forms uniform dark brown liquid；
2) it is slowly added to alkaline reagent 0.2-1.0 gram, continues ultrasonic or back flow reaction 1 hour, obtain graphene oxide
Dispersion liquid；
3) weigh curcumin derivate 0.1-0.5 gram, add 30-200 milliliter organic solvent and dissolve, the lysate of gained is delayed
Slowly drop in the dispersion liquid of graphene oxide, and add 0.1 gram of potassium iodide, then in 70-110 under the protection of noble gas
Ultrasonic or back flow reaction 4-8 hour at DEG C；
4) to step 3) after the solution of gained filters, by organic solvent washing, finally in the vacuum drying of 50 DEG C
Case is dried to obtain product.
Concrete, described curcumin derivate is dihalo curcumin derivate, and concrete structure formula is:
Wherein n span be 1-8, m value be-1,0 or 1, X is one or more in F, Cl, Br or I, R1=R2
=CH30 or R1=R2=H or R1=CH30, R2=H.
Concrete, described step 3) in noble gas be nitrogen or argon.
Concrete, described step 3) in detect whole reaction process by TLC.
Further, the graphene oxide that the curcumin derivate prepared by said method is modified, there is following knot
Structure formula:
Wherein GO is graphene oxide, n span be 1-8, m value be-1,0 or 1, X is in F, Cl, Br or I
Plant or multiple, R1=R2=CH30 or R1=R2=H or R1=CH30, R2=H.
The beneficial effects of the present invention is:
One, the present invention is with dihalo curcumin derivate as linking arm, and curcumin derivate is grafted to graphene oxide
On, substantially increase water solublity and the stability of hydrophobicity curcumin derivate.
Two, the method for the graphene oxide that the curcumin derivate that the present invention provides is modified, the product prepared, its light
Learn performance apparently higher than graphene oxide.
Three, product prepared by the graphene oxide method that the curcumin derivate that the present invention provides is modified has biological utilisation
Spend the advantages such as high and low bio-toxicity.Whole building-up process mild condition, reaction is simple, and cost of material is low, is prone to industrialization promotion
Produce.
Accompanying drawing explanation
Fig. 1 is the red of the graphene oxide of the curcumin derivate modification of graphene oxide and the embodiment of the present invention 1 preparation
External spectrum figure；
Fig. 2 is drawing of the graphene oxide of the curcumin derivate modification of graphene oxide and the embodiment of the present invention 1 preparation
Graceful spectrogram；
Fig. 3 is that the X of the graphene oxide of the curcumin derivate modification of graphene oxide and the embodiment of the present invention 1 preparation penetrates
Photoelectron energy (XPS) spectrogram；
Fig. 4 is dividing of the graphene oxide of the curcumin derivate modification of graphene oxide and the embodiment of the present invention 1 preparation
Dissipate performance map；
Fig. 5 is the graphene oxide of the curcumin derivate modification of curcumin derivate and the embodiment of the present invention 1 preparation
Toxicity figure；
Fig. 6 is the light of the graphene oxide of the curcumin derivate modification of graphene oxide and the embodiment of the present invention 1 preparation
Learn character figure.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further details.
Embodiment 1
(1) weigh graphene oxide (GO) 10 milligrams in the beaker of 100 milliliters, add 30 milliliters of organic reagents, in 40
DEG C ultrasonic reaction 2 hours, is dispersed into uniform dark brown liquid；
(2) it is slowly added to alkaline reagent 0.2 gram, continues ultrasonic reaction 1 hour, obtain the dispersion liquid of graphene oxide；
(3) weigh dihalo curcumin derivate [double (4-bromine butoxy-3-the methoxyphenyl)-1,6-heptadiene of 1,7--
3,5-diketone] 0.1 gram in beaker, and dissolve with 30 milliliters of organic reagents, be slowly added dropwise the dispersion to graphene oxide (GO)
In liquid, add KI 0.1 gram, continue back flow reaction 4.0 hours in 70 DEG C under nitrogen protection；Whole reaction is anti-by TLC detection
Answer process (detection graphene oxide and the reaction optimum degree of dihalo curcumin derivate).
(4) filter above-mentioned solution, wash successively with acetone, ethanol respectively, rear thing will be washed in the vacuum drying oven of 50 DEG C
Air-dry 4 hours, obtain target product.Productivity 42.3%
The alkaline reagent mentioned in above-mentioned steps can select sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, hydrogen-oxygen
Change sodium, potassium hydroxide, diethylamine, one or more the combination in triethylamine and pyridine.Organic solvent can be selected for dichloromethane
Alkane, chloroform, alcohols, N, N-dimethylimino, dimethyl sulfoxide, a kind of in pyridine or or multiple combination.
The structural formula of the target product obtained is as follows:
Shown in each experimental features reference Fig. 1-Fig. 6 of gained target product, concrete:
Fig. 1 is that the curcumin of graphene oxide (GO), curcumin derivate (CUDE) and the embodiment of the present invention 1 preparation derives
The infrared spectrogram of the graphene oxide (GO-f-CUDE) that thing is modified.Contrast infrared spectrum understands, the GO-f-CUDE spectrum of modification
In figure, at 500-2000cm-1The characteristic peak of many curcumin derivates, the change of the infrared spectrum after modification occur between wave number
Demonstrate curcumin derivate from an angle to be grafted on GO.
Fig. 2 is the graphene oxide of the curcumin derivate modification of graphene oxide (GO) and the embodiment of the present invention 1 preparation
(GO-f-CUDE) Raman spectrogram；As can be seen from Figure 2, the D band in GO-f-CUDE carries (1350cm-1) and G band (1590cm-1)
The generation significant change compared with original GO of strong ratio I D/IG in peak, this be due to GO grafting curcumin derivate molecule after, sample
The reason that middle defect and disordered structure increase.
Fig. 3 is the graphene oxide of the curcumin derivate modification of graphene oxide (GO) and the embodiment of the present invention 1 preparation
(GO-f-CUDE) x-ray photoelectron energy (XPS) spectrogram.As it is shown on figure 3, full spectrum scanning shows depositing of C, O element
, GO-f-CUDE scanning discovery Br element is occurred in that the new absworption peak of Br3d at 70.4eV simultaneously, thus be further characterized by connecing
There is curcumin derivate structure in the product that branch is later.
Fig. 4 is the graphene oxide of the curcumin derivate modification of graphene oxide (GO) and the embodiment of the present invention 1 preparation
(GO-f-CUDE) dispersive property schematic diagram.As shown in Figure 4, GO and GO-f-CUDE is dispersed in respectively PBS and DMSO solution
In, ultrasonic disperse, the photo photographed after then standing 5 days shows: GO bad dispersibility in PBS and DMSO solution, one day is not
To occurring as soon as significant precipitated and separated, and after graphene oxide grafting curcumin derivate, either molten at PBS and DMSO
Liquid all shows good dispersion stabilization.
Fig. 5 is the graphite oxide of the curcumin derivate modification of curcumin derivate (GO) and the embodiment of the present invention 1 preparation
The toxicity figure of alkene (GO-f-CUDE).Knowable to figure, under the same terms and same concentrations, the oxidation stone that curcumin derivate is modified
Ink alkene toxicity (GO-f-CUDE) is significantly lower than corresponding curcumin derivate.
Fig. 6 is graphene oxide (GO), and the curcumin of curcumin derivate (CUDE) and the embodiment of the present invention 1 preparation derives
The optical property figure of the graphene oxide (GO-f-CUDE) that thing is modified.Fig. 6 shows the graphene oxide that curcumin derivate is modified
Optical property apparently higher than graphene oxide, but less than its curcumin derivate.
Embodiment 2
(1) weigh graphene oxide (GO) 30 milligrams in the beaker of 200 milliliters, add 120 milliliters of organic reagents, in 70
DEG C ultrasonic reaction 2 hours, is dispersed into uniform dark brown liquid；
(2) it is slowly added to alkaline reagent 0.6 gram, continues ultrasonic reaction 1 hour, obtain the dispersion liquid of graphene oxide；
(3) weigh dihalo curcumin derivate [double (4-bromine butoxy-3-the methoxyphenyl)-1,6-heptadiene of 1,7--
3,5-diketone] 0.35 gram in beaker, and dissolve with 120 milliliters of organic reagents, be slowly added dropwise to graphene oxide (GO) point
Dissipate in liquid, add KI 0.1 gram, under argon shield, continue back flow reaction 6.0 hours in 90 DEG C；
(4) filter above-mentioned solution, wash successively with dichloromethane, ethanol respectively, rear thing will be washed in the vacuum drying of 50 DEG C
Case air-dries 4 hours, obtains target product.Productivity 46.5%.
The alkaline reagent mentioned in above-mentioned steps can select sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, hydrogen-oxygen
Change sodium, potassium hydroxide, diethylamine, one or more the combination in triethylamine and pyridine.Organic solvent can be selected for dichloromethane
Alkane, chloroform, alcohols, N, N-dimethylimino, dimethyl sulfoxide, a kind of in pyridine or or multiple combination.
Each experimental features of the present embodiment 2 gained target product can refer to, shown in Fig. 1-Fig. 6, be not detailed equally.
Embodiment 3
(1) weigh graphene oxide (GO) 50 milligrams in the beaker of 250 milliliters, add 200 milliliters of organic reagents, in 90
DEG C ultrasonic reaction 2 hours, is dispersed into uniform dark brown liquid；
(2) it is slowly added to alkaline reagent 1.0 grams, continues ultrasonic reaction 1 hour, obtain the dispersion liquid of graphene oxide；
(3) weigh dihalo curcumin derivate [double (4-bromine butoxy-3-the methoxyphenyl)-1,6-heptadiene of 1,7--
3,5-diketone] 0.5 gram in beaker, and dissolve with 200 milliliters of organic reagents, be slowly added dropwise the dispersion to graphene oxide (GO)
In liquid, add KI 0.1 gram, continue back flow reaction 8.0 hours in 110 DEG C under nitrogen protection；
(4) filter above-mentioned solution, wash successively with dichloromethane, ethanol respectively, rear thing will be washed in the vacuum drying of 50 DEG C
Case air-dries 4 hours, obtains target product.Productivity 48.4%
The alkaline reagent mentioned in above-mentioned steps can select sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, hydrogen-oxygen
Change sodium, potassium hydroxide, diethylamine, one or more the combination in triethylamine and pyridine.Organic solvent can be selected for dichloromethane
Alkane, chloroform, alcohols, N, N-dimethylimino, dimethyl sulfoxide, a kind of in pyridine or or multiple combination.
Each experimental features of the present embodiment 3 gained target product can refer to, shown in Fig. 1-Fig. 6, be not detailed equally.
Embodiment 4
(1) weigh graphene oxide (GO) 10 milligrams in the beaker of 100 milliliters, add 30 milliliters of organic reagents, in 40
DEG C ultrasonic reaction 2 hours, is dispersed into uniform dark brown liquid；
(2) it is slowly added to alkaline reagent 0.2 gram, continues ultrasonic reaction 1 hour, obtain the dispersion liquid of graphene oxide；
(3) weigh dihalo curcumin derivate [double (4-iodine propoxyl group-3-the methoxyphenyl)-1,6-heptadiene of 1,7--
3,5-diketone] 0.1 gram in beaker, and dissolve with 30 milliliters of organic reagents, be slowly added dropwise the dispersion to graphene oxide (GO)
In liquid, add KI 0.1 gram, continue back flow reaction 4.0 hours in 70 DEG C under nitrogen protection；Whole reaction is anti-by TLC detection
Answer process (detection graphene oxide and the reaction optimum degree of dihalo curcumin derivate).
(4) filter above-mentioned solution, wash successively with acetone, ethanol respectively, rear thing will be washed in the vacuum drying oven of 50 DEG C
Air-dry 4 hours, obtain target product.Productivity 44.2%
The alkaline reagent mentioned in above-mentioned steps can select sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, hydrogen-oxygen
Change sodium, potassium hydroxide, diethylamine, one or more the combination in triethylamine and pyridine.Organic solvent can be selected for dichloromethane
Alkane, chloroform, alcohols, N, N-dimethylimino, dimethyl sulfoxide, a kind of in pyridine or or multiple combination.
The structural formula of the target product obtained is as follows:
Each experimental features of the present embodiment 4 gained target product can refer to, shown in Fig. 1-Fig. 6, be not detailed equally.
Embodiment 5
(1) weigh graphene oxide (GO) 30 milligrams in the beaker of 200 milliliters, add 120 milliliters of organic reagents, in 70
DEG C ultrasonic reaction 2 hours, is dispersed into uniform dark brown liquid；
(2) it is slowly added to alkaline reagent 0.6 gram, continues ultrasonic reaction 1 hour, obtain the dispersion liquid of graphene oxide；
(3) dihalo curcumin derivate [1,7-double (the dilute epoxide of 4-bromine fourth)-3-methoxyphenyl-1,6-heptan two is weighed
Alkene-3,5-diketone] 0.30 gram in beaker, and dissolve with 100 milliliters of organic reagents, be slowly added dropwise to graphene oxide (GO)
In dispersion liquid, add KI 0.1 gram, under argon shield, continue back flow reaction 6.0 hours in 90 DEG C；
(4) filter above-mentioned solution, wash successively with dichloromethane, ethanol respectively, rear thing will be washed in the vacuum drying of 50 DEG C
Case air-dries 4 hours, obtains target product.Productivity 46.2%.
The alkaline reagent mentioned in above-mentioned steps can select sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, hydrogen-oxygen
Change sodium, potassium hydroxide, diethylamine, one or more the combination in triethylamine and pyridine.Organic solvent can be selected for dichloromethane
Alkane, chloroform, alcohols, N, N-dimethylimino, dimethyl sulfoxide, a kind of in pyridine or or multiple combination.
The structural formula of the target product obtained is as follows:
Each experimental features of the present embodiment 5 gained target product can refer to, shown in Fig. 1-Fig. 6, be not detailed equally.
The alkaline reagent mentioned in above-mentioned steps can select sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, hydrogen-oxygen
Change sodium, potassium hydroxide, diethylamine, one or more the combination in triethylamine and pyridine.Organic solvent can be selected for dichloromethane
Alkane, chloroform, alcohols, N, N-dimethylimino, dimethyl sulfoxide, a kind of in pyridine or or multiple combination.
Embodiment 6
(1) weigh graphene oxide (GO) 50 milligrams in the beaker of 250 milliliters, add 200 milliliters of organic reagents, in 90
DEG C ultrasonic reaction 2 hours, is dispersed into uniform dark brown liquid；
(2) it is slowly added to alkaline reagent 1.0 grams, continues ultrasonic reaction 1 hour, obtain the dispersion liquid of graphene oxide；
(3) dihalo curcumin derivate [double (the dilute epoxide of 4-chlorine penta) phenyl-1,6-heptadiene-3,5-two of 1,7-is weighed
Ketone] 0.5 gram in beaker, and dissolve with 200 milliliters of organic reagents, be slowly added dropwise to the dispersion liquid of graphene oxide (GO),
Add KI 0.1 gram, continue back flow reaction 8.0 hours in 110 DEG C under nitrogen protection；
(4) filter above-mentioned solution, wash successively with dichloromethane, ethanol respectively, rear thing will be washed in the vacuum drying of 50 DEG C
Case air-dries 4 hours, obtains target product.Productivity 45.7%.
Each experimental features of the present embodiment 6 gained target product can refer to, shown in Fig. 1-Fig. 6, be not detailed equally.
The alkaline reagent mentioned in above-mentioned steps can select sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, hydrogen-oxygen
Change sodium, potassium hydroxide, diethylamine, one or more the combination in triethylamine and pyridine.Organic solvent can be selected for dichloromethane
Alkane, chloroform, alcohols, N, N-dimethylimino, dimethyl sulfoxide, a kind of in pyridine or or multiple combination.
The above, the only preferable detailed description of the invention of the present invention, but scope is not limited thereto, and any
Those familiar with the art in the technical scope of present disclosure, the change that can readily occur in or replacement, all answer
Contain within protection scope of the present invention.Therefore scope is as the criterion with the protection domain of claims.
Claims (5)
1. the method that a curcumin derivate modifies graphene oxide, it is characterised in that comprise the following steps:
1) weighing graphene oxide 10-50 milligram, add 30-200 milliliter organic solvent, at 40-90 DEG C, ultrasonic reaction 2 is little
Time, dispersion forms uniform dark brown liquid；
2) it is slowly added to alkaline reagent 0.2-1.0 gram, continues ultrasonic or back flow reaction 1 hour, obtain the dispersion of graphene oxide
Liquid；
3) weigh curcumin derivate 0.1-0.5 gram, add 30-200 milliliter organic solvent and dissolve, the lysate of gained is slowly dripped
Add in the dispersion liquid of graphene oxide, and add 0.1 gram of potassium iodide, then under the protection of noble gas at 70-110 DEG C
Ultrasonic or back flow reaction 4-8 hour；
4) to step 3) after the solution of gained filters, by organic solvent washing, finally the vacuum drying oven in 50 DEG C is done
Dry obtain product.
A kind of curcumin derivate the most according to claim 1 modifies the method for graphene oxide, it is characterised in that described
Curcumin derivate is dihalo curcumin derivate, and concrete structure formula is:
Wherein n span be 1-8, m value be-1,0 or 1, X is one or more in F, Cl, Br or I, R1=R2=CH30
Or R1=R2=H or R1=CH30, R2=H.
A kind of curcumin derivate the most according to claim 1 modifies the method for graphene oxide, it is characterised in that described
Step 3) in noble gas be nitrogen or argon.
A kind of curcumin derivate the most according to claim 1 modifies the method for graphene oxide, it is characterised in that described
Step 3) in detect whole reaction process by TLC.
A kind of curcumin derivate the most according to claim 2 modifies the preparation-obtained Rhizoma Curcumae Longae of method of graphene oxide
The graphene oxide of element Derivatives Modified, it is characterised in that there is following general structure:
Wherein GO is graphene oxide, n span be 1-8, m value be-1,0 or 1, X be the one in F, Cl, Br or I or
Multiple, R1=R2=CH30 or R1=R2=H or R1=CH30, R2=H.
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