CN104027807A - Graphene oxide/copper selenide/PEG (Polyethylene Glycol) nanocomposite material, as well as preparation method and application thereof - Google Patents
Graphene oxide/copper selenide/PEG (Polyethylene Glycol) nanocomposite material, as well as preparation method and application thereof Download PDFInfo
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- CN104027807A CN104027807A CN201410245566.0A CN201410245566A CN104027807A CN 104027807 A CN104027807 A CN 104027807A CN 201410245566 A CN201410245566 A CN 201410245566A CN 104027807 A CN104027807 A CN 104027807A
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Abstract
The invention discloses a graphene oxide/copper selenide/PEG (Polyethylene Glycol) nanocomposite material; copper selenide nanoparticles and PEG are modified on the surface of graphene oxide; graphene oxide and copper selenide nanoparticles are mutually connected through deposition; and graphene oxide and PEG are exchanged and combined through a ligand. The nanocomposite material prepared by the method disclosed by the invention has high solar-thermal conversion efficiency and is a good solar-thermal reagent; and the preparation method disclosed by the invention has the advantages of being simple to operate, available in raw materials, low in cost and the like and is applied to industrial production.
Description
Technical field
The invention belongs to nanometer photo-thermal reagent technical field, be specifically related to a kind of graphene oxide/copper selenide/PEG nano composite material and its preparation method and application.
Background technology
Thereby the photo-thermal character of nanoparticle refers to that utilizing near infrared light to excite its surface plasma body resonant vibration or energy jump to produce a large amount of heat destroys cancerous cell, photo-thermal therapy derivative and that come has been proved to be a kind of and can effectively kills target cell and do not damage the method for surrounding health tissue thus.In addition, the wave-length coverage of the near infrared light that photo-thermal therapy uses is conventionally between 650-950nm, and this is that near infrared light is in tissue because in this wave-length coverage, and the penetration capacity in blood and water is the strongest, can kill in body the more tumor tissues of deep layer.Compare X-ray therapy and the chemotherapy of traditional treatment tumor, photo-thermal therapy is much smaller to the side effect of human body, first the near infrared light that photo-thermal therapy uses does not damage the normal structure of irradiated site, and it only to photo-thermal reagent place lesions position can excite high temperature kill tumor tissues and surrounding health tissue is not damaged, this has just been avoided the adverse effect of the clean cut of chemotherapy.
At present many optothermal materials of research have golden nanometer particle, germanium nanocrystal body, porous silicon, graphene platelet, the CNT of different-shape, the nanocrystal of sulfide and the ferrum cobalt nanocrystal body of graphitic carbon parcel etc. of copper (II), and these materials are applied the requirement that also needs to meet the little and good biocompatibility of size in vivo simultaneously.The reason that recently copper based semiconductor comes into one's own is exactly that its bio-toxicity is less than the nanoparticle of cadmio.
Graphene, due to its unique electrical properties, optical property and photo-thermal transfer capability, is described as the most potential material with carbon element of 21 century.And the nano material of the other types of comparing, graphene oxide all has absorption in ultraviolet near infrared region, and contains the more oxygen functional group that contains, and makes it in aqueous solution, have good dispersibility; Have bigger serface, low cytotoxicity, and extremely low production cost, can become a kind of new nano material with biocompatibility and be applied to biomedical sector.In addition, graphene oxide has two-dimensional layered structure, and surface area ratio is larger, can load many kinds of substance, and as tumor targeted molecular, antibumor molecules medicine, gene and there is the nanoparticle of photo-thermal conversion character.Thus research worker expect if by Graphene and functional nanoparticle combine the nano composite material prepared can integrated multiple imaging and treatment means on a kind of material, not only can reduce production costs, and can reduce drug use amount, will drop to minimum to patient's infringement.Therefore research and develop more graphene-based nano composite material significant, have a extensive future.
Summary of the invention
The object of this invention is to provide a kind of graphene oxide/copper selenide/PEG nano composite material.This material has good biocompatibility, in water good dispersion, and the toxicity of material own is little, in photo-thermal therapy, has a good application prospect.
Another object of the present invention is to provide the preparation method of this composite, and that the method has is simple to operate, raw material is easy to get and the advantage such as with low cost.
The object of the present invention is achieved like this:
A kind of graphene oxide/copper selenide/PEG nano composite material, graphene oxide finishing copper selenide nanoparticles and PEG, between graphene oxide and copper selenide nanoparticles, connecting by sedimentary facies, is to be combined by ligand exchange between graphene oxide and PEG.
The preparation method of above-mentioned graphene oxide/copper selenide/PEG nano composite material comprises the steps: nano graphene oxide to be dispersed in hydrophobic solvent, then Cu source Cu-lyt. and Se source selenourea are dissolved in respectively in described solvent, adopt high warm injection to react 10-30min at 220-240 DEG C, obtain graphene oxide/copper selenide, and then add Polyethylene Glycol (PEG) to improve water solublity, obtain graphene oxide/copper selenide/PEG nano composite material.
The mol ratio in described Cu source and Se source is 2:1.
Add PEG and graphene oxide/copper selenide weight ratio be 2-4:1.
The preferred oleyl amine of described hydrophobic solvent.
Graphene oxide/copper selenide/PEG the nano composite material obtaining by said method can be used for preparing photo-thermal therapy of cancer medicine.
Graphene oxide of the present invention adopts improved Hummers legal system standby, the copper selenide nanoparticles of graphene oxide and modification has good optical absorption near infrared region, can be used as good optothermal material performance synergism, can effectively kill tumor cell, thereby realize collaborative object of carrying out photo-thermal therapy.Meanwhile, the present invention has improved biocompatibility and the stability of material by modifying PEG, for material is laid a good foundation in the application of biomedical sector.
Advantage of the present invention is:
1. graphene oxide/copper selenide/PEG nano composite material that prepared by the present invention is a kind of nano composite material with collaborative photo-thermal therapy, and photo-thermal successful, can be good at killing tumor cell, and large in biomedical sector using value, prospect is wide;
2. preparation method of the present invention is simple to operate, low for equipment requirements;
3. raw material of the present invention is easy to get and is cheap.
Brief description of the drawings
Fig. 1 is the X-ray powder diffraction figure (XRD) of the graphene oxide of use in the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope photo (TEM) of the graphene oxide of use in the embodiment of the present invention 1.
Fig. 3 is the X-ray powder diffraction figure (XRD) of graphene oxide/copper selenide in the embodiment of the present invention 1/PEG nano composite material.
Fig. 4 is the transmission electron microscope picture (TEM) of oil-soluble graphene oxide/copper selenide nano composite material in the embodiment of the present invention 1.
Fig. 5 is the water solublity photo of the graphene oxide/copper selenide/PEG nano composite material before and after modification in embodiment 1.
Fig. 6 is the transmission electron microscope picture (TEM) that improves the graphene oxide/copper selenide/PEG nano composite material after water solublity in embodiment 1.
Fig. 7 is the UV, visible light absorption figure (UV-Vis) of variable concentrations material in the embodiment of the present invention 1.
Fig. 8 is that in the embodiment of the present invention 1, variable concentrations material laser irradiates material heating curve figure in time.
Fig. 9 is the UV, visible light absorption figure (UV-Vis) of variable concentrations material after laser irradiation in the embodiment of the present invention 1.
Figure 10 is the photo-thermal curve of stability figure of material in the embodiment of the present invention 1.
Detailed description of the invention
In order to understand better essence of the present invention, describe technology contents of the present invention in detail below by embodiment, but content of the present invention is not limited to this.
Embodiment 1
1. get 25mg Cu-lyt. and be dissolved in 10mL oleyl amine, the graphene oxide (GO) of getting 18mg is dispersed in 10mL oleyl amine, with syringe injection cuprous chloride solution, stirs, at N
2in atmosphere, at 130 DEG C, stir 10min, solution is cooled to 100 DEG C.
2. getting 15mg selenourea is dissolved in 5mL oleyl amine, at N
2in atmosphere, at 200 DEG C, stir 10min, in the time that solution is cooled to 160 DEG C, be injected into rapidly with syringe sucking-off in the solution of the first step, mixed solution is continued to be warmed up to 220 DEG C, N
2under atmosphere, stir 30min, after reaction finishes, be cooled to while stirring room temperature.
3. by final solution centrifugal 2min under 10000r, discard blue supernatant, with absolute ethanol washing several, by nanoparticle GO/Cu
2-xse precipitation is dispersed in chloroform and saves backup.
4. get the GO/Cu of 4mg/mL
2-xse solution 10mL, in flask, takes the PEG of one end band carboxyl of 0.1g, joins in flask after being dissolved in 10mL chloroform, is stirring an evening in room temperature, with dehydrated alcohol cyclic washing, centrifugal, precipitation is dispersed in water.
With the aqueous solution of the material of the material formulation variable concentrations of preparation in embodiment 1, selecting Concentraton gradient is 150,100,75,50,25,0 μ g/mL;
Measure the uv absorption of variable concentrations material with ultraviolet spectrophotometer;
The material of variable concentrations at 808nm, 0.3W/cm
2under the laser of intensity, irradiate 5min, record the image of whole process with infrared temperature-sensitive photographic head, then draw the curve of temperature with irradiation time;
After irradiation, again measure the uv absorption of variable concentrations with ultraviolet spectrophotometer;
Choose the material of a concentration, under identical laser intensity, irradiate 5min, then allow it freely lower the temperature, reirradiation temperature-fall period 5 times, measures the stability under material illumination.Draw temperature variation curve according to the video recording of infrared temperature-sensitive photographic head.
Fig. 7 is the UV, visible light absorption figure (UV-vis) of variable concentrations material in the embodiment of the present invention 1, and as we know from the figure, material has good absorption near infrared region, can be used as optothermal material.
Fig. 8 is the variable concentrations material heating curve figure in time of laser irradiation in the embodiment of the present invention 1, known, the photo-thermal effect comparative superiority of material.
Fig. 9 is the UV, visible light absorption figure (UV-vis) of variable concentrations material after laser irradiation in the embodiment of the present invention 1, with prelaser uv absorption figure contrast, can obtain after pre-irradiation uv absorption changes little, can the stability of illustrative material under illumination fine.
Figure 10 is the photo-thermal curve of stability figure of material in the embodiment of the present invention 1, and material is in the process of reirradiation cooling as we know from the figure, and the temperature of rising can remain unchanged substantially, has more proved that the stability of material after illumination is relatively good.
Claims (6)
1. graphene oxide/copper selenide/PEG nano composite material, it is characterized in that, graphene oxide finishing copper selenide nanoparticles and PEG, connect by sedimentary facies between graphene oxide and copper selenide nanoparticles, between graphene oxide and PEG, is to be combined by ligand exchange.
2. the preparation method of graphene oxide/copper selenide described in claim 1/PEG nano composite material, it is characterized in that, comprise the steps: nano graphene oxide to be dispersed in hydrophobic solvent, then Cu source Cu-lyt. and Se source selenourea are dissolved in respectively in described solvent, adopt high warm injection to react 10-30min at 220-240 DEG C, obtain graphene oxide/copper selenide, and then add PEG to improve water solublity, obtain graphene oxide/copper selenide/PEG nano composite material.
3. the preparation method of graphene oxide/copper selenide described in claim 2/PEG nano composite material, is characterized in that, the mol ratio in described Cu source and Se source is 2:1.
4. the preparation method of graphene oxide/copper selenide described in claim 2/PEG nano composite material, is characterized in that, add PEG and graphene oxide/copper selenide weight ratio be 2-4:1.
5. the preparation method of graphene oxide/copper selenide described in claim 2/PEG nano composite material, is characterized in that, described hydrophobic solvent is oleyl amine.
6. graphene oxide/copper selenide described in claim 1/PEG nano composite material is for the preparation of photo-thermal therapy of cancer medicine.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106033790A (en) * | 2015-02-15 | 2016-10-19 | 武汉理工大学 | Cu2-xSe/graphene composite material and preparation method thereof |
| CN106963951A (en) * | 2017-02-27 | 2017-07-21 | 上海师范大学 | Graphene oxide/manganese tungstate/polyethylene glycol nano-hybrid material and its preparation |
| CN107496444A (en) * | 2017-08-29 | 2017-12-22 | 深圳大学 | A kind of selenium doping black phosphorus prodrug and preparation method thereof |
| CN108207995A (en) * | 2017-11-28 | 2018-06-29 | 南通强生石墨烯科技有限公司 | The copper-based pesticide compound of the degradable graphene oxide-selenizing of slow-release and preparation |
| CN110477012A (en) * | 2019-08-22 | 2019-11-22 | 河南省人民医院 | A kind of GO-PEG/Ag-SD composite material and preparation method and application |
| CN111849585A (en) * | 2020-07-07 | 2020-10-30 | 西安航空职业技术学院 | Preparation method of graphene oxide-polyethylene glycol cross-linked network/carbon microsphere composite material |
Citations (1)
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| CN103505730A (en) * | 2013-10-15 | 2014-01-15 | 东华大学 | Copper selenide/mesoporous silica core-shell nanoparticles and preparation method and application thereof |
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Patent Citations (1)
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| CN103505730A (en) * | 2013-10-15 | 2014-01-15 | 东华大学 | Copper selenide/mesoporous silica core-shell nanoparticles and preparation method and application thereof |
Non-Patent Citations (1)
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| JING BAI 等: "Multifunctional PEG-GO/CuS nanocomposites for near-infrared chemo-photothermal therapy", 《BIOMATERIALS》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106033790A (en) * | 2015-02-15 | 2016-10-19 | 武汉理工大学 | Cu2-xSe/graphene composite material and preparation method thereof |
| CN106033790B (en) * | 2015-02-15 | 2018-10-09 | 武汉理工大学 | A kind of Cu2-xSe/ graphene composite materials and preparation method thereof |
| CN106963951A (en) * | 2017-02-27 | 2017-07-21 | 上海师范大学 | Graphene oxide/manganese tungstate/polyethylene glycol nano-hybrid material and its preparation |
| CN107496444A (en) * | 2017-08-29 | 2017-12-22 | 深圳大学 | A kind of selenium doping black phosphorus prodrug and preparation method thereof |
| CN108207995A (en) * | 2017-11-28 | 2018-06-29 | 南通强生石墨烯科技有限公司 | The copper-based pesticide compound of the degradable graphene oxide-selenizing of slow-release and preparation |
| CN110477012A (en) * | 2019-08-22 | 2019-11-22 | 河南省人民医院 | A kind of GO-PEG/Ag-SD composite material and preparation method and application |
| CN110477012B (en) * | 2019-08-22 | 2021-05-18 | 河南省人民医院 | GO-PEG/Ag-SD composite material and preparation method and application thereof |
| CN111849585A (en) * | 2020-07-07 | 2020-10-30 | 西安航空职业技术学院 | Preparation method of graphene oxide-polyethylene glycol cross-linked network/carbon microsphere composite material |
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