CN108753283A - A kind of safe and simple method for preparing codope nitrogen and phosphorus carbon quantum dot - Google Patents
A kind of safe and simple method for preparing codope nitrogen and phosphorus carbon quantum dot Download PDFInfo
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- CN108753283A CN108753283A CN201810866243.1A CN201810866243A CN108753283A CN 108753283 A CN108753283 A CN 108753283A CN 201810866243 A CN201810866243 A CN 201810866243A CN 108753283 A CN108753283 A CN 108753283A
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Abstract
The invention discloses a kind of safe and simple method for preparing codope nitrogen and phosphorus carbon quantum dot, this method first dissolves amino acid, carbon matrix precursor in deionized water, and phosphoric acid solution is added, and stirring is made into clear solution；Then mixed solution is placed in ultrasonic drilling machine and is handled, ultrasonic time is 1~2h；By the solution after ultrasound oil bath heating 1-5 hours at 90-150 DEG C, nitrogen, phosphor codoping carbon dots solution are prepared, is cooled to room temperature；Large granular impurity in solution is removed by centrifugation, then is dialysed in bag filter, unreacted raw material and other little particle impurity are removed.Raw material of the present invention are safe and non-toxic, mild condition, and process is simple.By changing amino acid classes, adjust raw material than etc. can obtain blue, green, yellow or orange light the carbon quantum dot of transmitting, can be applied to the fields such as bio-imaging and ion detection.
Description
Technical field
The present invention relates to carbon quantum dots, more particularly to a kind of safe and simple side for preparing codope nitrogen and phosphorus carbon quantum dot
Method belongs to nanometer material science field.
Background technology
Carbon quantum dot is also known as carbon dots, refers to the carbon nano-particle of torispherical of the grain size generally within 10nm, in 2004 years
(J.Am.Chem.Soc.2004,126,12736-is surprisingly prepared when arc discharge prepares single-walled carbon nanotube by Xu
12737), and 2006 by Sun find its with high fluorescence quantum efficiency (J.Am.Chem.Soc.2006,128,7756-
7757) concern of people, is thus gradually obtained.Compared with conventional organic dyes or quantum dot, carbon dots are low to cytotoxicity, raw
Object compatibility is good, and preparation method is simple, physics, good in optical property, and in bio-imaging, photocatalysis, the fields such as biological medicine are all obtained
Great concern was obtained, pharmaceutical carrier, gene delivery vehicle or fluorescence probe diagnosis body tumor tissue etc. is such as used as to have big
Quantifier elimination.
The method of carbon dots is prepared including method (electrochemical oxidation process, arc process, laser ablation etc.) from top to bottom and under
And upper method (microwave assisting method, hydro-thermal method, strong acid oxidation etc.).But above method or operating condition are complicated harsh, need to use
To specific equipment, or strong acid and strong base, high-temperature and high-pressure conditions are needed, there is certain risk.
The carbon dots defect prepared at present is apparent, and the fluorescence quantum efficiency of carbon dots is relatively low, and transmitting light also concentrates on blue green light,
The application of carbon dots is limited to a certain degree.There is a large amount of research to find that transmitting can be made by adulterating other atom in carbon dots
Peak red shift and improve fluorescence quantum efficiency, wherein research and prepare it is most be nitrating and phosphorus carbon dots.In previous research
Mostly by mixing carbon matrix precursor and organic amine such as ethylenediamine, polyethyleneimine etc., in carbon dots surface introducing-NH2It is glimmering to improve
Optical property, however ethylenediamine is inflammable, corrosivity is strong, big to human injury, and polyethyleneimine is even more to have strong toxicity, is applied to biology
There is certain risk in vivo, needs to find in addition safer material improvement performance.
Invention content
To solve the problem of that existing carbon quantum dot prepares that cumbersome, fluorescence property is poor and nitrating agent is more toxic, the present invention
One kind is provided using amino acid as nitrating source, phosphoric acid is oxidant, and by ultrasonic pretreated feedstock, then oil bath heating is prepared
The method of nitrogen, phosphor codoping carbon dots.The preparation method is safe and simple, environmentally protective, and the fluorescence property of carbon dots is good, and carbon dots
Fluorescence can change the red shift occurred from blue light to feux rouges with amino acid classes.
Amino acid of the present invention is safe and non-toxic as a kind of biological micromolecule, derives from a wealth of sources, it is often more important that amino acid structure
There are amino and carboxyl, it is easy to polycondensation reaction occur, can be used for preparing carbon dots, nitrogen is mixed in carbon dots, and phosphoric acid oxygen is added
Change, to prepare nitrogen, phosphor codoping carbon dots.
Oil bath heating of the present invention has many advantages, such as easy to operate, is easy to control reaction condition, however at present seen in about oil
The research that bath method prepares carbon dots is seldom, and especially oil bath heating prepares carbon dots at a lower temperature, such as can successfully realize, not only
Operation is safer, can also reduce the energy consumption and cost for preparing carbon dots.
A kind of safe and simple method for preparing codope nitrogen and phosphorus carbon quantum dot, includes the following steps：
1) it in deionized water by amino acid and carbon matrix precursor dissolving, then adds in phosphoric acid solution, stirring is made into clear
Clear solution；The carbon matrix precursor is one or both of glucose, monohydrate potassium or cyclodextrin；The amino acid
It is 1 with carbon matrix precursor molar ratio:2~2:1；
2) solution is transferred in ultrasonic drilling machine and is ultrasonically treated, ultrasonic time is 1~2h；
3) by the solution after ultrasound under the conditions of 80~150 DEG C oil bath heating, reflux 1~5h, solution is by clear
Gradually become pale brown, muddy, naturally cool to room temperature, prepares while the carbon dots of codope nitrogen, phosphorus；
4) step 3) solution after cooling is centrifuged, removes large granular impurity, clear liquid is dialysed in bag filter, removed again
Fall unreacted raw material and other little particle impurity, obtains high-purity fluorescent carbon point.
To further realize the object of the invention, it is preferable that the amino acid refers to 20 needed for human body synthetic protein
Kind amino acid.The amino acid is preferably glutamic acid, aspartic acid, tryptophan, tyrosine, a kind of in serine and histidine；Structure
Type is L-type.
Preferably, the mass fraction 80-90% of the phosphoric acid solution；The volume of the phosphoric acid solution and deionized water
Than being 1:1-2.0.
Preferably, the ultrasonic frequency is 40-80kHz.
Preferably, the oil bath heating time is in 1~5h.
Preferably, the range of speeds of the centrifugation is ten thousand revs/min of 1-3.
Preferably, the molecular cut off of the bag filter is 500-1000Da.
Compared with the existing technology, the invention has the advantages that：
1) polyethyleneimine being substituted with amino acid, for the amines such as ethylenediamine as nitrating source, supplied materials is extensive, safe and non-toxic, and
Nitrogen, phosphor codoping carbon dots are prepared by the way that phosphoric acid oxidation is added, enhance the fluorescence property of carbon dots；
2) it uses ultrasonication joint oil bath heating method to substitute hydro-thermal method and microwave assisting method, avoids high temperature and pressure
Reaction condition, oil bath heating can carry out under the conditions of less than 100 DEG C, and reaction is safer, and can make quickly, on a large scale
Standby carbon dots；
3) it according to the difference in the molar ratio of amino acid classes and amino acid/carbon matrix precursor, reaction time etc., can obtain
Difference emits the carbon dots of different fluorescence, disclosure satisfy that the needs of multiple use；
4) carbon dots show the hydroxyl for having abundant, and dissolubility is good in water, and contains amino, can by chemical reaction or
Person's hydrogen bond action connects other substance, is applied to the fields such as cell detection, human body imaging.
Description of the drawings
Fig. 1 is the uv absorption spectra for tryptophan-carbon dots that embodiment 1 is prepared.
Fig. 2 is the infrared absorpting light spectra for tryptophan-carbon dots that embodiment 1 is prepared.
Fig. 3 is fluorescence spectra of the tryptophan-carbon dots prepared of embodiment 1 when 510nm is excited.
Fig. 4 is the fluorescence spectrum of the various concentration tryptophan-carbon dots in 510nm excitations of embodiment 1.
Fig. 5 is the tryptophan-carbon that in 510nm excitations prepared by different aminoacids/glucose molar ratio of embodiment 4
The fluorescence spectrum of point.
Fig. 6 is the fluorescence spectra for tryptophan-carbon dots that embodiment 5 synthesizes under the different heating time.
Fig. 7 is the fluorescence spectra for tryptophan-carbon dots that embodiment 6 synthesizes under different ultrasonic times.
Fig. 8 is the fluorescence spectra of the tryptophan-carbon dots solution in different pH of embodiment 7.
Fig. 9 is the fluorescence spectra of the solution under different folic acid, tryptophan-carbon dots ratio of embodiment 8.
Specific implementation mode
To more fully understand the present invention, with reference to the accompanying drawings and examples come further describe the present invention preparation method and
Its effect, but embodiments of the present invention are unlimited so.
Embodiment 1
The preparation of tryptophan-carbon dots：
It weighs 0.005mol tryptophans and 0.005mol glucose pours into beaker, 5ml deionized waters are added, 5ml is added
The phosphoric acid solution of mass fraction 80% stirs to being completely dissolved, forms the solution of clear；
Beaker is placed in ultrasonic drilling machine and is ultrasonically treated 2h, ultrasonic frequency 40Hz.Do not have in solution appearance after ultrasound
Variation.
It transfers the solution into 25ml round-bottomed flasks, is heated to reflux in constant-temperature heating magnetic stirring apparatus, temperature remains
It 90 DEG C, heats 5 hours, in heating process, solution colour gradually gradually reddens from clear, eventually becomes aubergine.Heating
After, it is cooled to room temperature.Carbon dots are red under sunlight, are issued in 365nm ultraviolet lights orange red by appropriate dilution
Fluorescence.
10min is centrifuged the 10000rmp under the conditions of and removes large granular impurity, in molecular cut off is again then 1000Da
It dialyses in bag filter, per a water is changed for 24 hours, dialyses two days altogether, remove unreacted raw material and short grained impurity.
Fig. 1 is the uv absorption spectra of tryptophan-carbon dots, characterizes the ultraviolet absorption characteristic of carbon dots.Carbon dots have in 510nm
Absorption peak illustrates a length of 510nm of maximum absorption wave.
Fig. 2 is the infrared absorpting light spectra of tryptophan-carbon dots, 3464cm-1It is the stretching vibration of O-H, the peak intensity at this
It is very big, illustrate the hydroxyl for having more in carbon dots, this is preferably consistent with the dissolubility of carbon dots in water.2375cm-1It is stretching for P-H
Contracting vibration, illustrates to mix phosphorus atoms in the feed, P-H groups can be introduced in carbon dots, successfully obtains phosphorus atoms being incorporated into carbon
In point, the fluorescence property of carbon dots is improved.1640cm-1It is the stretching vibration of C=N, 1156cm-1It is the stretching vibration of C-N, says
Nitrogen-atoms on bright amino acid is incorporated into carbon dots, to sum up, has successfully prepared the carbon dots of nitrogen, phosphor codoping.
Fig. 3 is the fluorescence spectra of tryptophan-carbon dots when 510nm is excited, it can be seen that the emission peak of carbon dots is in 610nm
Left and right, sends out apparent fluorescent red-orange.
The fluorescence spectra of various concentration tryptophan-carbon dots when Fig. 4 is 510nm excitations, it can be seen that with carbon dots concentration
Increase, fluorescence intensity declines, and red shift occurs for emission peak.
Its pattern and grain size are characterized with transmission electron microscope, can prove carbon quantum dot be grain size 10nm with
The carbon nano-particle of interior torispherical.
Embodiment 2
The preparation of glutamic acid-carbon dots：
It weighs 0.0005mol glutamic acid and 0.005mol glucose pours into beaker, 5ml deionized waters are added, then pour into
The phosphoric acid solution of 5ml mass fractions 85% stirs to being completely dissolved, forms the solution of clear；
Beaker is placed in ultrasonic drilling machine and is ultrasonically treated 2h, ultrasonic frequency 50kHz.
It transfers the solution into 25ml round-bottomed flasks, is heated to reflux in constant-temperature heating magnetic stirring apparatus, temperature remains
It 150 DEG C, heats 1 hour, in heating process, solution colour gradually gradually becomes brown from clear.It is cooling after heating
To room temperature.The high concentration carbon dots of acquisition are light yellow under sunlight, turn to be yellow under 365nm ultraviolet lights after dilution
Light.
Under the conditions of 20000rmp centrifuge 10min remove large granular impurity, then again molecular cut off be 500Da it is saturating
It dialyses in analysis bag, per a water is changed for 24 hours, dialyses 4 days altogether, to remove unreacted raw material and short grained impurity.
Embodiment 3
The preparation of aspartic acid-carbon dots：
It weighs 0.005mol aspartic acids and 0.005mol monohydrate potassiums pours into beaker, 5ml deionized waters are added,
The phosphoric acid solution of 5ml mass fractions 90% is added, stirs to being completely dissolved, forms the solution of clear；
Beaker is placed in ultrasonic drilling machine and is ultrasonically treated 2h, ultrasonic frequency 60kHz.Do not have in solution appearance after ultrasound
Variation.
It transfers the solution into 25ml round-bottomed flasks, is heated to reflux in constant-temperature heating magnetic stirring apparatus, temperature remains
It 120 DEG C, heats 2 hours, in heating process, solution colour gradually gradually reddens from clear, eventually becomes dark brown.Heating
After, it is cooled to room temperature.Carbon dots are brown under sunlight, turn blue under 365nm ultraviolet lights by appropriate dilution
Light.
Under the conditions of 30000rmp centrifuge 10min remove large granular impurity, then again molecular cut off be 800Da it is saturating
It dialyses in analysis bag, per a water is changed for 24 hours, dialyses two days altogether, remove unreacted raw material and short grained impurity.
Embodiment 4
The preparation of tryptophan-carbon dots of different aminoacids/glucose molar ratio：
Under the conditions of glucose and tryptophan total concentration are 1mol/L, it is 2 to weigh glucose and amino acid molar ratio:1,3:
2,1:1,2:3,2:1 raw material is respectively placed in 5 beakers, and the phosphoric acid that 5ml deionized waters and 5ml mass fractions 85% is added is molten
Liquid stirs to being completely dissolved, forms the solution of clear；
Beaker is placed in ultrasonic drilling machine respectively and is ultrasonically treated 2h, ultrasonic frequency 40kHz.After ultrasound in solution appearance
Do not change.
It transfers the solution into 25ml round-bottomed flasks, is heated to reflux in constant-temperature heating magnetic stirring apparatus respectively, temperature is protected
It is 100 DEG C to hold, and is heated 2 hours, in heating process, solution colour gradually gradually reddens from clear, eventually becomes aubergine.
After heating, it is cooled to room temperature.Carbon dots are red under sunlight, are issued in 365nm ultraviolet lights by appropriate dilution
Orange red fluorescence.
10min is centrifuged the 10000rmp under the conditions of and removes large granular impurity, in molecular cut off is again then 1000Da
It dialyses in bag filter, per a water is changed for 24 hours, dialyses two days altogether, remove unreacted raw material and short grained impurity.
The fluorescence spectra for tryptophan-carbon dots that when Fig. 5 is 510nm excitations prepared by different aminoacids/glucose molar ratio,
It can be seen that increasing with glucose content, red shift occurs for emission peak, but fluorescence intensity reduction decreases.
Embodiment 5
The preparation of different heating time tryptophan-carbon dots
It weighs 0.005mol tryptophans and 0.005mol glucose pours into beaker, 5ml deionized waters are added, 5ml is added
The phosphoric acid solution of mass fraction 85% stirs to being completely dissolved, forms the solution of clear；
Beaker is placed in ultrasonic drilling machine and is ultrasonically treated 2h, ultrasonic frequency 40kHz.Do not have in solution appearance after ultrasound
Variation.
It transfers the solution into 25ml round-bottomed flasks, is heated to reflux in constant-temperature heating magnetic stirring apparatus, temperature remains
It 90 DEG C, heats 1-5 hours, in heating process, solution colour gradually gradually reddens from clear, eventually becomes aubergine.Add
After heat, it is cooled to room temperature.Carbon dots are brown, the carbon dots under 365nm ultraviolet lights under sunlight by appropriate dilution
Increase with heating time, shines by being blue shifted to green light again after green light red shift to orange light.
10min is centrifuged the 10000rmp under the conditions of and removes large granular impurity, in molecular cut off is again then 1000Da
It dialyses in bag filter, per a water is changed for 24 hours, dialyses two days altogether, remove unreacted raw material and short grained impurity.
Fig. 6 is the fluorescence spectra of the carbon dots synthesized under the different heating time.It can be seen that with the increase of heating time,
Fluorescent emission peak intensity first increases and then decreases, heating time are that 3h carbon dots fluorescence intensities reach maximum value.
Embodiment 6
The preparation of different ultrasonic time tryptophan-carbon dots：
It weighs 0.005mol tryptophans and 0.005mol glucose pours into beaker, 5ml deionized waters are added, 5ml is added
The phosphoric acid solution of mass fraction 85% stirs to being completely dissolved, forms the solution of clear；
Beaker is placed in supersound process 40~140min, ultrasonic frequency 40kHz in ultrasonic drilling machine.After ultrasound outside solution
Do not change in sight.
It transfers the solution into 25ml round-bottomed flasks, is heated to reflux in constant-temperature heating magnetic stirring apparatus, temperature remains
It 90 DEG C, heats 2 hours, in heating process, solution colour gradually gradually reddens from clear, eventually becomes aubergine.Heating
After, it is cooled to room temperature.Carbon dots are brown under sunlight by appropriate dilution, under 365nm ultraviolet lights carbon dots with
Heating time increases, and shines by being blue shifted to green light again after green light red shift to orange light.
10min is centrifuged the 10000rmp under the conditions of and removes large granular impurity, in molecular cut off is again then 1000Da
It dialyses in bag filter, per a water is changed for 24 hours, dialyses two days altogether, remove unreacted raw material and short grained impurity.
Fig. 7 is the fluorescence spectra of the carbon dots synthesized under the different heating time.It can be seen that with the increase of ultrasonic time,
The excitation wavelength and fluorescence intensity of carbon dots solution are substantially in the trend of reduction after first increasing, when ultrasonic time is 120min,
Fluorescence intensity is maximum.
Embodiment 7
The preparation of different pH tryptophans-carbon dots solutions：
It weighs the tryptophan-carbon dots 0.3g prepared in embodiment 1 and enters beaker, weigh 4 parts, marked as 1,2,3,4, add respectively
Enter the NaOH solution of 30mL pH=12, the HCl solution of deionized water, the HCl solution of pH=4, pH=2, stirring and dissolving.
Fig. 8 is the fluorescence spectra of different pH tryptophans-carbon dots solutions.It can be seen that carbon dots solution is glimmering under alkaline condition
Luminous intensity is minimum, and fluorescence intensity is maximum when pH=4, illustrates that carbon dots solution fluorescence under weak basic condition is most strong.
Embodiment 8
The preparation of folic acid-tryptophan-carbon dots：
It weighs the tryptophan-carbon dots 0.3g prepared in embodiment 1 and enters beaker, weigh 3 parts, marked as 1,2,3, be separately added into
30ml deionized waters.0.05g folic acid is added into No. 2 solution, stirs evenly, 0.1g folic acid is added in No. 3 solution and stirs evenly.
Fig. 9 is the fluorescence spectra of different folic acid, solution under carbon dots ratio.It can be seen that the fluorescence of solution is with folic acid
Concentration increases and gradually weakens, when folic acid and tryptophan-carbon dots ratio rise to 1：When 1, fluorescent quenching occurs.Illustrate this technology
Tryptophan-carbon dots obtained can connect folic acid by chemical reaction or hydrogen bond action, be allowed to that fluorescent quenching occurs, therefore can
Applied to fields such as cell detection, human body imagings.
For above-described embodiment as it can be seen that carbon dots of the present invention show the hydroxyl for having abundant, dissolubility is good in water, and contains ammonia
Base can connect other substances such as folic acid by chemical reaction or hydrogen bond action, be applied to cell detection, human body imaging etc.
Field.Compared with general carbon dots, carbon dots of the present invention have the case where increase with concentration, emission peak red shift, therefore adjustable carbon
Point concentration obtains shining as that by blue to red solution, can apply and polychrome imaging field.
Prior art preparation carbon dots need mostly strong acid and strong base, high temperature and pressure condition, have certain risk.The present invention
Carbon dots, easy to operate, safety, energy consumption can be prepared by pre-processing then progress oil bath heating at low temperature to raw material ultrasound
It is low, and can quickly prepare a large amount of carbon dots.For the present invention using glucose as presoma, amino acid is nitrogen source, and phosphoric acid is oxidant,
Water is solvent, and raw material sources are extensive, and safe and non-toxic, and nitrating, phosphorus, the fluorescence property of carbon dots are good simultaneously for the carbon dots prepared.
The present invention, can be with according to the difference in the molar ratio of amino acid classes and amino acid/carbon matrix precursor, reaction time etc.
The different carbon dots for emitting different fluorescence are obtained, disclosure satisfy that the needs of multiple use.
The present invention is not constrained by above-described embodiment, and others are any to be made without departing from the spirit and principles of the present invention
Changes, modifications, substitutions, combinations, simplifications, should be equivalent alternative, be included within the scope of the present invention.
Claims (8)
1. a kind of safe and simple method for preparing codope nitrogen and phosphorus carbon quantum dot, it is characterised in that include the following steps：
1) it in deionized water by amino acid and carbon matrix precursor dissolving, then adds in phosphoric acid solution, it is molten that stirring is made into clarification
Liquid；The carbon matrix precursor is one or both of glucose, monohydrate potassium or cyclodextrin；The amino acid and carbon
Presoma molar ratio is 1:2~2:1；
2) solution is transferred in ultrasonic drilling machine and is ultrasonically treated, ultrasonic time is 1~2h；
3) by the solution after ultrasound, oil bath heating, 1~5h of reflux, solution are gradual by clear under the conditions of 80~150 DEG C
Become pale brown, muddy, naturally cool to room temperature, prepares while the carbon dots of codope nitrogen, phosphorus；
4) step 3) solution after cooling is centrifuged, removes large granular impurity, clear liquid is dialysed in bag filter, removed not again
The raw material of reaction and other little particle impurity, obtain high-purity fluorescent carbon point.
2. the safe and simple method for preparing codope nitrogen and phosphorus carbon quantum dot according to claim 1, which is characterized in that described
Amino acid refer to 20 kinds of amino acid needed for human body synthetic protein.
3. the safe and simple method for preparing codope nitrogen and phosphorus carbon quantum dot according to claim 1, which is characterized in that described
Phosphoric acid solution mass fraction 80-90%；The volume ratio of the phosphoric acid solution and deionized water is 1:1‐2.0.
4. the safe and simple method for preparing codope nitrogen and phosphorus carbon quantum dot according to claim 1, which is characterized in that described
Ultrasonic frequency be 40-80kHz.
5. the safe and simple method for preparing codope nitrogen and phosphorus carbon quantum dot according to claim 1, which is characterized in that described
The oil bath heating time in 1~5h.
6. the safe and simple method for preparing codope nitrogen and phosphorus carbon quantum dot according to claim 1, which is characterized in that described
The range of speeds of centrifugation be ten thousand revs/min of 1-3.
7. the safe and simple method for preparing codope nitrogen and phosphorus carbon quantum dot according to claim 1, which is characterized in that described
Bag filter molecular cut off be 500-1000Da.
8. the safe and simple method for preparing codope nitrogen and phosphorus carbon quantum dot according to claim 1, which is characterized in that described
Dialysis time be 2-4 days, change a water within every 24 hours.
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| CN112552906A (en) * | 2020-12-29 | 2021-03-26 | 兰州大学 | Preparation method of nitrogen-doped carbon quantum dots in coffee grounds and method for detecting VB12 through fluorescence |
| CN113185972A (en) * | 2021-03-25 | 2021-07-30 | 清华大学 | Multi-mode luminescent carbon dot and preparation method and application thereof |
| CN113502159A (en) * | 2021-08-17 | 2021-10-15 | 岭南师范学院 | Preparation method of pH activated carbon quantum dot emitting fluorescence in near-infrared region I, product and application thereof |
| CN113736456A (en) * | 2021-09-10 | 2021-12-03 | 四川大学 | Tumor targeting nanoprobe based on folic acid coupled carbon quantum dots and preparation method thereof |
| CN114748364A (en) * | 2022-04-07 | 2022-07-15 | 华南师范大学 | Tooth bleaching method utilizing afterglow light dynamic effect, tooth bleaching carbon point reagent and preparation method thereof |
| CN115287065A (en) * | 2022-08-09 | 2022-11-04 | 山西大学 | Preparation method and application of nitrogen-phosphorus co-doped carbon dots |
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| CN109336087A (en) * | 2018-12-26 | 2019-02-15 | 南京林业大学 | Cork oak acorn-cup base carbon quantum dot and its application on fluorescent ink are prepared using cork oak acorn-cup |
| CN112552906A (en) * | 2020-12-29 | 2021-03-26 | 兰州大学 | Preparation method of nitrogen-doped carbon quantum dots in coffee grounds and method for detecting VB12 through fluorescence |
| CN113185972A (en) * | 2021-03-25 | 2021-07-30 | 清华大学 | Multi-mode luminescent carbon dot and preparation method and application thereof |
| CN113502159A (en) * | 2021-08-17 | 2021-10-15 | 岭南师范学院 | Preparation method of pH activated carbon quantum dot emitting fluorescence in near-infrared region I, product and application thereof |
| CN113736456A (en) * | 2021-09-10 | 2021-12-03 | 四川大学 | Tumor targeting nanoprobe based on folic acid coupled carbon quantum dots and preparation method thereof |
| CN114748364A (en) * | 2022-04-07 | 2022-07-15 | 华南师范大学 | Tooth bleaching method utilizing afterglow light dynamic effect, tooth bleaching carbon point reagent and preparation method thereof |
| CN114748364B (en) * | 2022-04-07 | 2023-06-23 | 华南师范大学 | Tooth bleaching method and tooth bleaching carbon spot reagent utilizing afterglow photodynamic effect and preparation method thereof |
| CN115287065A (en) * | 2022-08-09 | 2022-11-04 | 山西大学 | Preparation method and application of nitrogen-phosphorus co-doped carbon dots |
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