CN104861967B - The preparation method and applications of nitrogen-doped graphene quantum dot - Google Patents
The preparation method and applications of nitrogen-doped graphene quantum dot Download PDFInfo
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Abstract
The invention discloses the preparation method and applications of a kind of nitrogen-doped graphene quantum dot, the method selects the TATB (photoacoustic spectroscopy) that nitrogen content is high to be raw material, through pyrogenically prepared nitrogen-doped graphene quantum dot (N GQDs).The size of this nitrogen-doped graphene quantum dot is 2～10nm, and thickness is 0.5～1.5nm, and nitrogen content is 4%～30%, can exist steadily in the long term in aqueous.Additionally, found by cell imaging research, this nitrogen-doped graphene quantum dot can send bright green fluorescence, have good bio-compatibility, does not almost have toxicity to biological cell.Preparation method of the present invention is simple, and raw material is cheap, low for equipment requirements, and the nitrogen-doped graphene quantum dot prepared has the luminescent properties of excellence.
Description
Technical field
The invention belongs to the preparing technical field of nano material, relate to a kind of graphene quantum dot preparation and
Application, more particularly to the preparation of a kind of nitrogen-doped graphene quantum dot and the application in living cells imaging thereof.
Background technology
Recent years, the nano material with fluorescent characteristic has caused the concern of the most many researcheres,
Wherein, the graphene quantum dot (GQDs) of zero dimension is especially prominent.GQDs be thickness be 0.5～1.5nm,
Particle diameter is the graphene sheet layer of about 10nm, and its surface is contained the groups such as hydroxyl, carboxyl, carbonyl and made it
There is good water solublity.GQDs not only shows the excellent properties as Graphene, the most also has good
Good bio-compatibility, hypotoxicity, low quenching, the excellent properties such as stable chemical characteristic.At present, GQDs
As fluorescent probe for cell imaging and relevant environmental monitoring.If Peng et al. is by green emitting
GQDs is applied to the bio-imaging of high contrast.Liu seminar utilize graphene oxide prepare can send multiple
The GQDs of color, utilizes TNT Yu GQDs to be combined the character causing fluorescent quenching to detect TNT.Dong's class
Topic group also utilizes Cl ion and GQDs to be combined the character making GQDs fluorescent quenching to detect Cl ion.
Although GQDs has so many advantage, but the characteristic of Graphene zero band gap limits it widely
Application, in order to open the band gap of Graphene, one of them feasible method is adulterated nitrogen-atoms exactly.Cai et al.
Graphene quantum dot (N-GQDs) fluorescence quantum yield after report doping nitrogen is unadulterated 7 times.Li
Et al. have found that the sucting electronic effect of nitrogen-atoms make N-GQDs particle performance go out uniqueness photoelectric characteristic.
Liu et al. finds that N-GQDs not only can send bright fluorescence letter through exciting in the deep tissue of 1800 μm
Number, and N-GQDs still shows optical stability under the radiation repeatedly of laser.Ju et al. utilizes
The high quantum production rate of N-GQDs detects glutathion as fluorescent probe.
The method preparing N-GQDs at present mainly has hydro-thermal method, organic synthesis method, chemical cleavage and electrification
Method etc., but these methods all come with some shortcomings from raw material, preparation flow, multiselect as big in raw material
Take is graphene oxide, Graphene or graphene quantum dot, and this makes preparation cost significantly improve.Remove
Outside this, apparatus expensive, troublesome poeration is time-consuming, and technique is loaded down with trivial details, needs these shortcomings such as High Temperature High Pressure very big
Limit the extensive application of nitrogen-doped graphene quantum dot.Therefore, how to select raw material cheap and easy to get,
The nitrogen-doped graphene quantum dot possessing excellent luminance performance is prepared, it has also become this field by single step reaction
Significant challenge.
Summary of the invention
The invention aims to overcome defect present in above-mentioned prior art, it is provided that a kind of nitrating graphite
Alkene quantum dot, its preparation method and as fluorescent probe in the biomedical researches such as living cells imaging should
With.
In order to reach above-mentioned technique effect, the present invention takes techniques below scheme:
The preparation method of a kind of nitrogen-doped graphene quantum dot, comprises the steps:
A) polymer of nitrogen-doped graphene quantum dot is prepared
Being placed in by photoacoustic spectroscopy in Muffle furnace under nitrogen protection, at 400～1000 DEG C, pyrolysis is anti-
Answer 10～360min, then allow it naturally cool to room temperature and obtain the polymer of nitrogen-doped graphene quantum dot；
B) ultrasonic stripping, stir process polymer
The polymer of the nitrogen-doped graphene quantum dot obtained in step a is placed in dense H2SO4With dense HNO3Mixed
Supersound process 0.5～3h in acid, then stirs 20～30h at 90～120 DEG C, obtains nitrogen-doped graphene quantum dot
Solution；
C) regulation pH value
The solution of the nitrogen-doped graphene quantum dot obtained in step b adds water and the pH of sodium carbonate regulating solution
Value is 7, and then dialysis solution obtains nitrogen-doped graphene quantum dot.
Further technical scheme, the programming rate of described pyrolysis temperature is 1～20 DEG C/min.
Further technical scheme, dense H in described nitration mixture2SO4With dense HNO3Volume ratio be 3:1.
Further technical scheme, described ultrasonic power is: 100～400W.
Further technical scheme, the speed of described stirring is: 100～900r/min.
In another aspect of the present invention, it is provided that a kind of nitrogen-doped graphene quantum dot, described nitrogen-doped graphene
Quantum dot has the property that the length dimension of this nitrogen-doped graphene quantum dot is 2～10nm, and thickness is
0.5～1.5nm, nitrogen content is 4～30%, and this nitrogen-doped graphene quantum dot surface contains hydroxyl and carboxyl.
The present invention have chosen TATB as raw material, only needs an a kind of material just can settle prepared nitrogen at one go and mixes graphite
Alkene quantum dot.Reaction mechanism is: TATB is the organic crystal of layer structure, in pyrolytic process, You Ji little
Nitrogen-containing group-the NH of molecule TATB2With-NO2Degraded is occurred to produce substantial amounts of gas so that interlayer occurs swollen
Swollen even peeling off, the nitrogen-doped graphene quantum dot for preparation monolayer provides favourable molecular structure.With
Time, TATB molecule produces highly active containing nitrogen free radical in pyrolytic process so that nitrogen-atoms divides at TATB
Introduce during generation carbonization between son in the lattice of carbon.Peel off through simple sonochemistry the most again and just can make easily
Obtain nitrogen-doped graphene quantum dot.
The present invention compared with prior art, has a following beneficial effect: the present invention is with high organic of nitrogen content
Little molecule TATB replaces the expensive reaction substrate needed for tradition preparation, such as graphene oxide, graphite
Alkene or graphene quantum dot etc., and be not required to additionally introduce nitrogen source, low in raw material price, wide material sources, equipment
Simply, preparation process is not introduced into other impurity, it is adaptable to industrialized large-scale production.
Meanwhile, the nitrogen-doped graphene quantum dot surface prepared through pyrolysismethod of the present invention has hydroxyl and carboxyl, makes
Obtain it and there is in water good dispersibility, after placing some months, the most still do not observe precipitation, and
This nitrogen-doped graphene quantum dot can send the fluorescence of green, has good bio-compatibility, to biological cell
Almost do not have toxicity, fluorescent probe, cell imaging field can be widely used in.
Accompanying drawing explanation
Fig. 1 is the polymeric field emission scanning electron microscope of nitrogen-doped graphene quantum dot that the embodiment of the present invention 1 prepares
Photo；
Fig. 2 is the atomic force microscopy of the nitrogen-doped graphene quantum dot that the embodiment of the present invention 1 prepares；
Fig. 3 is the transmission electron microscope photo of the nitrogen-doped graphene quantum dot that the embodiment of the present invention 1 prepares；
Fig. 4 is the height statistics photo of the nitrogen-doped graphene quantum dot that the embodiment of the present invention 1 prepares；
Fig. 5 is the Raman spectrogram of the nitrogen-doped graphene quantum dot that the embodiment of the present invention 1 prepares；
Fig. 6 is the fluorescence spectrum figure of the nitrogen-doped graphene quantum dot that the embodiment of the present invention 1 prepares；
Fig. 7 is the XPS spectrum figure of the N1s of the nitrogen-doped graphene quantum dot that the embodiment of the present invention 1 prepares；
Fig. 8 is that the nitrogen-doped graphene quantum dot using different volumes embodiment 1 to prepare processes cervical cancer cell
(HeLa) cytoactive block diagram after 24h；
Fig. 9 is that the quantum dot-labeled cervical cancer cell of the nitrogen-doped graphene (HeLa) prepared by embodiment 1 exists
Fluorogram under light field；
Figure 10 is the quantum dot-labeled cervical cancer cell of the nitrogen-doped graphene (HeLa) prepared by embodiment 1
Fluorescence imaging figure.
Detailed description of the invention
Below in conjunction with embodiments of the invention and accompanying drawing, the invention will be further elaborated.
Embodiment 1
0.5g TATB is placed in Muffle furnace under nitrogen protection, is warmed up to the programming rate of 2 DEG C/min
750 DEG C, it is incubated pyrolytic reaction 20min, is the most naturally down to room temperature and obtains the polymerization of nitrogen-doped graphene quantum dot
Body, the polymer 0.1g taking this nitrogen-doped graphene quantum dot is placed in the dense H of 18.75ml2SO4Dense with 5.25ml
HNO3Mixed acid under ultrasonic power is 300W ultrasonic stripping 2h, then stirring is set at 100 DEG C
Speed is the solution that 600r/min stirring 24h obtains nitrogen-doped graphene quantum dot, to this nitrogen-doped graphene quantum
The solution of point adds 50ml water and the pH value of solution is adjusted to 7 by sodium carbonate, finally solution dialysis is obtained
Nitrogen-doped graphene quantum dot.
Embodiment 2
0.5gTATB is placed in Muffle furnace under nitrogen protection, is warmed up to the programming rate of 5 DEG C/min
500 DEG C, it is incubated pyrolytic reaction 240min, is the most naturally down to room temperature and obtains the polymerization of nitrogen-doped graphene quantum dot
Body, the polymer 0.1g taking this nitrogen-doped graphene quantum dot is placed in the dense H of 18.75ml2SO4Dense with 5.25ml
HNO3Mixed acid under ultrasonic power is 400W ultrasonic stripping 2h, then stirring is set at 100 DEG C
Speed is the solution that 500r/min stirring 24h obtains nitrogen-doped graphene quantum dot, to this nitrogen-doped graphene quantum
The solution of point adds 50ml water and the pH value of solution is adjusted to 7 by sodium carbonate, finally solution dialysis is obtained
Nitrogen-doped graphene quantum dot.
Embodiment 3
0.5gTATB is placed in Muffle furnace under nitrogen protection, heats up with the programming rate of 10 DEG C/min
To 900 DEG C, it is incubated pyrolytic reaction 40min, is the most naturally down to room temperature and obtains the poly-of nitrogen-doped graphene quantum dot
Zoarium, the polymer 0.1g taking this nitrogen-doped graphene quantum dot is placed in the dense H of 18.75ml2SO4Dense with 5.25ml
HNO3Mixed acid under ultrasonic power is 400W ultrasonic stripping 2h, then stirring is set at 100 DEG C
Speed is the solution that 800r/min stirring 24h obtains nitrogen-doped graphene quantum dot, to this nitrogen-doped graphene quantum
The solution of point adds 50ml water and the pH value of solution is adjusted to 7 by sodium carbonate, finally solution dialysis is obtained
Nitrogen-doped graphene quantum dot.
Embodiment 4
0.5gTATB is placed in Muffle furnace under nitrogen protection, heats up with the programming rate of 20 DEG C/min
To 1000 DEG C, it is incubated pyrolytic reaction 20min, is the most naturally down to room temperature and obtains nitrogen-doped graphene quantum dot
Polymer, the polymer 0.1g taking this nitrogen-doped graphene quantum dot is placed in the dense H of 18.75ml2SO4And 5.25ml
Dense HNO3Mixed acid under ultrasonic power is 200W ultrasonic stripping 2h, then arrange at 100 DEG C and stir
Mixing speed is the solution that 300r/min stirring 24h obtains nitrogen-doped graphene quantum dot, to this nitrogen-doped graphene amount
The solution of son point adds 50ml water and the pH value of solution is adjusted to 7 by sodium carbonate, finally solution is dialysed
To nitrogen-doped graphene quantum dot.
Embodiment 5
To the nitrogen-doped graphene quantum dot obtained by the present invention as fluorescent probe answering in biomedical research
With testing, the cytotoxicity of the nitrogen-doped graphene quantum dot obtained by mensuration.
Specific experiment method is: first by HeLa cell at 37 DEG C, 50%CO2Under atmosphere with DMEM it is
Culture medium is cultivated, wherein containing 10% hyclone and 1% penicillin/streptomycin, HeLa in culture medium
After cell cultivates 24h in 96 orifice plates, add the different volumes nitrogen-doped graphene quantum that embodiment 1 prepares
Point 1 μ l, 5 μ l, 10 μ l, 15 μ l, 20 μ l, wherein the concentration of nitrogen-doped graphene quantum dot is 14 μ g/ml, continues
The continuous 24h that cultivates, then adds Alamar Blue indicator in cell culture fluid, treats that culture medium color is by indigo plant
When complexion changed is pink colour, measure its fluorescence intensity.
Seeing Fig. 8, result shows, the cervical cancer after using different volumes nitrogen-doped graphene quantum dot to process is thin
Its activity of born of the same parents (HeLa), without notable change, shows that nitrogen-doped graphene quantum dot prepared by the present invention is thin to biology
Born of the same parents have no or only the cytotoxicity of trace.
Embodiment 6
Nitrogen-doped graphene quantum dot prepared by the present invention is as fluorescent probe application in cell imaging.
Specific experiment process is: first by HeLa cell at 37 DEG C, 50%CO2Under atmosphere after overnight incubation,
Add nitrogen-doped graphene quantum dot 100 μ l (concentration is 14 μ g/ml) the continuation cultivation 4h that embodiment 1 prepares,
Then observe under excitation wavelength is 460nm with laser confocal microscope after rinsing 3～5 times by PBS solution
HeLa cell.
Seeing Fig. 9 is the quantum dot-labeled cervical cancer cell of the nitrogen-doped graphene (HeLa) prepared by embodiment 1
Fluorogram under light field.
Seeing Figure 10 is the quantum dot-labeled cervical cancer cell of the nitrogen-doped graphene (HeLa) prepared by embodiment 1
A fluorescence imaging figure, in figure, the part of HeLa cell peripheral bright white is actual is nitrogen-doped graphene quantum
Point presents the fluorescence of green, shows that the nitrogen-doped graphene quantum dot entering cell is distributed only over nuclear membrane simultaneously
Near.
Although reference be made herein to invention has been described for the explanatory embodiment of the present invention, and above-described embodiment is only
For the present invention preferably embodiment, embodiments of the present invention are also not restricted to the described embodiments, it should
Understanding, those skilled in the art can be designed that a lot of other amendments and embodiment, and these are revised and real
The mode of executing will fall within spirit disclosed in the present application and spirit.
Claims (7)
1. the preparation method of a nitrogen-doped graphene quantum dot, it is characterised in that comprise the steps:
A) polymer of nitrogen-doped graphene quantum dot is prepared
Photoacoustic spectroscopy is placed in Muffle furnace under nitrogen protection, is pyrolyzed at 400～1000 DEG C
Reaction 10～360min, then allows it naturally cool to room temperature and obtains the polymer of nitrogen-doped graphene quantum dot；
B) ultrasonic stripping, stir process polymer
The polymer of the nitrogen-doped graphene quantum dot obtained in step a is placed in dense H2SO4With dense HNO3's
Ultrasonic stripping 0.5～3h in nitration mixture, then stirs 20～30h at 90～120 DEG C, obtains nitrogen-doped graphene amount
The solution of son point；
C) regulation pH value
The solution of the nitrogen-doped graphene quantum dot obtained in step b adds water and sodium carbonate regulating solution
PH value is 7, and then dialysis solution obtains nitrogen-doped graphene quantum dot.
The preparation method of nitrogen-doped graphene quantum dot the most according to claim 1, it is characterised in that:
The programming rate of described pyrolysis temperature is 1～20 DEG C/min.
The preparation method of nitrogen-doped graphene quantum dot the most according to claim 1, it is characterised in that:
Dense H in described nitration mixture2SO4With dense HNO3Volume ratio be 3:1.
The preparation method of nitrogen-doped graphene quantum dot the most according to claim 1, it is characterised in that:
Described ultrasonic power is: 100～400W.
The preparation method of nitrogen-doped graphene quantum dot the most according to claim 1, it is characterised in that:
The speed of described stirring is: 100～900r/min.
6. the nitrating graphite prepared according to the preparation method described in claim any one of Claims 1 to 5
Alkene quantum dot.
Nitrogen-doped graphene quantum dot the most according to claim 6, it is characterised in that it has following spy
Property: the length dimension of this nitrogen-doped graphene quantum dot is 2～10nm, and thickness is 0.5～1.5nm, and nitrogen content is
4～30%, and this nitrogen-doped graphene quantum dot surface contains hydroxyl and carboxyl.
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| CN105271217B (en) * | 2015-12-10 | 2017-08-11 | 湖南师范大学 | A kind of preparation method of the three-dimensional grapheme of N doping |
| CN106898774A (en) * | 2015-12-18 | 2017-06-27 | 中国科学院大连化学物理研究所 | One kind peels off carbon block and its preparation and application |
| CN106276880B (en) * | 2016-08-22 | 2018-08-14 | 中国工程物理研究院化工材料研究所 | The preparation method of nitrogen-doped graphene quantum dot |
| CN108485659B (en) * | 2018-02-12 | 2021-06-04 | 上海大学 | Amphiphilic graphene quantum dot material, preparation method and application of amphiphilic graphene quantum dot material as cell nucleus targeted imaging fluorescent probe |
| CN110917212A (en) * | 2019-08-29 | 2020-03-27 | 上海烯参生物科技有限公司 | Graphene base targeting DNA major groove and inhibiting topoisomerase and preparation method and application thereof |
| CN111484840B (en) * | 2020-04-24 | 2022-04-19 | 四川大学 | Conjugated c (RGDFC) sulfur-nitrogen double-doped graphene quantum dot and preparation method and application thereof |
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| CN102992311B (en) * | 2012-12-10 | 2014-12-10 | 福州大学 | Method for preparing graphene quantum dots through carbon nano tube |
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