CN105567228B - A kind of fluorescent carbon quantum dot of N, P, S codope and its preparation method and application - Google Patents
A kind of fluorescent carbon quantum dot of N, P, S codope and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of N, P, the fluorescent carbon quantum dot of S codopes and its preparation method and application, belong to Illuminant nanometer field of material technology.Preparation process:With biological mushroom (saccharomycete or Escherichia coli or staphylococcus aureus, or aspergillus niger) for carbon source, the water of respective volume is added, hydro-thermal reaction obtains dark brown solution;Question response stops, after reactor natural cooling, and the removal of impurity is gone in dialysis, that is, obtains obtaining N after the carbon quantum dot aqueous solution, freeze-drying, P, the carbon quantum dot of S codopes.The present invention is using biomass as carbon source, and raw material sources are extensive and cheap, environmental protection, and technique is simple, and preparation condition requires low.The carbon quantum dot of gained can be used for Cr (VI) ion, MnO as " switching mode " fluorescence probe4 ‑And the detection of ascorbic acid, it can also be used to cell imaging.
Description
Technical field
The present invention relates to Illuminant nanometer material, more particularly to carbon quantum dot, the one kind specifically prepared using biological mushroom
The carbon quantum dot of N, P, S codope and its be used as fluorescence probe detection Cr (VI) ion, MnO4 -And ascorbic acid etc., and thin
Application in born of the same parents' imaging.
Background technology
Quantum dot has superior optics and electrical properties by great concern and extensive research, its conduct due to it
Quasi-zero dimension nano material has the superior property such as quantum confined effect, skin effect, dimensional effect, therefore quantum dot is in optics
Good application has been obtained in terms of device, electricity device, bio-imaging, biological load medicine.Traditional quantum dot research is more
For semiconductor-quantum-point (such as CdSe, PbTe, CdTe), it is in biomedical sector especially in the dynamic of cell, live body
Application in spike and imaging has shown huge potentiality, but has simultaneously because the introducing of heavy metal element is that its toxicity is larger
Have luminous unstable, easily flicker, and then limit its application on bio-imaging and biomarker, therefore find preferable nothing
Malicious nanoscale alternative materials turn into study hotspot.
Carbon quantum dot is a kind of new nano material, in recent years by the extensive concern of vast researcher.Carbon amounts
Son point refers to that size is less than 10nm carbon ball shape nano-particle, and it has the fluorescence excitation dependence of characteristic.With traditional half
Conductor quantum dot is compared, and it has high good water solubility, chemical stability, easy functionalization, resistance to photobleaching, low toxicity, biocompatibility
The advantages of good.These advantages cause carbon quantum dot to have broad application prospects in fields such as biological and medical science.
The preparation method of carbon quantum dot mainly has two kinds at present, method (Top-down) and from bottom to top method from top to bottom
(Bottom-up).Top-to-bottom method mainly includes arc discharge, laser ablation, electrochemical oxidation, electron beam irradiation etc.,
Such method generally requires strict experiment condition or the special energy, and cost is high, and the fluorescence volume of the carbon quantum dot obtained
Sub- yield is relatively low;Bottom-to-top method mainly includes combustion method, hydrothermal carbonization method, supports synthetic method, microwave method, supercritical ultrasonics technology
Deng, but be due to that the raw material of such method selection is all non-renewable energy resources and needs strict aftertreatment technology, so also not
Beneficial to continuing and large-scale production carbon quantum dot.Therefore, cheap and easy to get, aboundresources, Nantural non-toxic and environmentally friendly are found
Biological raw material prepares dopingization, the carbon quantum dot of high-fluorescence quantum yield to Pharmaceutical Analysis and cell imaging application as carbon source
Have great importance.Largely carbon quantum dot is synthesized under the premise of environmental protection from inexpensive green carbon source to be very important.It is biological
Matter is widespread in nature, cheap and easy to get, inexhaustible.Biomass is applied to the green of nano material
Preparation and the functional modification of some nanostructureds, had both extended the application field of biomass, and environment, therefore tool are protected again
There is vast potential for future development.
The content of the invention
It is an object of the invention to provide a kind of N, P, the fluorescent carbon quantum dot of S codopes, and set up it is a kind of it is simple to operate,
Device simple, the preparation method of raw material environmental protection;And by described N, P, the carbon quantum dot of S codopes is used as fluorescence probe
For ion, Pharmaceutical Analysis and cell imaging.
A kind of N that the present invention is provided, P, the preparation method of the carbon quantum dot of S codopes comprise the following steps:
1) dry biological mushroom powder is added in the water of certain volume, obtains scattered bacterium solution;
2) obtained bacterium solution is transferred in hydrothermal reaction kettle, 4h-12h is reacted at 160 DEG C -240 DEG C, question response stops
Only, after reactor natural cooling, centrifugation removes the dark brown solution that insoluble matter is clarified, and passes through 500-1000Da dialysis
Bag, dialysis treatment at least 3 days in glass container obtain pure N, P, the aqueous solution of the carbon quantum dot of S codopes;
3) target N, P, the carbon quantum dot of S codopes are obtained after the above-mentioned carbon quantum dot aqueous solution is freeze-dried.
Step 1) described in biological mushroom be saccharomycete, Escherichia coli, staphylococcus aureus or aspergillus niger.
The above method is with saccharomycete or Escherichia coli or staphylococcus aureus, or aspergillus niger is carbon source, utilizes hydro-thermal
Synthetic method, while adulterating nitrogen phosphate and sulfur in carbon quantum dot, has obtained N, P, the carbon quantum dot of S codopes.
N prepared by the above method, P, the carbon quantum dot of S codopes can be used to detect Cr as " switching mode " fluorescence probe
(VI) ion, MnO4 -And ascorbic acid etc., it can also be applied to cell imaging.
Compared with prior art, the invention has the advantages that:
(1) operating procedure of the present invention is simple, it is not necessary to which it is that can obtain nitrogen phosphorus sulphur to be total to handle or modify by surface passivator
The carbon quantum dot of doping.
(2) biomass is widespread in nature, cheap and easy to get, inexhaustible.Raw material of the present invention are only
Biological mushroom is needed, wide material sources, environmental protection is cheap.
(3) the target carbon quantum dot obtained by the present invention all has good solubility and dispersiveness in aqueous.
(4) launch wavelength of target carbon quantum dot in itself red shift with the red shift of excitation wavelength.
(5) biological bacteria yeast-like fungi, staphylococcus aureus, Escherichia coli, aspergillus niger be as the microorganism being widely present,
It is applied to first in synthesis, while this method can expand to other microorganisms.
(6) quantum yield of target carbon quantum dot is higher, with quinine sulfate (quantum yield 54%) for object of reference, gained carbon
The quantum efficiency of quantum dot is general between 6.40%-12.68%.
In a word, operating procedure of the present invention is simple, and raw material sources are extensive, environmental protection and cheap, preparation condition requirement
Low, the carbon quantum dot optical property of gained nitrogen phosphorus sulphur codope is stable, and fluorescence quantum yield is high, solves existing carbon quantum dot system
Preparation Method because technique and raw material limitation can not large-scale production and obtain carbon quantum dot fluorescence quantum efficiency it is relatively low the problem of,
Also, the carbon quantum dot can be applied to Cr (VI) ion, MnO4 -And the detection of ascorbic acid, and the field such as cell imaging.
Brief description of the drawings
Fig. 1 is N, P prepared by embodiment 1, the ultra-violet absorption spectrum and fluorescence excitation-emission of the carbon quantum dot of S codopes
Spectrum;The carbon quantum dot aqueous solution is wherein filled in quartz colorimetric utensil, is positioned on ultraviolet transmission platform, is swashed through 365nm excitation sources
Blue-fluorescence is sent after hair.
Fig. 2 is N prepared by embodiment 1, P, the light that the carbon quantum dot fluorescence emission curves of S codopes change with excitation wavelength
Spectrogram.
Abscissa is detection in the N that Fig. 3 is prepared for embodiment 1, P, the infrared spectrogram of the carbon quantum dot of S codopes, figure
Wavelength, ordinate is transmitance.
Fig. 4 is N, P, the XPS spectrum figure of the carbon quantum dot of S codopes prepared by embodiment 1.
Fig. 5 is N, P prepared by embodiment 1, the transmission electron microscope picture (left side) and grain size distribution of the carbon quantum dot of S codopes
(right side).
Fig. 6 is the N, P, the fluorescence spectra of the carbon quantum dot of S codopes that the preparation of embodiment 1 is quenched in Cr (VI).
Fig. 7 be ascorbic acid recover Cr (VI) be quenched after embodiment 1 prepare N, P, the carbon quantum dot of S codopes it is glimmering
Light spectrogram.
Fig. 8 is MnO4 -The N, P, the fluorescence spectra of the carbon quantum dot of S codopes of the preparation of embodiment 1 is quenched.
Fig. 9 is that ascorbic acid recovers MnO4 -N, P, the fluorescence of the carbon quantum dot of S codopes prepared by the embodiment 1 after being quenched
Spectrogram.
Figure 10 be embodiment 1 prepare N, P, S codopes carbon quantum dot mark SiHa cells laser co-focusing into
As figure;
Embodiment
The present invention is elaborated with reference to embodiment, embodiment gives detailed embodiment and specific behaviour
Make process, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
The preparation of the carbon quantum dot of N, P, S codope:
Step 1, the saccharomycete for weighing 0.5g dryings is added in 10mL deionized waters, and the scattered aqueous solution is made;
Step 2, mixed liquor step (1) obtained is transferred in hydrothermal reaction kettle, the hydro-thermal reaction 8h at 240 DEG C;
Step 3, product centrifuge step (2) obtained centrifuges 10min with 6000r/min rotating speeds, then is divided with retention
Son amount is dialysed 3 days for 500~1000Da bag filter, finally gives N, P, the carbon quantum dot solution of S codopes.Its relative quantum
Yield (using quinine sulfate as standard) is 12.54%.
Fig. 1-10 is shown in property representation and application.
Embodiment 2
The preparation of the carbon quantum dot of N, P, S codope:
Step 1, the saccharomycete for weighing 0.5g dryings is added in 10mL deionized waters, and the scattered aqueous solution is made;
Step 2, mixed liquor step (1) obtained is transferred in hydrothermal reaction kettle, the hydro-thermal reaction 12h at 240 DEG C;
Step 3, product centrifuge step (2) obtained centrifuges 10min with 6000r/min rotating speeds, then is divided with retention
Son amount is dialysed 3 days for 500~1000Da bag filter, finally gives N, P, the carbon quantum dot solution of S codopes.Its relative quantum
Yield (using quinine sulfate as standard) is 12%.
Embodiment 3
The preparation of the carbon quantum dot of N, P, S codope:
Step 1, the saccharomycete for weighing 0.5g dryings is added in 10mL deionized waters, and the scattered aqueous solution is made;
Step 2, mixed liquor step (1) obtained is transferred in hydrothermal reaction kettle, the hydro-thermal reaction 12h at 160 DEG C;
Step 3, product centrifuge step (2) obtained centrifuges 10min with 6000r/min rotating speeds, then is divided with retention
Son amount is dialysed 3 days for 500~1000Da bag filter, finally gives N, P, the carbon quantum dot solution of S codopes.Its relative quantum
Yield (using quinine sulfate as standard) is 6.82%.
Embodiment 4
The preparation of the carbon quantum dot of N, P, S codope:
Step 1, the saccharomycete for weighing 0.5g dryings is added in 10mL deionized waters, and the scattered aqueous solution is made;
Step 2, mixed liquor step (1) obtained is transferred in hydrothermal reaction kettle, the hydro-thermal reaction 12h at 200 DEG C;
Step 3, product centrifuge step (2) obtained centrifuges 10min with 6000r/min rotating speeds, then is divided with retention
Son amount is dialysed 3 days for 500~1000Da bag filter, finally gives N, P, the carbon quantum dot solution of S codopes.Its relative quantum
Yield (using quinine sulfate as standard) is 8.88%.
Embodiment 5
The preparation of the carbon quantum dot of N, P, S codope:
Step 1, the saccharomycete for weighing 0.5g dryings is added in 10mL deionized waters, and the scattered aqueous solution is made;
Step 2, mixed liquor step (1) obtained is transferred in hydrothermal reaction kettle, the hydro-thermal reaction 4h at 240 DEG C;
Step 3, product centrifuge step (2) obtained centrifuges 10min with 6000r/min rotating speeds, then is divided with retention
Son amount is dialysed 3 days for 500~1000Da bag filter, finally gives N, P, the carbon quantum dot solution of S codopes.Its relative quantum
Yield (using quinine sulfate as standard) is 11.67%.
Embodiment 6
The preparation of the carbon quantum dot of N, P, S codope:
Step 1, the staphylococcus aureus for weighing 0.5g dryings is added in 10mL deionized waters, is made scattered water-soluble
Liquid;
Step 2, mixed liquor step (1) obtained is transferred in hydrothermal reaction kettle, the hydro-thermal reaction 8h at 240 DEG C;
Step 3, product centrifuge step (2) obtained centrifuges 10min with 6000r/min rotating speeds, then is divided with retention
Son amount is dialysed 3 days for 500~1000Da bag filter, finally gives N, P, the carbon quantum dot solution of S codopes.Its relative quantum
Yield (using quinine sulfate as standard) is 12.68%.
Embodiment 7
The preparation of the carbon quantum dot of N, P, S codope:
Step 1, the Escherichia coli for weighing 0.5g dryings are added in 10mL deionized waters, and the scattered aqueous solution is made;
Step 2, mixed liquor step (1) obtained is transferred in hydrothermal reaction kettle, the hydro-thermal reaction 8h at 240 DEG C;
Step 3, product centrifuge step (2) obtained centrifuges 10min with 6000r/min rotating speeds, then is divided with retention
Son amount is dialysed 3 days for 500~1000Da bag filter, finally gives N, P, the carbon quantum dot solution of S codopes.Its relative quantum
Yield (using quinine sulfate as standard) is 9.7%.
Embodiment 8
The preparation of the carbon quantum dot of N, P, S codope:
Step 1, the aspergillus niger for weighing 0.5g dryings is added in 10mL deionized waters, and the scattered aqueous solution is made;
Step 2, mixed liquor step (1) obtained is transferred in hydrothermal reaction kettle, the hydro-thermal reaction 8h at 240 DEG C;
Step 3, product centrifuge step (2) obtained centrifuges 10min with 6000r/min rotating speeds, then is divided with retention
Son amount is dialysed 3 days for 500~1000Da bag filter, finally gives N, P, the carbon quantum dot solution of S codopes.Its relative quantum
Yield (using quinine sulfate as standard) is 11.75%.
Embodiment 9
Quartz colorimetric utensil fills the N of embodiment 1, and P, the fluorescent carbon quantum dot aqueous solution of S codopes is positioned over ultraviolet transmission
On platform, bright blue-fluorescence is sent after being excited through 365nm excitation sources.
Embodiment 10
N prepared by embodiment 1, P, the carbon quantum dot aqueous solution fluorescence of S codopes can be quenched by Cr (VI), as shown in fig. 6,
With the increase of Cr (VI) ion concentration, the fluorescence intensity of carbon quantum dot is gradually reduced.
Embodiment 11
Embodiment 1 prepare N, P, the fluorescent carbon quantum dot aqueous solution of S codopes be quenched by Cr (VI) after by ascorbic acid
Recover fluorescence, as shown in fig. 7, with the increase of ascorbic acid concentrations, the fluorescence intensity of carbon quantum dot is gradually recovered, and illustrates made
Standby carbon quantum dot can be used as " switching mode " fluorescence probe.
Embodiment 12
N, P prepared by embodiment 1, the carbon quantum dot aqueous solution fluorescence of S codopes can be by MnO4 -It is quenched, as shown in figure 8, with
MnO4 -The increase of ion concentration, the fluorescence intensity of carbon quantum dot is gradually reduced.
Embodiment 13
N, P prepared by embodiment 1, the fluorescent carbon quantum dot aqueous solution of S codopes is by MnO4 -It is extensive by ascorbic acid after being quenched
Multiple fluorescence, as shown in figure 9, with the increase of ascorbic acid concentrations, the fluorescence intensity of carbon quantum dot is gradually recovered, illustrates prepared
Carbon quantum dot can be used as " switching mode " fluorescence probe.
Embodiment 14
N prepared by embodiment 1, P, the carbon quantum dot aqueous solution (5mg/mL) of S codopes are used to mark SiHa cells, such as scheme
Shown in 10, cellular morphology is good, it is seen that target carbon quantum dot does not have cytotoxicity, available for viable cell labelling.Figure 10 from a left side to
The right side is followed successively by:Details in a play not acted out on stage, but told through dialogues (excites as 405nm) cytological map (blueness), and details in a play not acted out on stage, but told through dialogues (excites as 488nm) cytological map (green), blue and green
Color stacking chart.
Claims (2)
- The fluorescent carbon quantum dot of 1.N, P, S codope is in detection Cr (VI) ion, MnO4 -Application in ion or ascorbic acid, institute N, P are stated, the fluorescent carbon quantum dot of S codopes, which is prepared by a method comprising the following steps, to be obtained:1) dry biological mushroom powder is added in the water of certain volume, obtains scattered bacterium solution;2) obtained bacterium solution is transferred in hydrothermal reaction kettle, 4h-12h is reacted at 160 DEG C -240 DEG C, question response stops, After reactor natural cooling, centrifugation removes the dark brown solution clarified of insoluble matter, by 500-1000Da bag filter, Dialysis treatment at least 3 days in glass container, that is, obtain pure N, P, the aqueous solution of the carbon quantum dot of S codopes;3) target N, P, the carbon quantum dot of S codopes are obtained after the above-mentioned carbon quantum dot aqueous solution is freeze-dried;Step 1) described in biological mushroom be saccharomycete, Escherichia coli, staphylococcus aureus or aspergillus niger.
- 2. the fluorescent carbon quantum dot of N as claimed in claim 1, P, S codope is in detection Cr (VI) ion, MnO4 -Ion is anti- Application in bad hematic acid, it is characterised in that step 2) described in hydrothermal temperature be 240 DEG C, reaction time 8h.
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