CN104861967A - Preparation method and application of nitrogen-doped graphene quantum dots - Google Patents
Preparation method and application of nitrogen-doped graphene quantum dots Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims description 9
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Abstract
The invention discloses a preparation method and an application of nitrogen-doped graphene quantum dots. According to the method, TATB (triamino trinitrobenzene) with a high nitrogen content is adopted as a raw material; pyrolysis is carried out; and the nitrogen-doped graphene quantum dots (N-GQDs) are prepared. The size of the nitrogen-doped graphene quantum dots is 2-10nm, the thickness of the nitrogen-doped graphene quantum dots is 0.5-1.5nm, and the nitrogen content of the nitrogen-doped graphene quantum dots is 4-30%. The nitrogen-doped graphene quantum dots can stably exist in a water solution for a long time. As a result of cell imaging studies, the nitrogen-doped graphene quantum dots can emit bright green fluorescence, has good biocompatibility, and almost has no toxicity against biological cells. The preparation method is simple; raw material cost is low; the requirement on equipment is low; and the prepared nitrogen-doped graphene quantum dots have excellent light-emitting performance.
Description
Technical field
The invention belongs to the preparing technical field of nano material, relate to a kind of preparation and application thereof of graphene quantum dot, relate to a kind of preparation of nitrating graphene quantum dot and the application in viable cell imaging thereof particularly.
Background technology
Recent years, the nano material with fluorescent characteristic has caused the concern of domestic and international many investigators, and wherein, the graphene quantum dot (GQDs) of zero dimension is particularly outstanding.GQDs is thickness is 0.5 ~ 1.5nm, and particle diameter is the graphene sheet layer of about 10nm, and it is good water-soluble that its surface makes it have containing the group such as hydroxyl, carboxyl, carbonyl.GQDs not only shows the excellent properties as Graphene, also has good bio-compatibility, hypotoxicity simultaneously, low quenching, the excellent properties such as stable chemical property.At present, GQDs is used for cell imaging and relevant environmental monitoring as fluorescent probe.As the GQDs of green emitting is applied to the high bio-imaging contrasted by the people such as Peng.Liu seminar utilizes graphene oxide to prepare the GQDs that can send multiple color, utilizes TNT and GQDs compound to cause the character of fluorescent quenching to detect TNT.Dong seminar also utilizes Cl ion and GQDs compound to make the character of GQDs fluorescent quenching to detect Cl ion.
Although GQDs has so many advantage, the characteristic of Graphene zero band gap limits it and applies widely, and in order to open the band gap of Graphene, one of them feasible method is adulterated nitrogen-atoms exactly.The people such as Cai report that graphene quantum dot (N-GQDs) fluorescence quantum yield after doping nitrogen is unadulterated 7 times.The people such as Li find because the sucting electronic effect of nitrogen-atoms makes N-GQDs particle performance go out unique photoelectric characteristic.The people such as Liu find that N-GQDs not only can send bright fluorescent signal through exciting in 1800 μm of dark tissues, and N-GQDs still shows optical stability under the radiation repeatedly of laser.The people such as Ju utilize the high quantum production rate of N-GQDs to detect gsh as fluorescent probe.
The method of the current N-GQDs of preparation mainly contains hydrothermal method, organic synthesis method, chemical cleavage and electrochemical method etc., but these methods all come with some shortcomings from raw material, preparation flow, what mostly choose as raw material is graphene oxide, Graphene or graphene quantum dot, and this makes preparation cost significantly improve.In addition, apparatus expensive, troublesome poeration is consuming time, and technique is loaded down with trivial details, needs these shortcomings such as High Temperature High Pressure to significantly limit the widespread use of nitrating graphene quantum dot.Therefore, how to select starting material cheap and easy to get, prepared the nitrating graphene quantum dot possessing excellent luminance performance by single step reaction, become the significant challenge in this field.
Summary of the invention
The object of the invention is, in order to overcome the defect existed in above-mentioned prior art, to provide a kind of nitrating graphene quantum dot, its preparation method and as the application of fluorescent probe in the biomedical researches such as viable cell imaging.
In order to reach above-mentioned technique effect, the present invention takes following technical scheme:
A preparation method for nitrating graphene quantum dot, comprises the steps:
A) polymer of nitrating graphene quantum dot is prepared
Photoacoustic spectroscopy is placed in retort furnace under nitrogen protection, pyrolytic reaction 10 ~ 360min at 400 ~ 1000 DEG C, then allow it naturally cool to polymer that room temperature obtains nitrating graphene quantum dot;
B) ultrasonic stripping, stir process polymer
The polymer of the nitrating graphene quantum dot obtained in step a is placed in dense H
2sO
4with dense HNO
3nitration mixture in supersound process 0.5 ~ 3h, then at 90 ~ 120 DEG C stir 20 ~ 30h, obtain the solution of nitrating graphene quantum dot;
C) pH value is regulated
The pH value that the solution of the nitrating graphene quantum dot obtained in step b adds water and sodium carbonate regulating solution is 7, and then dialysis solution obtains nitrating graphene quantum dot.
Further technical scheme, the heat-up rate of described pyrolysis temperature is 1 ~ 20 DEG C/min.
Further technical scheme, dense H in described nitration mixture
2sO
4with dense HNO
3volume 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, provide a kind of nitrating graphene quantum dot, described nitrating graphene quantum dot has following characteristic: the length dimension of this nitrating graphene quantum dot is 2 ~ 10nm, thickness is 0.5 ~ 1.5nm, nitrogen content is 4 ~ 30%, and this nitrating graphene quantum dot surface is containing hydroxyl and carboxyl.
The present invention have chosen TATB as raw material, only needs a kind of material just can settle obtained nitrogen at one go and mixes graphene quantum dot.Reaction mechanism is: TATB is the organic crystal of laminate structure, in pyrolytic process, and the nitrogen-containing group-NH of organic molecule TATB
2with-NO
2there is degraded and produce a large amount of gas, interlayer is expanded and even peels off, for the nitrating graphene quantum dot preparing unimolecular layer provides favourable molecular structure.Meanwhile, TATB molecule produces highly active containing nitrogen free radical in pyrolytic process, and nitrogen-atoms is introduced in the lattice of carbon when the intermolecular generation carbonization of TATB.After this peel off through simple sonochemistry again and just can obtain nitrating graphene quantum dot easily.
The present invention compared with prior art, there is following beneficial effect: the present invention replaces the expensive reaction substrate needed for tradition preparation with the organic molecule TATB that nitrogen content is high, as graphene oxide, Graphene or graphene quantum dot etc., and do not need additionally to introduce nitrogenous source, low in raw material price, wide material sources, equipment is simple, in preparation process, do not introduce other impurity, be applicable to industrialized scale operation.
Simultaneously, the nitrating graphene quantum dot surface of preparing through pyrolysis method of the present invention has hydroxyl and carboxyl, make it in water, have good dispersiveness, still precipitation is not observed in aqueous after placing some months, and this nitrating graphene quantum dot can send green fluorescence, there is good bio-compatibility, almost toxicity is not had to biomass cells, fluorescent probe, cell imaging field can be widely used in.
Accompanying drawing explanation
Fig. 1 is the polymeric field emission scanning electron microscope photo of nitrating graphene quantum dot that the embodiment of the present invention 1 obtains;
Fig. 2 is the atomic force microscopy of the nitrating graphene quantum dot that the embodiment of the present invention 1 obtains;
Fig. 3 is the transmission electron microscope photo of the nitrating graphene quantum dot that the embodiment of the present invention 1 obtains;
Fig. 4 is the height statistics photo of the nitrating graphene quantum dot that the embodiment of the present invention 1 obtains;
Fig. 5 is the Raman spectrogram of the nitrating graphene quantum dot that the embodiment of the present invention 1 obtains;
Fig. 6 is the fluorescence spectrum figure of the nitrating graphene quantum dot that the embodiment of the present invention 1 obtains;
Fig. 7 is the XPS spectrum figure of the N1s of the nitrating graphene quantum dot that the embodiment of the present invention 1 obtains;
Fig. 8 is cytoactive histogram after nitrating graphene quantum dot process cervical cancer cell (HeLa) 24h using different volumes embodiment 1 obtained;
Fig. 9 is with obtained nitrating graphene quantum dot mark cervical cancer cell (HeLa) fluorogram under light field of embodiment 1;
Figure 10 is the fluorescence imaging figure with obtained nitrating graphene quantum dot mark cervical cancer cell (HeLa) of embodiment 1.
Embodiment
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 retort furnace under nitrogen protection; 750 DEG C are warmed up to the heat-up rate of 2 DEG C/min; insulation pyrolytic reaction 20min, be naturally down to the polymer that room temperature obtains nitrating graphene quantum dot subsequently, the polymer 0.1g getting this nitrating graphene quantum dot is placed in the dense H of 18.75ml
2sO
4hNO dense with 5.25ml
3mixing acid under ultrasonic power is 300W ultrasonic stripping 2h, then at 100 DEG C, arrange stirring velocity is the solution that 600r/min stirs that 24h obtains nitrating graphene quantum dot, in the solution of this nitrating graphene quantum dot, add 50ml water and the pH value of solution is adjusted to 7 by sodium carbonate, finally solution dialysis is obtained nitrating graphene quantum dot.
Embodiment 2
0.5gTATB is placed in retort furnace under nitrogen protection; 500 DEG C are warmed up to the heat-up rate of 5 DEG C/min; insulation pyrolytic reaction 240min, be naturally down to the polymer that room temperature obtains nitrating graphene quantum dot subsequently, the polymer 0.1g getting this nitrating graphene quantum dot is placed in the dense H of 18.75ml
2sO
4hNO dense with 5.25ml
3mixing acid under ultrasonic power is 400W ultrasonic stripping 2h, then at 100 DEG C, arrange stirring velocity is the solution that 500r/min stirs that 24h obtains nitrating graphene quantum dot, in the solution of this nitrating graphene quantum dot, add 50ml water and the pH value of solution is adjusted to 7 by sodium carbonate, finally solution dialysis is obtained nitrating graphene quantum dot.
Embodiment 3
0.5gTATB is placed in retort furnace under nitrogen protection; 900 DEG C are warmed up to the heat-up rate of 10 DEG C/min; insulation pyrolytic reaction 40min, be naturally down to the polymer that room temperature obtains nitrating graphene quantum dot subsequently, the polymer 0.1g getting this nitrating graphene quantum dot is placed in the dense H of 18.75ml
2sO
4hNO dense with 5.25ml
3mixing acid under ultrasonic power is 400W ultrasonic stripping 2h, then at 100 DEG C, arrange stirring velocity is the solution that 800r/min stirs that 24h obtains nitrating graphene quantum dot, in the solution of this nitrating graphene quantum dot, add 50ml water and the pH value of solution is adjusted to 7 by sodium carbonate, finally solution dialysis is obtained nitrating graphene quantum dot.
Embodiment 4
0.5gTATB is placed in retort furnace under nitrogen protection; 1000 DEG C are warmed up to the heat-up rate of 20 DEG C/min; insulation pyrolytic reaction 20min, be naturally down to the polymer that room temperature obtains nitrating graphene quantum dot subsequently, the polymer 0.1g getting this nitrating graphene quantum dot is placed in the dense H of 18.75ml
2sO
4hNO dense with 5.25ml
3mixing acid under ultrasonic power is 200W ultrasonic stripping 2h, then at 100 DEG C, arrange stirring velocity is the solution that 300r/min stirs that 24h obtains nitrating graphene quantum dot, in the solution of this nitrating graphene quantum dot, add 50ml water and the pH value of solution is adjusted to 7 by sodium carbonate, finally solution dialysis is obtained nitrating graphene quantum dot.
Embodiment 5
Nitrating graphene quantum dot obtained by the present invention is tested as the application of fluorescent probe in biomedical research, the cytotoxicity of the nitrating graphene quantum dot obtained by mensuration.
Specific experiment method is: first by HeLa cell at 37 DEG C, 50%CO
2be that substratum is cultivated with DMEM under atmosphere, wherein contain 10% foetal calf serum and 1% penicillin/streptomycin in substratum, after HeLa cell cultivates 24h in 96 orifice plates, add the obtained different volumes nitrating graphene quantum dot 1 μ l of embodiment 1,5 μ l, 10 μ l, 15 μ l, 20 μ l, wherein the concentration of nitrating graphene quantum dot is 14 μ g/ml, continue to cultivate 24h, then in cell culture fluid, Alamar Blue indicator is added, when substratum color becomes pink colour from blueness, measure its fluorescence intensity.
See Fig. 8, result shows, it is active in noticeable change to use the cervical cancer cell (HeLa) after the process of different volumes nitrating graphene quantum dot, shows that nitrating graphene quantum dot prepared by the present invention does not have biomass cells or only has the cytotoxicity of trace.
Embodiment 6
Nitrating graphene quantum dot prepared by the present invention is as the application of fluorescent probe in cell imaging.
Specific experiment process is: first by HeLa cell at 37 DEG C, 50%CO
2under atmosphere after overnight incubation, add the obtained nitrating graphene quantum dot 100 μ l (concentration is 14 μ g/ml) of embodiment 1 to continue to cultivate 4h, then rinse by PBS solution and under excitation wavelength is 460nm, observe HeLa cell with laser confocal microscope afterwards 3 ~ 5 times.
It is nitrating graphene quantum dot mark cervical cancer cell (HeLa) fluorogram under light field obtained by embodiment 1 see Fig. 9.
See the fluorescence imaging figure that Figure 10 is with obtained nitrating graphene quantum dot mark cervical cancer cell (HeLa) of embodiment 1, in figure, the part of HeLa cell peripheral bright white is actual presents green fluorescence for nitrating graphene quantum dot, shows that the nitrating graphene quantum dot entering cell is only distributed near nuclear membrane simultaneously.
Although with reference to explanatory embodiment of the present invention, invention has been described here, above-described embodiment is only the present invention's preferably embodiment, embodiments of the present invention are not restricted to the described embodiments, should be appreciated that, those skilled in the art can design a lot of other amendment and embodiment, these amendments and embodiment will drop within spirit disclosed in the present application and spirit.
Claims (7)
1. a preparation method for nitrating graphene quantum dot, is characterized in that, comprises the steps:
A) polymer of nitrating graphene quantum dot is prepared
Photoacoustic spectroscopy is placed in retort furnace under nitrogen protection, pyrolytic reaction 10 ~ 360min at 400 ~ 1000 DEG C, then allow it naturally cool to polymer that room temperature obtains nitrating graphene quantum dot;
B) ultrasonic stripping, stir process polymer
The polymer of the nitrating graphene quantum dot obtained in step a is placed in dense H
2sO
4with dense HNO
3nitration mixture in ultrasonic stripping 0.5 ~ 3h, then at 90 ~ 120 DEG C stir 20 ~ 30h, obtain the solution of nitrating graphene quantum dot;
C) pH value is regulated
The pH value that the solution of the nitrating graphene quantum dot obtained in step b adds water and sodium carbonate regulating solution is 7, and then dialysis solution obtains nitrating graphene quantum dot.
2. the preparation method of nitrating graphene quantum dot according to claim 1, is characterized in that: the heat-up rate of described pyrolysis temperature is 1 ~ 20 DEG C/min.
3. the preparation method of nitrating graphene quantum dot according to claim 1, is characterized in that: dense H in described nitration mixture
2sO
4with dense HNO
3volume ratio be 3:1.
4. the preparation method of nitrating graphene quantum dot according to claim 1, is characterized in that: described ultrasonic power is: 100 ~ 400W.
5. the preparation method of nitrating graphene quantum dot according to claim 1, is characterized in that: the speed of described stirring is: 100 ~ 900r/min.
6. nitrating graphene quantum dot prepared by the preparation method any one of Claims 1 to 5 described in claim.
7. nitrating graphene quantum dot according to claim 6, it is characterized in that it has following characteristic: the length dimension of this nitrating graphene quantum dot is 2 ~ 10nm, thickness is 0.5 ~ 1.5nm, and nitrogen content is 4 ~ 30%, and this nitrating graphene quantum dot surface is containing hydroxyl and carboxyl.
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| 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 |
| CN106276880A (en) * | 2016-08-22 | 2017-01-04 | 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 |
| CN108485659A (en) * | 2018-02-12 | 2018-09-04 | 上海大学 | Amphiphilic graphene quantum dot material, preparation method and its application that fluorescence probe is imaged as cell nucleus targeting |
| 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 |
| 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 |
| CN111484840A (en) * | 2020-04-24 | 2020-08-04 | 四川大学 | Conjugated c (RGDFC) sulfur-nitrogen double-doped graphene quantum dot 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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