CN103405791A - Graphene oxide/BaGdF5/PEG multifunctional material as well as preparation method and application thereof - Google Patents
Graphene oxide/BaGdF5/PEG multifunctional material as well as preparation method and application thereof Download PDFInfo
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- CN103405791A CN103405791A CN2013103478720A CN201310347872A CN103405791A CN 103405791 A CN103405791 A CN 103405791A CN 2013103478720 A CN2013103478720 A CN 2013103478720A CN 201310347872 A CN201310347872 A CN 201310347872A CN 103405791 A CN103405791 A CN 103405791A
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Abstract
The invention discloses a graphene oxide/BaGdF5/PEG multifunctional material. A preparation method of the material comprises the following steps: dispersing nano graphene oxide into alcohol, adding inorganic salts containing Gd, Ba and F respectively as per the molar ratio of 1 to 1 to 5 of Gd to Ba to F, then adding PEG as per weight ratio of (3-5) to 1 of PEG to graphene oxide, stirring for 30 minutes, and finally, reacting for 23-24 hours at the temperature of 180-190 DEG C by adopting the solvothermal method. The material, as well as the preparation method and application thereof has the following advantages: the prepared graphene oxide/BaGdF5/PEG multifunctional material is obvious in photo-thermal effect and can satisfactorily kill tumor cells; the operation is simple, and the requirement for equipment is low; the prepared graphene oxide sheet is thin, good in dispersibility and excellent in water solubility; the raw materials can be acquired easily, and the price is low; the material is a multifunctional materials with functions of magnetic resonance, CT double-mode imaging and photo-thermal treatment, and has a great application value in the field of biomedicine.
Description
Technical field
The invention belongs to the nano-contrast agent technical field, be specifically related to a kind of graphene oxide/BaGdF
5/ PEG multifunctional material and its preparation method and application.
Background technology
Carbon is the most magical element of nature, in Nanometer World, the performance of carbon is amazing too, the strong K sea nurse of the peace moral of Univ Manchester UK in 2004 (Andre K.Geim) produces Graphene first, it is in the world the thinnest New Two Dimensional nano material, and its thickness is only 0.35nm.Its peculiar property has attracted countless scientists, can say that it is that in many new materials, tool is potential, is called as " miracle material ", all has great application prospect in industry, power industry and electronic industry.
With the graphite-phase ratio, in graphene oxide, contain the chemical groups such as carboxyl, hydroxyl, carbonyl and epoxy radicals, wherein carboxyl and hydroxyl modified are in the edge of oxidized graphite flake, carbonyl and epoxy radicals are between the graphene oxide layer, graphite is water-fast material originally, and graphene oxide has extremely strong hydrophilic, easily be scattered in the stable colloidal sol of formation in polarizable medium, this is the existence due to these active groups of graphene oxide surface.
The 1950's, scientist has proposed the structure of graphene oxide in succession, it is generally acknowledged, graphene oxide has two-dimensional layered structure, and surface area ratio is larger, can the load many kinds of substance, and graphene oxide has good optical absorption near infrared region, can be used as photo-thermal agent preferably.Ba is the main component of the present CT contrast agent of commonly using, and containing the Gd material known is good T
1Contrast agent.At present, the research of graphene oxide starts to pay close attention to its application aspect biological medicine, and such as medicine, gene transportation, particularly the research for the treatment of of cancer targeted drug transmission system has caused very large concern.
Summary of the invention
The purpose of this invention is to provide a kind of graphene oxide/BaGdF
5/ PEG multifunctional material.This material has good biocompatibility, dispersibility is fine in water, and the toxicity of material own is very little.In nuclear magnetic resonance, CT imaging and photo-thermal therapy, has good application.
Another object of the present invention is to provide the preparation method of this multifunctional material, 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:
Graphene oxide/BaGdF
5The preparation method of/PEG multifunctional material, comprise the steps: nano graphene oxide is dispersed in alcohol, mol ratio 1:1:5 according to Gd, Ba, tri-kinds of elements of F adds the inorganic salt that contains Gd, Ba, F element, weight ratio according to PEG and graphene oxide is that 3-5:1 adds PEG again, after stirring 30min, adopt solvent-thermal method to react 23~24h under 180~190 ℃, make graphene oxide/BaGdF
5/ PEG multifunctional material.
The preparation method of described nano graphene oxide comprises the steps: powdered graphite and NaCl mixed grinding 25-35min, wash with water and remove by filter NaCl, powdered graphite after being expanded, add Chile saltpeter and 95wt%-98wt% concentrated sulphuric acid, then the speed according to 0.05-0.1g/min adds KMnO
4, stirring 6-12d, mixture stirs 40-60min under 65-80 ℃, then under 98-110 ℃, stir 100-120min; Use the hydrogen peroxide cessation reaction, be cooled to room temperature, ultrasonic 5~8hr, washing is got solid, ultrasonic dispersion in water; The mass ratio of powdered graphite and Chile saltpeter is 5:2-5:3, powdered graphite and KMnO
4Mass ratio be 0.9:3-1:3.
The inorganic salt of the described Gd of containing, Ba, F element is respectively Gd (NO
3)
36H
2O, BaCl
2And NH
4F.
Described alcohol is ethylene glycol.
The molecular weight of described PEG is 1000-3000.
Graphene oxide/the BaGdF obtained by said method
5/ PEG multifunctional material, can be used for nuclear magnetic resonance, NMR T
1Contrast agent, CT contrast agent and photo-thermal therapy of cancer medicine.
At first the present invention adopts the standby graphene oxide of improved Hummers legal system, then by this graphene oxide finishing BaGdF
5Nanoparticle, graphene oxide and BaGdF
5Between nanoparticle, connect by sedimentary facies; Graphene oxide and nanoparticle are combined by static and hydrogen bond action between PEG, can be used for improving biocompatibility and the stability of material.The BaGdF modified
5Gd ion in nanoparticle has paramagnetism, is to apply at present T more widely
1The contrast agent raw material; And the combined effect of the Ba in nanoparticle and Gd makes material, it is also a kind of good CT contrast agent; Utilize graphene oxide in the good optical absorption of near infrared region, graphene oxide can be used as good photo-thermal conversion agent, kill tumor cell effectively.Comprehensive above-mentioned functions, thus realized having the purpose of MR and CT Double-mode imaging and photo-thermal therapy multifunctional material.Resulting materials has good biocompatibility simultaneously, has established the basis of material in the biomedical sector application.
Essential implementation of the present invention is: while adopting Hummers method and supercritical ultrasonics technology to prepare graphene oxide, note adding the amount of potassium permanganate and the grasp of time, to add potassium permanganate with the time of 30min left and right, the last ultrasonic time will be grown, and the temperature when ultrasonic can not be too high, the graphene oxide lamella of preparation is thinner like this, and evenly.Meet BaGdF
5The whipping process of material will be controlled well, and mixing time is crucial, and the mixing time nanoparticle of controlling well could be modified to the graphene oxide thin slice uniformly.The material that this method prepares can be dispersed in water well, and has good biocompatibility.This method is simple to operate, low for equipment requirements, and the needed raw material price is low, and by-product is nuisanceless, environmentally safe.The present invention has novelty, creativeness and practicality is widely being arranged aspect bio-imaging and treatment of cancer.
Advantage of the present invention is:
1. graphene oxide/the BaGdF prepared
5/ PEG multifunctional material, photo-thermal successful, kill tumor cell well;
2. experimental implementation is simple, low for equipment requirements;
3. thinner, the good dispersion of graphene oxide lamella, the good water solubility of preparation;
4. raw material is easy to get, cheap;
5. be a kind of multifunctional material with magnetic resonance and CT Double-mode imaging, photo-thermal therapy, large in the biomedical sector using value.
The accompanying drawing explanation
Fig. 1 is the infrared spectrogram (IR figure) of the graphene oxide of preparation in the embodiment of the present invention 1; A in Fig. 1 is graphite, and b is graphene oxide.
Fig. 2 is the transmission electron microscope photo (TEM) of the graphene oxide of preparation in the embodiment of the present invention 1.
Fig. 3 is graphene oxide/BaGdF in the embodiment of the present invention 2
5The transmission electron microscope picture of/PEG (TEM).
Fig. 4 is graphene oxide/BaGdF in the embodiment of the present invention 2
5The X-ray powder diffraction figure (XRD) of/PEG.
Fig. 5 is graphene oxide/BaGdF in the embodiment of the present invention 2
5The infrared spectrogram of/PEG (IR).
Fig. 6 is the graphene oxide/BaGdF of preparation in case study on implementation 3
5The transmission electron microscope picture of/PEG material (TEM).
Fig. 7 is the UV, visible light near infrared absorption figure (UV-Vis-NIR) of variable concentrations material in the embodiment of the present invention 3.
Fig. 8 is that in the embodiment of the present invention 3, the variable concentrations material laser irradiates material heating curve figure in time.
Fig. 9 is the UV, visible light near infrared absorption figure (UV-Vis-NIR) of variable concentrations material after laser irradiation in the embodiment of the present invention 3.
Figure 10 is the photo-thermal curve of stability figure of material in the embodiment of the present invention 3.
Figure 11 is graphene oxide/BaGdF in the embodiment of the present invention 2
5The T of/PEG dispersion of materials in water
1Weighted imaging figure.
Figure 12 is graphene oxide/BaGdF in the embodiment of the present invention 2
5/ PEG material relaxation rate R
1(1/T
1) and sample in linear relationship chart between gadolinium concentration.
Figure 13 is graphene oxide/BaGdF in the embodiment of the present invention 2
5The T of/PEG dispersion of materials in water
2Weighted imaging figure.
Figure 14 is graphene oxide/BaGdF in the embodiment of the present invention 2
5/ PEG material relaxation rate R
2(1/T
2) and sample in linear relationship chart between gadolinium concentration.
The specific embodiment
In order to understand better essence of the present invention, below by embodiment, describe technology contents of the present invention in detail, but content of the present invention is not limited to this.
1) powdered graphite and NaCl mixed grinding 25-35min, wash with water and remove by filter NaCl; Take respectively the graphite powder after 1g expands, 0.5g Chile saltpeter, 3g potassium permanganate;
2) graphite powder and the Chile saltpeter after the expansion is placed in three-necked bottle, and three-necked bottle is placed in the ice-water bath of 6 ℃, measures the 23mL98wt% concentrated sulphuric acid and adds in three-necked bottle, stirs 30min, and then adds potassium permanganate with the speed of 0.1g/min, stirs 6d;
3) mixture stirs 1h at 80 ℃, then is warming up to 100 ℃, stirs 2h, adds afterwards the 46mL distilled water, stirs 0.5h; Add afterwards the 140mL distilled water, the 10mL30% hydrogenperoxide steam generator stirs 1h again;
4) be cooled to room temperature, ultrasonic 5h;
5) repeatedly centrifugal with hydrochloric acid and the distilled water of 5wt%, obtain nano graphene oxide, ultrasonic being scattered in water, solution colour is brown.
Fig. 1 is the infrared spectrogram (IR figure) of the graphene oxide of preparation in embodiment 1, from infrared spectrogram, seeing, at 1737cm
-1C=O stretching vibration on carboxyl appears in place, illustrates that graphite powder is oxidized to graphene oxide, and surface is with carboxyl; A in Fig. 1 is graphite, and b is graphene oxide.
Fig. 2 is the transmission electron microscope photo (TEM) of the graphene oxide of preparation in embodiment 1, on scheming, can find out that the structure of graphene platelet shape is very obvious, and on the whole Graphene is not fully smooth, but lamella is very thin, in edge, have comparatively significantly fold and Fold generation, this is because the thermodynamics fluctuation of two dimensional crystal is caused.
1) take graphene oxide 100mg in embodiment 1, add in 40mL ethylene glycol, ultrasonic dispersion 30min;
2) take 0.4g PEG (molecular weight 1500) stirring and dissolving in 20mL ethylene glycol;
3) take respectively 12.6mg Gd (NO
3)
36H
2O, 5.8mg BaCl
2, 5.6mg NH
4F, add in above-mentioned scattered graphene oxide solution;
4) by 2) and 3) solution mix, magnetic agitation 30min at normal temperatures;
5) solution is transferred in the politef inner liner of reaction kettle of 100mL, tightened the reactor lid, put into baking oven, react 24h at 190 ℃ of temperature;
Reactant is carried out to centrifugal treating, first use ethanol centrifugal three times, then use deionized water centrifugal three times.Then distributed and saved is in water.
Fig. 3 is graphene oxide/BaGdF in the embodiment of the present invention 2
5The transmission electron microscope picture of/PEG (TEM), nanoparticle evenly is modified on the graphene oxide thin slice as we can see from the figure.
Fig. 4 is graphene oxide/BaGdF in the embodiment of the present invention 2
5The X-ray powder diffraction figure (XRD) of/PEG, with BaGdF
5Each peak position of standard card coincide fine.The nanoparticle that proof is modified on graphene oxide sheet is BaGdF really
5.
In Fig. 5, c is graphene oxide/BaGdF in the embodiment of the present invention 2
5The infrared spectrogram of/PEG (IR), from collection of illustrative plates, drawing, at 2900cm
-1The absworption peak at place is the stretching vibration of the C-H on PEG, compares with simple graphene oxide infared spectrum, can prove that PEG modifies to have arrived on graphene oxide sheet.
1) take graphene oxide 250mg in embodiment 1, add in 40mL ethylene glycol, ultrasonic dispersion 30min;
2) take 1.0g PEG (molecular weight 1500) stirring and dissolving in 20mL ethylene glycol;
3) take respectively 57mg Gd (NO
3)
36H
2O, 27mg BaCl
2, 26mg NH
4F, add in above-mentioned scattered graphene oxide solution;
4) by 2) and 3) solution mix, magnetic agitation 30min at normal temperatures;
5) solution is transferred in the politef inner liner of reaction kettle of 100mL, tightened the reactor lid, put into baking oven, react 24h at 190 ℃ of temperature;
Reactant is carried out to centrifugal treating, first use ethanol centrifugal three times, then use deionized water centrifugal three times.
Fig. 6 is the graphene oxide/BaGdF of preparation in case study on implementation 3
5The transmission electron microscope picture of/PEG material (TEM).Nanoparticle can be modified on the graphene oxide thin slice uniformly as we can see from the figure.
1) with the aqueous solution of the material of the material formulation variable concentrations of preparation in embodiment 2, selecting Concentraton gradient is 200,150,100,75,50,25,0 μ g/mL;
2) with ultraviolet-uisible spectrophotometer, measure the ultraviolet-visible-near infrared absorption of variable concentrations material;
3) the material of variable concentrations at 808nm, 0.4W/cm
2Under the laser of intensity, irradiate 5min, with infrared temperature-sensitive photographic head, record the image of whole process, then draw the curve of temperature with irradiation time;
4) after the irradiation, again with ultraviolet-uisible spectrophotometer, measure the ultraviolet-visible-near infrared absorption of variable concentrations material;
5) choose the material of a concentration, irradiate 5min under identical laser intensity, then allow it freely lower the temperature, reirradiation temperature-fall period 5 times, measure the stability under material illumination.According to the video recording of infrared temperature-sensitive photographic head, draw temperature variation curve.
Fig. 7 is the UV, visible light near infrared absorption figure (UV-Vis-NIR) of variable concentrations material in the embodiment of the present invention 4, and as we know from the figure, material has certain absorption near infrared region, can be used as optothermal material.
Fig. 8 is that in the embodiment of the present invention 4, the variable concentrations material laser irradiates material heating curve figure in time, as can be known, the photo-thermal effect comparative superiority of material.
Fig. 9 is the UV, visible light near infrared absorption figure (UV-Vis-NIR) of variable concentrations material after laser irradiation in the embodiment of the present invention 4, with prelaser UV-Vis-NIR, absorb the figure contrast, after can obtaining pre-irradiation, the UV-Vis-NIR Change of absorption is 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 4, 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 proved that more the stability of material after illumination is relatively good.
Figure 11 and Figure 12 are respectively graphene oxide/BaGdF in the embodiment of the present invention 2
5The T of/PEG dispersion of materials in water
1Weighted imaging figure and relaxation rate R
1(1/T
1) and sample in linear relationship chart between gadolinium concentration.
Figure 13 and Figure 14 are respectively graphene oxide/BaGdF in the embodiment of the present invention 2
5The T of/PEG dispersion of materials in water
2Weighted imaging figure and relaxation rate R
2(1/T
2) and sample in linear relationship chart between gadolinium concentration; T
1And T
2Imaging signal intensity changes along with the increase of Gd ion concentration, is embodied in: T
1Imaging signal intensity is along with the increase image of Gd ion concentration obviously brightens; T
2Imaging signal intensity is along with the increase image of Gd ion concentration is obviously dimmed.Relaxation rate is along with the increase of sample concentration is linear growth, and the longitudinal relaxation coefficient is r
1For 16.51Gd Mm
-1s
-1, transverse relaxation coefficient r
2For 32.92Gd Mm
-1s
-1, and the r under 0.5T
2/ r
1Value is 2, is applicable to being T
1Contrast agent.These data also illustrate graphene oxide/BaGdF
5/ PEG nano material can be used as a good T
1Contrast agent.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment.So every, do not break away from the equivalence completed under principles of this disclosure or revise, all falling into the scope of protection of the invention.
Claims (9)
1. graphene oxide/BaGdF
5The preparation method of/PEG multifunctional material, it is characterized in that, comprise the steps: nano graphene oxide is dispersed in alcohol, mol ratio 1:1:5 according to Gd, Ba, tri-kinds of elements of F adds the inorganic salt that contains Gd, Ba, F element, weight ratio according to PEG and graphene oxide is that 3-5:1 adds PEG again, after stirring 30min, adopt solvent-thermal method to react 23~24h under 180~190 ℃, make target material.
2. the described graphene oxide/BaGdF of claim 1
5The preparation method of/PEG multifunctional material, it is characterized in that, the preparation method of described nano graphene oxide comprises the steps: powdered graphite and NaCl mixed grinding 25-35min, wash with water and remove by filter NaCl, powdered graphite after being expanded, add Chile saltpeter and 95wt%-98wt% concentrated sulphuric acid, then the speed according to 0.05-0.1g/min adds KMnO
4, stirring 6-12d, mixture stirs 40-60min under 65-80 ℃, then under 98-110 ℃, stir 100-120min; Use the hydrogen peroxide cessation reaction, be cooled to room temperature, ultrasonic 5~8hr, washing is got solid, ultrasonic dispersion in water; The mass ratio of powdered graphite and Chile saltpeter is 5:2-5:3, powdered graphite and KMnO
4Mass ratio be 0.9:3-1:3.
3. the described graphene oxide/BaGdF of claim 1
5The preparation method of/PEG multifunctional material, is characterized in that, the inorganic salt of the described Gd of containing, Ba, F element is respectively Gd (NO
3)
36H
2O, BaCl
2And NH
4F.
4. the described graphene oxide/BaGdF of claim 1
5The preparation method of/PEG multifunctional material, is characterized in that, described alcohol is ethylene glycol.
5. the described graphene oxide/BaGdF of claim 1
5The preparation method of/PEG multifunctional material, is characterized in that, the molecular weight of described PEG is 1000-3000.
6. graphene oxide/BaGdF
5/ PEG multifunctional material, is characterized in that, by the described method preparation of claim 1-5 any one.
7. the described graphene oxide/BaGdF of claim 6
5The application of/PEG multifunctional material aspect the preparation NMR contrast agent.
8. the described graphene oxide/BaGdF of claim 6
5The application of/PEG multifunctional material aspect preparation CT image-forming contrast medium.
9. the described graphene oxide/BaGdF of claim 6
5/ PEG multifunctional material is for the preparation of cancer treatment drugs.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105031669A (en) * | 2015-06-23 | 2015-11-11 | 上海师范大学 | Core-shell structured nano composite material and a preparing method and application thereof |
GB2532449A (en) * | 2014-11-19 | 2016-05-25 | Univ Manchester | Use of Nanomaterials in treating cancer |
CN105963721A (en) * | 2016-06-06 | 2016-09-28 | 湖北大学 | BaGdF5 and europium-polyphenols reticulation nanocomposite and preparation method and application 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 |
-
2013
- 2013-08-09 CN CN201310347872.0A patent/CN103405791B/en not_active Expired - Fee Related
Non-Patent Citations (2)
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SONGJUN ZENG 等: "PEG modified BaGdF5:Yb/Er nanoprobes for multi-modal upconversion fluorescent, in vivo X-ray computed tomography and biomagnetic imaging", 《BIOMATERIALS》, vol. 33, 1 October 2012 (2012-10-01), pages 9232 - 9238, XP028945385, DOI: doi:10.1016/j.biomaterials.2012.09.019 * |
嵇天浩 等: "NaYF4∶Yb,Er/氧化石墨烯纳米复合材料的制备、表征及上转换发光性能", 《光谱学与光谱分析》, vol. 33, no. 03, 31 March 2013 (2013-03-31), pages 642 - 646 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2532449A (en) * | 2014-11-19 | 2016-05-25 | Univ Manchester | Use of Nanomaterials in treating cancer |
CN105031669A (en) * | 2015-06-23 | 2015-11-11 | 上海师范大学 | Core-shell structured nano composite material and a preparing method and application thereof |
CN105031669B (en) * | 2015-06-23 | 2018-10-16 | 上海师范大学 | A kind of nuclear-shell structured nano-composite material and the preparation method and application thereof |
CN105963721A (en) * | 2016-06-06 | 2016-09-28 | 湖北大学 | BaGdF5 and europium-polyphenols reticulation nanocomposite and preparation method and application 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 |
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