CN102633257A - Method for synthesizing less than 10 nm of single-layer graphene quantum dot biological imaging agent - Google Patents
Method for synthesizing less than 10 nm of single-layer graphene quantum dot biological imaging agent Download PDFInfo
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Abstract
The invention relates to a method for synthesizing a less than 10 nm of single-layer graphene quantum dot biological imaging agent. The method comprises the following steps of: after carrying out ultrasonic treatment on a graphene oxide solution, dispersing the graphene oxide solution in de-ionized water, adding a sodium hydroxide solution to adjust the pH value, then, transferring the solution into a polytetrafluoroethylene high-pressure kettle, and carrying out hydrothermal reaction for a certain time; and, after ending the reaction, centrifugally separating suspension. According to the invention, a prepared graphene quantum dot product is uniform in size, is less than 10 nm, and is in a single-layer structure, and the graphene quantum dot product can serve as a biological imaging agent to be applied to biological imaging due to fluorescence; no organic matter serving as a surface active agent is added into the reaction system, so that the product is pure, and a complex separation and purification process is not required; no toxic and harmful reagent exists in the preparation method, so that the method is environmentally-friendly and free from pollution; and the method has the characteristics of being rapid and convenient, simple and easy for leaning, good in reproducibility, low in manufacture cost, simple in process and high in efficiency.
Description
Technical field
The invention belongs to the graphene quantum dot technical field of nano material, relate in particular to the simple synthesis of a kind of preparation less than 10nm single-layer graphene quanta point biological preparation.
Background technology
Prior art: Graphene has caused great concern because its excellent optics, calorifics, chemistry and mechanical characteristic and potential are used.Because quantum confined effect, the function of quantum dot can be adjusted through controlling its size simply.Therefore, quantum dot detects in a new generation, microelectronics, and biological medicine or the like aspect has potential and uses.Theoretical show, owing to its quantum confined effect and fringing effect, can induce pl-less than the graphene quantum dot of 10nm with experimental study.
[1,2]
Graphene quantum dot is classified as a kind of fluorescence c-based nanomaterial, is applied to numerous infusive fields, comprises medical diagnosis, photochemical catalysis and solar cell etc.
[3]In addition, owing to its chemicalstability, biocompatibility and cell nontoxicity, can be used as the fluorescent probe of bio-imaging.Graphene quantum dot can adopt electrochemical method
[4], hydrothermal method
[5]And other method
[6,7]Preparation.But the operation steps complicacy of these methods is loaded down with trivial details, and the size of graphene quantum dot of preparation is multilayer often greater than 10nm, and the dispersiveness in solution also remains to be improved, in the practical application that has to a certain degree fettered graphene quantum dot.
[1]Ponomarenko,L.A.;Schedin,F.;Katsnelson,M.I.;Yang,R.;Hill,E.W.;Novoselov，K.S.;Geim,A.K.Science?2008,320,356.
[2]Son,Y.W.;Cohen,M.L.;Louie,S.G.Nature?2006,444,347.
[3]Baker,S.N.;Baker,G.A.Angew.Chem.,Int.Ed．2010,49,6726.
[4]Li,Y.;Hu,Y.;Zhao,Y.;Shi,G.Q.;Deng,L.;Hou,Y.B.;Qu,L.T.Adv．Mater.2011,23,776.
[5]Pan,D.;Zhang,J.;Li,Z.;Wu,M.Adv．Mater.2010,22,734.
[6]Shen,J.;Zhu,Y.;Chen,C.;Yang,X.;Li,C.Chem.Commun.2011,47,2580.
[7]Mei,Q.;Zhang,K.;Guan,G.;Liu,B.;Wang,S.;Zhang,Z.Chem.Commun.2010,46,7319.
Summary of the invention
Technical problem: the present invention provides a kind of simple synthesis less than 10nm single-layer graphene quanta point biological preparation; Utilize ultrasonic-hydrothermal method; Graphene oxide is reduced to Graphene, product be can be applicable to bio-imaging, size is less than the single-layer graphene quantum dot of 10nm.
Technical scheme: less than the compound method of 10nm single-layer graphene quanta point biological preparation, preparation process is:
A. graphene oxide solution is ultrasonic, the graphene oxide strength of solution is 5.10-49.75mg/mL, and ultrasonic power is 100-500W, and ultrasonic time is 1-4h;
B. above-mentioned solution is dispersed in the deionized water, adds sodium hydroxide solution and regulate pH=8-14;
C. above-mentioned solution is transferred in the tetrafluoroethylene autoclave and heats, Heating temperature is 180-250 ℃, and be 10-40h heat-up time;
D. after reaction finishes, again with the product spinning, dry bio-imaging agent.
Described graphene oxide solution ultrasonic power is 100W, and ultrasonic time is 1h.
Add sodium hydroxide solution in the said graphene oxide solution that is dispersed in the deionized water and regulate pH=8.
Said Heating temperature is 200 ℃, and be 10h heat-up time.
Said centrifugal speed is 12000-18000rpm, and centrifugation time is 5-60min.
After ultrasonic-hydro-thermal reaction, graphene oxide is reduced, and can obtain finely dispersed graphene quantum dot product, and size presents single layer structure less than 10nm, has fluorescent characteristic.
Beneficial effect:
Patent of invention is that method is easy less than the compound method of 10nm single-layer graphene quanta point biological preparation; Adopt ultrasonic-hydrothermal method redox graphene, product has good dispersiveness in water.The graphene quantum dot size of preparation is single layer structure less than 10nm, and its fluorescent characteristic can be used as fluorescent probe and is applied to bio-imaging; The product surface has hydrophilic oxygen-containing functional group (epoxy group(ing), hydroxyl, carboxyl etc.), in water, has good dispersion; The product surface has negative electricity, can effectively avoid the generation of agglomeration; Reaction system is not added any organism as tensio-active agent, and product is pure, need not complicated separation, purification process; With water as reaction solvent, wide material sources, cheap; No any poisonous and harmful reagent is environmentally friendly, pollution-free among the preparation method; Method rapid and convenient, easy to learn, favorable reproducibility, and low cost of manufacture, technology is simple, and efficient is high.
Description of drawings
(A) high resolving power transmission electron microscope (HRTEM) photo of Fig. 1 graphene quantum dot and AFM (AFM) photo that (B) raps under the pattern;
Fig. 2 is the graphene quantum dot figure of the pl-(PL) under 320nm, 365nm and 400nm excitation wavelength respectively.
Fig. 1 (A) high resolving power transmission electron microscope (HRTEM) photo shows that the size of graphene quantum dot is about 5nm; (B) rap AFM (AFM) photo under the pattern, prove that graphene quantum dot thickness is about 0.43nm, is single layer structure.
Fig. 2 proves that the product graphene quantum dot of preparation has the pl-effect, and along with the increase of excitation wavelength, the maximum emission peak generation red shift of graphene quantum dot.
Embodiment
Embodiment 1:
A, with graphene oxide solution ultrasonic (100W) 1h of the 10.50mg/mL of 1.11mL.
B, above-mentioned solution is dispersed in the deionized water, adds sodium hydroxide solution and regulate pH=8.
C, above-mentioned solution is transferred in the tetrafluoroethylene autoclave, is heated to 200 ℃, keep 10h.
After d, reaction finished, centrifugal 30min separated product under the 18000rpm rotating speed, and drying at room temperature gets the bio-imaging agent.
Reaction product is seen Fig. 1.Can be known that by Fig. 1 the size of products therefrom graphene quantum dot is about 5nm, mean thickness 0.43nm proves that it is a single layer structure.Fig. 2 shows that the product graphene quantum dot of preparation has the pl-effect, therefore can be applied to bio-imaging.
Embodiment 2:
A, with graphene oxide solution ultrasonic (100W) 1h of the 13.00mg/mL of 0.90mL.
B, above-mentioned solution is dispersed in the deionized water, adds sodium hydroxide solution and regulate pH=10.
C, above-mentioned solution is transferred in the tetrafluoroethylene autoclave, is heated to 180 ℃, keep 20h.
After d, reaction finished, centrifugal 30min separated product under the 18000rpm rotating speed, and drying at room temperature gets the bio-imaging agent.
Embodiment 3:
A, with graphene oxide solution ultrasonic (100W) 4h of the 10.50mg/mL of 1.11mL.
B, above-mentioned solution is dispersed in the deionized water, adds sodium hydroxide solution and regulate pH=12.
C, above-mentioned solution is transferred in the tetrafluoroethylene autoclave, is heated to 250 ℃, keep 10h.
After d, reaction finished, centrifugal 10min separated product under the 15000rpm rotating speed, and drying at room temperature gets the bio-imaging agent.
Embodiment 4:
A, with graphene oxide solution ultrasonic (300W) 1h of the 11.67mg/mL of 1.00mL.
B, above-mentioned solution is dispersed in the deionized water, adds sodium hydroxide solution and regulate pH=14.
C, above-mentioned solution is transferred in the tetrafluoroethylene autoclave, is heated to 200 ℃, keep 40h.
After d, reaction finished, centrifugal 5min separated product under the 12000rpm rotating speed, and drying at room temperature gets the bio-imaging agent.
Embodiment 5:
A, with graphene oxide solution ultrasonic (100W) 4h of the 5.10mg/mL of 2.29mL.
B, above-mentioned solution is dispersed in the deionized water, adds sodium hydroxide solution and regulate pH=8.
C, above-mentioned solution is transferred in the tetrafluoroethylene autoclave, is heated to 200 ℃, keep 10h.
After d, reaction finished, centrifugal 30min separated product under the 15000rpm rotating speed, and drying at room temperature gets the bio-imaging agent.
Embodiment 6:
A, with graphene oxide solution ultrasonic (500W) 1h of the 5.10mg/mL of 2.29mL.
B, above-mentioned solution is dispersed in the deionized water, adds sodium hydroxide solution and regulate pH=8.
C, above-mentioned solution is transferred in the tetrafluoroethylene autoclave, is heated to 180 ℃, keep 20h.
After d, reaction finished, centrifugal 60min separated product under the 15000rpm rotating speed, and drying at room temperature gets the bio-imaging agent.
Embodiment 7:
A, with graphene oxide solution ultrasonic (300W) 1h of the 49.75mg/mL of 0.23mL.
B, above-mentioned solution is dispersed in the deionized water, adds sodium hydroxide solution and regulate pH=8.
C, above-mentioned solution is transferred in the tetrafluoroethylene autoclave, is heated to 200 ℃, keep 40h.
After d, reaction finished, centrifugal 10min separated product under the 18000rpm rotating speed, and drying at room temperature gets the bio-imaging agent.
Embodiment 8:
A, with graphene oxide solution ultrasonic (500W) 2h of the 5.10mg/mL of 2.29mL.
B, above-mentioned solution is dispersed in the deionized water, adds sodium hydroxide solution and regulate pH=10.
C, above-mentioned solution is transferred in the tetrafluoroethylene autoclave, is heated to 250 ℃, keep 10h.
After d, reaction finished, centrifugal 10min separated product under the 15000rpm rotating speed, and drying at room temperature gets the bio-imaging agent.
Embodiment 9:
A, with graphene oxide solution ultrasonic (500W) 4h of the 5.10mg/mL of 2.29mL.
B, above-mentioned solution is dispersed in the deionized water, adds sodium hydroxide solution and regulate pH=12.
C, above-mentioned solution is transferred in the tetrafluoroethylene autoclave, is heated to 200 ℃, keep 20h.
After d, reaction finished, centrifugal 10min separated product under the 18000rpm rotating speed, and drying at room temperature gets the bio-imaging agent.
Embodiment 10:
A, with graphene oxide solution ultrasonic (100W) 2h of the 49.75mg/mL of 0.23mL.
B, above-mentioned solution is dispersed in the deionized water, adds sodium hydroxide solution and regulate pH=14.
C, above-mentioned solution is transferred in the tetrafluoroethylene autoclave, is heated to 180 ℃, keep 10h.
After d, reaction finished, centrifugal 5min separated product under the 15000rpm rotating speed, and drying at room temperature gets the bio-imaging agent.
Claims (5)
1. less than the compound method of 10 nm single-layer graphene quanta point biological preparations, it is characterized in that preparation process is:
A. graphene oxide solution is ultrasonic, the graphene oxide strength of solution is 5.10-49.75 mg/mL, and ultrasonic power is 100-500 W, and ultrasonic time is 1-4 h;
B. above-mentioned solution is dispersed in the deionized water, adds sodium hydroxide solution and regulate pH=8-14;
C. above-mentioned solution is transferred in the tetrafluoroethylene autoclave and heats, Heating temperature is 180-250 ℃, and be 10-40 h heat-up time;
D. after reaction finishes, again with the product spinning, dry bio-imaging agent.
2. the compound method less than 10 nm single-layer graphene quanta point biological preparations according to claim 1 is characterized in that described graphene oxide solution ultrasonic power is 100 W, and ultrasonic time is 1h.
3. the compound method less than 10 nm single-layer graphene quanta point biological preparations according to claim 1 is characterized in that adding in the said graphene oxide solution that is dispersed in the deionized water sodium hydroxide solution and regulates pH=8.
4. the compound method less than 10 nm single-layer graphene quanta point biological preparations according to claim 1 is characterized in that said Heating temperature is 200 ℃, and be 10h heat-up time.
5. the compound method less than 10 nm single-layer graphene quanta point biological preparations according to claim 1 is characterized in that said centrifugal speed is 12000-18000 rpm, and centrifugation time is 5-60 min.
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Cited By (7)
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| CN104386673A (en) * | 2014-10-29 | 2015-03-04 | 安徽师范大学 | Graphene quantum dots (GQDs) and preparation method thereof |
| CN104909356A (en) * | 2015-05-22 | 2015-09-16 | 南京工业大学 | Graphene oxide and graphene oxide quantum dot solvothermal controllable preparation method and use thereof |
| CN105244415A (en) * | 2015-10-19 | 2016-01-13 | 南京工程学院 | Preparation process of quantum-dot hybrid reduced graphene oxide nanometer film photosensitive sensor |
| CN106348281A (en) * | 2015-07-13 | 2017-01-25 | 南京理工大学 | Method for preparing bifluorescence graphene quantum dots hydrothermally |
| CN107601466A (en) * | 2017-10-12 | 2018-01-19 | 青岛科技大学 | A kind of preparation method and applications of the graphene quantum dot of size uniform |
| CN108394886A (en) * | 2018-04-03 | 2018-08-14 | 中国工程物理研究院材料研究所 | A kind of method, its product and application preparing carbon quantum dot based on highly basic cutting graphite oxide |
| CN111671771A (en) * | 2019-08-29 | 2020-09-18 | 上海大学 | Graphene base targeting DNA major groove and inhibiting topoisomerase and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104386673A (en) * | 2014-10-29 | 2015-03-04 | 安徽师范大学 | Graphene quantum dots (GQDs) and preparation method thereof |
| CN104386673B (en) * | 2014-10-29 | 2016-03-30 | 安徽师范大学 | A kind of graphene quantum dot (GQDs) and preparation method thereof |
| CN104909356A (en) * | 2015-05-22 | 2015-09-16 | 南京工业大学 | Graphene oxide and graphene oxide quantum dot solvothermal controllable preparation method and use thereof |
| CN106348281A (en) * | 2015-07-13 | 2017-01-25 | 南京理工大学 | Method for preparing bifluorescence graphene quantum dots hydrothermally |
| CN105244415A (en) * | 2015-10-19 | 2016-01-13 | 南京工程学院 | Preparation process of quantum-dot hybrid reduced graphene oxide nanometer film photosensitive sensor |
| CN107601466A (en) * | 2017-10-12 | 2018-01-19 | 青岛科技大学 | A kind of preparation method and applications of the graphene quantum dot of size uniform |
| CN107601466B (en) * | 2017-10-12 | 2018-08-03 | 青岛科技大学 | A kind of preparation method and applications of the graphene quantum dot of size uniform |
| CN108394886A (en) * | 2018-04-03 | 2018-08-14 | 中国工程物理研究院材料研究所 | A kind of method, its product and application preparing carbon quantum dot based on highly basic cutting graphite oxide |
| CN111671771A (en) * | 2019-08-29 | 2020-09-18 | 上海大学 | Graphene base targeting DNA major groove and inhibiting topoisomerase and preparation method and application thereof |
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Inventor after: Dai Yunqian Inventor after: Long Huan Inventor after: Sun Yueming Inventor after: Jing Yao Inventor after: Zhang Lan Inventor after: He Yijia Inventor before: Sun Yueming Inventor before: Long Huan Inventor before: Dai Yunqian Inventor before: Jing Yao Inventor before: Zhang Lan Inventor before: He Yijia |
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Free format text: CORRECT: INVENTOR; FROM: SUN YUEMING LONG HUAN DAI YUNXI JING YAO ZHANG LAN HE YIJIA TO: DAI YUNXI LONG HUAN SUN YUEMING JING YAO ZHANG LAN HE YIJIA |
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Application publication date: 20120815 |