CN108410455A - A kind of method of simultaneously synthesizing hydrophilic, hydrophobic carbon dots and its in detection Au3+With the application prepared in white light emitting diode - Google Patents

A kind of method of simultaneously synthesizing hydrophilic, hydrophobic carbon dots and its in detection Au3+With the application prepared in white light emitting diode Download PDF

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CN108410455A
CN108410455A CN201810183982.0A CN201810183982A CN108410455A CN 108410455 A CN108410455 A CN 108410455A CN 201810183982 A CN201810183982 A CN 201810183982A CN 108410455 A CN108410455 A CN 108410455A
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周艳梅
高文莉
祁志冲
刘山虎
徐成功
宋昊翰
王晓
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Abstract

A kind of method of simultaneously synthesizing hydrophilic, hydrophobic carbon dots and its in detection Au3+With the application prepared in white light emitting diode, belong to fluorescent carbon field of nanometer material technology, use sulfuric acid as raw material, ethyl alcohol dissolves sulfuric acid, and stirring forms it into uniform mixed solution;Mixed solution is transferred in polytetrafluoroethylene (PTFE) autoclave after 200 DEG C of heating, it is cooled to room temperature, the lower layer's solution for obtaining black is hydrophilic carbon dots and red supernatant liquid is hydrophobic carbon dots, the present invention provides the methods of simple simultaneously synthesizing hydrophilic carbon dots and hydrophobic carbon dots, 8 mg methylene blues are added in the feed simultaneously, the hydrophilic carbon dots prepared can be used for manufacturing white light emitting diode under the ultraviolet light of 365 nm, and the hydrophilic carbon dots for preparing the present invention can be delicately as fluorescence probe, selectively detect gold ion, gold ion in cell may be implemented visually to test and analyze.

Description

A kind of method of simultaneously synthesizing hydrophilic, hydrophobic carbon dots and its in detection Au3+With prepare white light Application in light emitting diode
Technical field
The invention belongs to fluorescent carbon field of nanometer material technology, and in particular to a kind of method of simultaneously synthesizing hydrophilic, hydrophobic carbon dots and It is in detection Au3+With the application prepared in white light emitting diode.
Background technology
Fluorescent carbon point because of good characteristics such as its excellent optical property, good photostability, lower cytotoxicities Through showing huge application potential in fields such as sensing, bio-imaging, photocatalysis, photovoltaic device, solar cells.
The carbon dots synthesized at present show hydrophilic property mostly, and in a recent study hydrophobic carbon dots due to its The application of electronic device and drug delivery etc. also has received widespread attention, however is can not achieve in the prior art using relatively low Cost and the simultaneously synthesizing hydrophilic and hydrophobic carbon dots of simple step.Therefore, the presoma of low cost and rational skill are selected Art prepares hydrophilic and hydrophobic carbon dots simultaneously and has very important significance.
Gold is used as a kind of noble metal, is all played an important role in fields such as catalysis, biology and medicine, however, being based on Au catalyst and gold nanoparticle dramatically increase, with Au3+Relevant toxicity also dramatically increases, and is found to have potential life Object toxicity.Au3+It can combine closely, and liver, kidney and peripheral nervous system may be damaged with a variety of enzymes and DNA, But it can not achieve visual detection point when being detected in the prior art to the gold ion in tissue and cell using carbon dots Analysis.
White light emitting diode is the green light source of a new generation, long lifespan, energy conservation and environmental protection.Semiconductor-quantum-point is due to it Adjustable transmitting, high quantum yield and narrow transmitted bandwidth, cause more and more in white light emitting diode field Concern.However, traditional quantum dot generally includes toxic heavy metal, there are certain toxicity for these heavy metals, it will to ring Border and the mankind cause damages, this will limit their development to a certain extent, developing low-cost, hypotoxicity new material be used for It will be significantly to prepare white light emitting diode.
Invention content
It is simultaneously synthesizing hydrophilic and hydrophobic using lower cost and simple step to solve to can not achieve in the prior art Carbon dots, carbon dots can not achieve visual detection and analysis and white-light emitting when being detected to the gold ion in tissue and cell Usually there is certain toxicity in the quantum dot that diode uses, it will the problems such as causing damages to environment and the mankind.Mesh of the present invention Be the provision of the method for simple simultaneously synthesizing hydrophilic carbon dots and hydrophobic carbon dots, while 8 mg methylene being added in the feed The hydrophilic carbon dots of indigo plant, preparation can be used for manufacturing white light emitting diode under the ultraviolet light of 365 nm, and will be of the invention The hydrophilic carbon dots prepared as fluorescence probe can delicately, selectively detect gold ion, can be with to the gold ion in cell Realize visual detection and analysis.
The above-mentioned purpose of the present invention is achieved through the following technical solutions:A kind of method of simultaneously synthesizing hydrophilic, hydrophobic carbon dots, Include the following steps:
(1)The 0.1 mL concentrated sulfuric acids are dissolved with ethyl alcohol(Normal concentration), 1~2 min is stirred, uniform mixed solution is formed it into;
(2)By step(1)Described in after mixed solution is transferred in polytetrafluoroethylene (PTFE) autoclave 200 DEG C of 6 h of heating, then it is cold But to room temperature, the lower layer's solution for obtaining black is hydrophilic carbon dots and red supernatant liquid is hydrophobic carbon dots.
Preferably, by step(2)Solution and lower layer's solution obtain pure respectively with 0.22 μM of membrane filtration at the middle and upper levels Hydrophilic, hydrophobic carbon dots.
Preferably, step(1)Middle ethanol solution is 10 mL, step(2)Middle polytetrafluoroethylene (PTFE) autoclave is 25 mL.
Preferably, step(1)Middle addition methylene blue dissolves methylene blue and sulfuric acid with ethyl alcohol, and stirring forms it into Even mixed solution.
Preferably, step(1)Methylene Blue is 8 mg.
Hydrophilic carbon dots are applied to prepare white light emitting diode:0.1 mL of methylene blue of 8 mg is dissolved with 10 mL ethyl alcohol The concentrated sulfuric acid stirs 1~2 min, forms it into uniform mixed solution;Obtained mixed solution is transferred to 25mL polytetrafluoroethyl-nes In alkene autoclave after 200 DEG C of 6 h of heating, it is cooled to room temperature, the lower layer's solution for obtaining black is hydrophilic carbon dots and red Supernatant liquid be hydrophobic carbon dots.Hydrophilic carbon dots and hydrophobic carbon dots are dissolved in distilled water and ethyl alcohol, in the ultraviolet light of 365 nm Hydrophilic carbon dots show that bright white, hydrophobic carbon dots show bright blue under the ultraviolet light of 365 nm under irradiation Fluorescence.The hydrophilic carbon dots to emit white light can manufacture two pole of white-light emitting with polyvinyl alcohol composite coating on UV LED Pipe.
Above-mentioned synthesis hydrophilic carbon dots are used equally for the detection of gold ion.
Preferably, gold ion is detected using hydrophilic carbon dots as fluorescence probe.
Preferably, the gold ion detection being used in water body.
Preferably, the gold ion detection being used in cell body.
The carbon dots synthesized in the past compare, beneficial effects of the present invention:
1, be raw material with sulfuric acid the present invention provides the method for simultaneously synthesizing hydrophilic carbon dots and hydrophobic carbon dots, ethyl alcohol as solvent, Have the characteristics that at low cost, synthetic method is simple, solves to can not achieve in the prior art and use lower cost and simple The shortcomings that step simultaneously synthesizing hydrophilic and hydrophobic carbon dots;
2 while the methylene blue of 8 mg being added in the feed, with sulfuric acid collectively as raw material, by the hydrophilic and hydrophobic carbon of preparation Point is dissolved in respectively in distilled water and ethyl alcohol, and hydrophilic carbon dots send out bright white and hydrophobic carbon under the ultraviolet light of 365 nm Point sends out blue-fluorescence, and the hydrophilic carbon dots to emit white light can manufacture white light with polyvinyl alcohol composite coating on UV LED Light emitting diode solves traditional quantum dot and usually there is certain toxicity, it will asks what environment and the mankind caused damages Topic;
3, the present invention prepare hydrophilic carbon dots can be used as fluorescence probe delicately, selectively detect gold ion, in cell Gold ion may be implemented visually to test and analyze, and with Au in follow-up analysis tissue and organism3+Potential application Value, solving the when of being detected in the prior art to the gold ion in tissue and cell using hydrophilic carbon dots can not achieve visually The detection and analysis of change.
Description of the drawings
The present invention provides the transmission electron microscope figures of hydrophilic, hydrophobic carbon dots and atom grain microscope figure by Fig. 1;
The present invention provides the x-ray photoelectron spectroscopies of hydrophilic, hydrophobic carbon dots by Fig. 2;
The present invention provides the FTIR spectrums of hydrophilic, hydrophobic carbon dots by Fig. 3;
The present invention provides the fluorescence photos under the fluorescence spectrum of hydrophilic, hydrophobic carbon dots and 365 nm ultra violet lamps by Fig. 4;
Fig. 5 is the hydrophilic carbon dots of the present invention to different metal ions selectivity and emulative fluorescence response;
Fig. 6 is the hydrophilic carbon dots of the present invention to the Au in cell3+Detection;
Fig. 7 is the white light emitting diode that the hydrophilic carbon dots of the present invention are prepared with polyvinyl alcohol composite coating UV LED Fluorescence emission spectrum, white light emitting diode photo and International Commission on Illumination's color coordinate diagram.
Specific implementation mode:
In order to better understand the present invention, with reference to the embodiment content that the present invention is further explained, but the present invention's is interior Appearance is not limited only to following embodiments.
Embodiment 1
A kind of method of simultaneously synthesizing hydrophilic, hydrophobic carbon dots and its in detection Au3+With the application prepared in white light emitting diode.
(One)The method for preparing hydrophilic, hydrophobic carbon dots, its step are as follows:
(1)8 mg methylene blues and 0.1 mL sulfuric acid are dissolved with the ethyl alcohol of 10 mL(The concentrated sulfuric acid of selection standard), stirring makes its shape At uniform mixed solution;
(2)Above-mentioned mixed solution is transferred to 200 DEG C of 6 h of heating in 25 mL polytetrafluoroethylene (PTFE) autoclaves, is cooled to After room temperature, the lower layer's solution for obtaining black is the hydrophobic carbon dots of hydrophilic carbon dots and red supernatant liquid;
(3)Upper solution and lower layer's solution obtain pure hydrophilic, hydrophobic carbon dots respectively with 0.22 μM of membrane filtration.
Above-mentioned hydrophilic carbon dots are detected different metal ions as fluorescence probe.
Using above-mentioned hydrophilic carbon dots as fluorescence probe to the Au in cell3+It is detected.
Hydrophilic, hydrophobic carbon dots obtained above are dissolved in distilled water and ethyl alcohol respectively, in the ultraviolet light of 365 nm.
(Two)As a result:
(1)The transmission electron microscope figure and atom grain microscope figure of the obtained hydrophilic, hydrophobic carbon dots of embodiment 1 are shown in Fig. 1:Parent, The transmission electron microscope figure and atom grain microscope figure of hydrophobic carbon dots, which show the knots that hydrophilic, hydrophobic carbon dots have class ball-type Structure.The grain size of wherein hydrophobic carbon dots is more than the grain size of hydrophilic carbon dots.
(2)The x-ray photoelectron spectroscopy of the obtained hydrophilic, hydrophobic carbon dots of embodiment 1 is shown in Fig. 2:The X of hydrophilic, hydrophobic carbon dots is penetrated Photoelectron spectra, four apparent peaks of display are corresponded in 532.1 eV, 401.9 eV, 284.6 eV and 168.9 eV O1s, N1s, C1s and S2p.The oxygen content of hydrophilic, hydrophobic carbon dots is respectively 42.93% and 28.45%, the O1s's of hydrophilic, hydrophobic carbon dots High-resolution energy spectrum diagram, which show contain hydrophilic hydroxy functional group in hydrophilic carbon dots.
(3)The FTIR spectrum of the obtained hydrophilic, hydrophobic carbon dots of embodiment 1 is shown in Fig. 3:In Fu of hydrophilic, hydrophobic carbon dots Leaf infrared spectrum, which show hydrophilic carbon dots surfaces to contain hydrophilic hydroxy functional group, and hydrophobic carbon dots do not have hydroxy functional group.
(4)Fluorescence photo under the fluorescence spectrum and 365 nm ultra violet lamps of the obtained hydrophilic, hydrophobic carbon dots of embodiment 1 See Fig. 4:The fluorescence spectrum of hydrophilic, hydrophobic carbon dots, which show hydrophilic, hydrophobic carbon dots to have the property that excitation wavelength relies on launch wavelength Matter.Fluorescence photo under the ultra violet lamp of hydrophilic, hydrophobic carbon dots, which show hydrophilic and hydrophobic carbon dots to shine in 365 nm ultraviolet lamps It penetrates and lower shows bright white and blue-fluorescence respectively.
(5)The obtained hydrophilic carbon dots of embodiment 1 are to different metal ions selectivity and emulative fluorescence intensity(F/ F0)Fig. 5 is shown in variation:Which show hydrophilic carbon dots can detect Au in specific manner3+, there is selectivity and anti-interference energy well Power.
(6)The obtained hydrophilic carbon dots of embodiment 1 are to the Au in cell3+Detection see Fig. 6:In figure, a1-e1It is PC12 thin Born of the same parents' photo under the bright visual field;a2-e2It is the Au that various concentration is added3+(0-400μM)The fluorescence photo of PC12 cells afterwards;a3-e3It closes Images after and;F is various concentration Au3+In the presence of, the figure of fluorescence intensity changes of cell.It can be seen that hydrophilic carbon dots are available The Visual retrieval Au in cell3+
(7)The obtained hydrophilic carbon dots of embodiment 1 can be used for polyvinyl alcohol composite coating on UV LED Manufacture white light emitting diode is shown in Fig. 7:Light emitting diode prepared by hydrophilic carbon dots can send out the light of white, international lighting committee member Color coordinates is(0.29,0.33), coordinate is shown in white light field.
Comparative example 1
The method for preparing hydrophilic, hydrophobic carbon dots, its step are as follows:
(1)32 mg methylene blues and 0.1 mL sulfuric acid are dissolved with the ethyl alcohol of 10 mL(The concentrated sulfuric acid of selection standard), stirring makes it Form uniform mixed solution;
(2)Above-mentioned mixed solution is transferred to 200 DEG C of 6 h of heating in 25 mL polytetrafluoroethylene (PTFE) autoclaves, is cooled to After room temperature, the lower layer's solution for obtaining black is the hydrophobic carbon dots of hydrophilic carbon dots and red supernatant liquid;
(3)Upper solution and lower layer's solution obtain pure hydrophilic, hydrophobic carbon dots respectively with 0.22 μM of membrane filtration.
Above-mentioned hydrophilic carbon dots are detected different metal ions as fluorescence probe.
Using above-mentioned hydrophilic carbon dots as fluorescence probe to the Au in cell3+It is detected.
Hydrophilic, hydrophobic carbon dots obtained above are dissolved in distilled water and ethyl alcohol respectively, in the ultraviolet light of 365 nm.
Comparative example 2
The preparation method of hydrophilic, hydrophobic carbon dots, its step are as follows:
(1)24 mg methylene blues and 0.1 mL sulfuric acid are dissolved with the ethyl alcohol of 10 mL(The concentrated sulfuric acid of selection standard), stirring makes it Form uniform mixed solution;、
(2)Above-mentioned mixed solution is transferred to 200 DEG C of 6 h of heating in 25 mL polytetrafluoroethylene (PTFE) autoclaves, is cooled to After room temperature, the lower layer's solution for obtaining black is the hydrophobic carbon dots of hydrophilic carbon dots and red supernatant liquid;
(3)Upper solution and lower layer's solution obtain pure hydrophilic, hydrophobic carbon dots respectively with 0.22 μM of membrane filtration.
Above-mentioned hydrophilic carbon dots are detected different metal ions as fluorescence probe.
Using above-mentioned hydrophilic carbon dots as fluorescence probe to the Au in cell3+It is detected.
Hydrophilic, hydrophobic carbon dots obtained above are dissolved in distilled water and ethyl alcohol respectively, in the ultraviolet light of 365 nm.
Comparative example 3
The method for preparing hydrophilic, hydrophobic carbon dots, its step are as follows:
(1)16 mg methylene blues and 0.1 mL sulfuric acid are dissolved with the ethyl alcohol of 10 mL(The concentrated sulfuric acid of selection standard), stirring makes it Form uniform mixed solution;
(2)Above-mentioned mixed solution is transferred to 200 DEG C of 6 h of heating in 25 mL polytetrafluoroethylene (PTFE) autoclaves, is cooled to After room temperature, the lower layer's solution for obtaining black is the hydrophobic carbon dots of hydrophilic carbon dots and red supernatant liquid;
(3)Upper solution and lower layer's solution obtain pure hydrophilic, hydrophobic carbon dots respectively with 0.22 μM of membrane filtration.
Above-mentioned hydrophilic carbon dots are detected different metal ions as fluorescence probe.
Using above-mentioned hydrophilic carbon dots as fluorescence probe to the Au in cell3+It is detected.
Hydrophilic, hydrophobic carbon dots obtained above are dissolved in distilled water and ethyl alcohol respectively, in the ultraviolet light of 365 nm.
Comparative example 4
The method for preparing hydrophilic, hydrophobic carbon dots, its step are as follows:
(4)0.1 mL sulfuric acid is dissolved with the ethyl alcohol of 10 mL(The concentrated sulfuric acid of selection standard), stir and form it into uniform mixing Solution;
(5)Above-mentioned mixed solution is transferred to 200 DEG C of 6 h of heating in 25 mL polytetrafluoroethylene (PTFE) autoclaves, is cooled to After room temperature, the lower layer's solution for obtaining black is the hydrophobic carbon dots of hydrophilic carbon dots and red supernatant liquid;
(6)Upper solution and lower layer's solution obtain pure hydrophilic, hydrophobic carbon dots respectively with 0.22 μM of membrane filtration.
Above-mentioned hydrophilic carbon dots are detected different metal ions as fluorescence probe.
Using above-mentioned hydrophilic carbon dots as fluorescence probe to the Au in cell3+It is detected.
Hydrophilic, hydrophobic carbon dots obtained above are dissolved in distilled water and ethyl alcohol respectively, in the ultraviolet light of 365 nm.
The hydrophilic carbon dots synthesized using the preparation method of embodiment 1 and comparative example 1~4 are made probe and can be used as fluorescence spy Needle delicately, selectively detect gold ion, the gold ion in cell may be implemented visually to test and analyze, and have Au in follow-up analysis tissue and organism3+Potential using value, solve in the prior art using hydrophilic carbon dots to tissue It can not achieve visual detection and analysis when being detected with the gold ion in cell.
The fluorescence in embodiment 1 and comparative example 1~4 under the ultraviolet light in 365 nm of hydrophilic carbon dots is observed simultaneously to shine The color of piece, comparing result are as shown in table 1
Embodiment 1 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Fluorescence color Bright white It is orange It is orange It is orange Pale orange
The color of fluorescence photo of the table 1 under the ultraviolet light of 365 nm
According to table 1, be added in the feed respectively 8 mg, 32 mg, 24 mg, 16 mg methylene blue and be not added with methylene Indigo plant synthesizes different hydrophilic carbon dots from 0.1 mL sulfuric acid.Hydrophilic carbon dots are under 365 nm ultraviolet lights, with methylene blue amount Increase synthesis hydrophilic carbon dots the gradual red shift of most hyperfluorescence emission peak, make the fluorescence that transmitting is orange, when being not added in raw material When methylene blue, it is only capable of displaying faint pale orange, only when the white fluorescent that methylene blue is 8 mg energy emitting brights, at this time The hydrophilic carbon dots of white light emission can be used for preparing the diode of white light emission.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its Inventive concept is subject to equivalent substitution or change, should all cover in protection scope of the present invention.

Claims (10)

1. a kind of method of simultaneously synthesizing hydrophilic, hydrophobic carbon dots, which is characterized in that include the following steps:
(1)The 0.1 mL concentrated sulfuric acids are dissolved with ethyl alcohol, 1~2 min is stirred, forms it into uniform mixed solution;
(2)By step(1)Described in after mixed solution is transferred in polytetrafluoroethylene (PTFE) autoclave 200 DEG C of 6 h of heating, then it is cold But to room temperature, the lower layer's solution for obtaining black is hydrophilic carbon dots and red supernatant liquid is hydrophobic carbon dots.
2. a kind of method of simultaneously synthesizing hydrophilic, hydrophobic carbon dots according to claim 1, which is characterized in that by step(2) Described in upper solution and lower layer's solution respectively with 0.22 μM of membrane filtration, obtain pure hydrophilic, hydrophobic carbon dots.
3. a kind of method of simultaneously synthesizing hydrophilic, hydrophobic carbon dots according to claim 2, which is characterized in that step(1)In The ethanol solution is 10 mL, step(2)Described in polytetrafluoroethylene (PTFE) autoclave be 25 mL.
4. according to a kind of method of any simultaneously synthesizing hydrophilic, hydrophobic carbon dots of claim 1-3, which is characterized in that step Suddenly(1)Middle addition methylene blue dissolves methylene blue and sulfuric acid with ethyl alcohol, and stirring forms it into uniform mixed solution.
5. a kind of method of simultaneously synthesizing hydrophilic, hydrophobic carbon dots according to claim 4, which is characterized in that step(1)In Methylene blue is 8 mg.
6. the hydrophobic carbon dots that claim 5 synthesizes are applied to prepare white light emitting diode, which is characterized in that the hydrophobic carbon dots It is dissolved in distilled water and ethyl alcohol, hydrophilic carbon dots show bright white under the ultraviolet light of 365 nm, the parent to emit white light Water carbon dots can manufacture white light emitting diode with polyvinyl alcohol composite coating on UV LED.
7. the application of the hydrophilic carbon dots of Claims 1 to 5 any one of them, which is characterized in that be used for the detection of gold ion.
8. the application of hydrophilic carbon dots according to claim 7, which is characterized in that using the hydrophilic carbon dots as fluorescence probe Detect gold ion.
9. the application of hydrophilic carbon dots according to claim 8, which is characterized in that for the gold ion detection in water body.
10. the application of hydrophilic carbon dots according to claim 8, which is characterized in that for the gold ion detection in cell body.
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CN109207149A (en) * 2018-11-02 2019-01-15 山西大学 A kind of nitrogen, sulphur codope yellow fluorescence carbon dots and its application in anticancer drug
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CN111718713A (en) * 2020-07-21 2020-09-29 中南民族大学 Carbon dot, preparation method and application thereof, and solid luminescent forming material
CN111718713B (en) * 2020-07-21 2022-11-29 中南民族大学 Carbon dot, preparation method and application thereof, and solid luminescent forming material
CN115820250A (en) * 2022-12-20 2023-03-21 珠海科技学院 Method for simultaneously synthesizing hydrophilic carbon quantum dots and hydrophobic carbon quantum dots
CN115820250B (en) * 2022-12-20 2023-10-17 珠海科技学院 Method for simultaneously synthesizing hydrophilic carbon quantum dots and hydrophobic carbon quantum dots

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