CN109971460A - A kind of preparation method of Ratiometric fluorescent probe and its application in detection water in terms of copper ion - Google Patents
A kind of preparation method of Ratiometric fluorescent probe and its application in detection water in terms of copper ion Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of Ratiometric fluorescent probe and utilize the method for copper ion concentration in Ratiometric fluorescent probe detection water.Method using copper ion concentration in Ratiometric fluorescent probe detection water includes: that (1) prepares Ratiometric fluorescent probe;(2) certain density copper ion standard solution is configured;(3) copper ion solution is added into fluorescence probe solution, makes probe gradually fluorescent quenching;(4) middle probe/copper ion reaction front and back fluorescence intensity is measured, standard curve is established according to the relationship between copper ion concentration and relative intensity of fluorescence changing value;(5) quantitative detection: the fluorescence intensity change of measurement sample to be tested and probe solution reaction front and back calculates relative intensity of fluorescence changing value, and the standard curve obtained in comparison step (4) obtains the content of copper ion in sample to be tested.The probe has outstanding specificity when detecting, and stability is good, it is simple to prepare, and the reaction time is short, and detection range is wider, and detection limit is lower.
Description
Technical field
The present invention relates to fluorescence probe preparation fields, more particularly to a kind of fluorescence probe preparation method and its are detecting
Application in water in terms of copper ion.
Background technique
One of the valuable source that water resource is depended on for existence and development as the mankind, water quality directly affects society and economy
Sustainable and stable development.In recent years, the pollution problem of water resource is more and more severeer, wherein using copper ion as the heavy metal pollution of representative
It is particularly problematic, therefore the extensive concern of scholar is caused to the research of copper ion detection method in water.
Fluorescence probe is since its analytical sensitivity is high, easy to operate, amount of samples is few, testing cost is low, quick, convenient etc.
Advantage becomes the important tool of detection copper ion.Therefore, the fluorescence probe based on artificial synthesized organic dyestuff has been designed
And it is used for Cu2+Detection, but there is the problems such as synthesis is excessively complicated with modification, and fluorescence intensity is low in such probe.
Summary of the invention
In view of the deficienciess of the prior art, it is an object of the present invention to provide a kind of preparations of Ratiometric fluorescent probe
Method.
It is a further object of the present invention to provide a kind of with above-mentioned Ratiometric fluorescent probe quickly, conveniently, intuitively detect water
The method of middle copper ion concentration.
In the present invention, using Ratiometric fluorescent probe detection water in copper ion concentration method the following steps are included:
(1) Ratiometric fluorescent probe is prepared;
(2) certain density copper ion standard solution is configured;
(3) copper ion solution is added into fluorescence probe solution, makes probe gradually fluorescent quenching;
(4) middle probe/copper ion reaction front and back fluorescence intensity is measured, is become according to copper ion concentration and relative intensity of fluorescence
Relationship between change value establishes standard curve;
(5) quantitative detection: the fluorescence intensity change of measurement sample to be tested and probe solution reaction front and back calculates relative fluorescence
Strength Changes value, the middle standard curve obtained of comparison step (4), obtains the content of copper ion in sample to be tested.
In the above method, the preparation method of Ratiometric fluorescent probe the following steps are included:
S1 prepares blue quantum dot dispersion liquid
Citric acid is dissolved in 10ml N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, by solution after stirring
It is transferred in polytetrafluoroethyllining lining reaction kettle, 2h is reacted at 240 DEG C, later by reaction kettle cooled to room temperature.To remove
Impurity and small molecule in reaction solution, first by the solution through organic membrane filter, then with petroleum ether extraction 3-5 times, later by it
It is scattered in dehydrated alcohol and obtains blue quantum dot dispersion liquid, and it is spare to be stored in 4 DEG C of refrigerators.
The preparation method of the blue quantum dot, it is characterised in that the N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxy
The amount of the substance of base silane and citric acid is respectively 45~50mmol and 9~11mmol;The organic film is that aperture is 0.22
Organic film.
S2, the nano SiO 2 particle dispersion liquid of the blue quantum dot of cladding of preparation amination modification
Triton x-100, n-hexyl alcohol and ultrapure water are added sequentially into hexamethylene, are vigorously stirred after being uniformly mixed
8~12min minutes, form microemulsion system;Then to blue quantum dot, ethyl orthosilicate and ammonium hydroxide are added in above-mentioned mixed liquor,
It is reacted for 24 hours at 20~30 DEG C;After reaction to the reaction system be added isopropanol, centrifugation, precipitating successively with dehydrated alcohol, go
Milli-Q water 1~2 time, obtain the nano SiO 2 particle for embedding blue quantum dot;The silica of blue quantum dot will be embedded
Nano particle is dispersed in dehydrated alcohol, rapidly joins 3- aminopropyl triethoxysilane to the reaction solution, use is snakelike
Condenser pipe oil bath heating to 90 DEG C flow back;After the reaction was completed, make its cooled to room temperature, be centrifugated the product, later will
It is scattered in the nano SiO 2 particle dispersion liquid that the blue quantum dot of cladding of amination modification is obtained in ultrapure water.
The indigo plant quantum dot is embedded in the preparation method of silicon dioxide nanosphere, it is characterised in that the Qula leads to X-
100 mass dosages are calculated as 70~80mg/1 μ l with blue quantum dot volume;The n-hexyl alcohol volumetric usage is in terms of blue quantum dot volume
For 80~100 μ l/1 μ l;The hexamethylene volumetric usage is calculated as 350~400 μ l/1 μ l with blue quantum dot volume;
The n-hexyl alcohol volumetric usage is calculated as 80~100 μ l/1 μ l with blue quantum dot volume;It is described that ultrapure water volume is gone to use
Amount is calculated as 18~20 μ l/1 μ l with blue quantum dot volume;The ethyl orthosilicate volumetric usage is calculated as 2~3 with blue quantum dot volume
μl/1μl;The ammonium hydroxide quality dosage is calculated as 10 μ l/1 μ l with blue quantum dot volume;The isopropanol volumetric usage is with reactant
It is that volume is calculated as 3~4ml/1ml.
The preparation method of the nano SiO 2 particle dispersion liquid of the blue quantum dot of cladding of the amination modification, feature
It is that the dehydrated alcohol quality dosage is calculated as 8~12ml/1mg with the nano SiO 2 particle quality for coating blue quantum dot;
The 3- aminopropyl triethoxysilane volumetric usage is calculated as 50 with the nano SiO 2 particle quality for being wrapped by blue quantum dot
~75 μ l/1mg.
S3, the preparation of Ratiometric fluorescent probe solution
It weighs 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and n-hydroxysuccinimide dissolves respectively
It in ultrapure water, is mixed later with the aqueous solution of red quantum dot, 27~33min of reaction stirring under dark condition;Then to above-mentioned
The nano SiO 2 particle dispersion liquid of the blue quantum dot of cladding of amination modification is added in reaction solution, and reacts at room temperature
12h;After reaction, it is centrifugated the product, and is scattered in ultrapure water and obtains Ratiometric fluorescent probe solution, and
It is spare to be stored in 4 DEG C of refrigerators.
The preparation method of Ratiometric fluorescent probe as described in claim 1, it is characterised in that 1- (the 3- dimethylamino
Propyl) -3- ethyl-carbodiimide hydrochloride quality dosage with red quantum dot volume is calculated as 80mg/1ml;N-hydroxysuccinimide
Quality dosage is calculated as 190mg/1ml with red quantum dot volume;Red quantum dot volumetric usage is embedded in silica with blue quantum dot
1ml/1ml is calculated as in nanosphere and in the dispersion liquid volume that silicon dioxide microsphere surface carries out amination modification.
The present invention provides a kind of application of double emission ratios type fluorescence probes in detection copper ion.Specific method
Are as follows: it takes multiple groups Ratiometric fluorescent probe solution in quartz colorimetric utensil respectively, is separately added into the different copper chloride of 10 μ L concentration, room
The lower standing 15min of temperature reacts it completely.Using 380nm as excitation wavelength, 400-750nm is scanning range, equal in slit width
For under conditions of 2.5nm in determination step 3 each sample fluorescence emission spectrum, with the fluorescence intensity ratio of Ratiometric fluorescent probe
(F0/FA) with copper ion ion concentration be coordinate draw standard curve, wherein F0And FARespectively Ratiometric fluorescent probe exists
Fluorescence intensity at 462nm and 643nm.Before measuring 50 μ L samples to be tested and Ratiometric fluorescent probe reaction using Fluorescence Spectrometer
Fluorescence intensity change afterwards, the fluorescence intensity ratio of calculating ratio type fluorescence probe, the standard curve obtained with step 4 are compared, are obtained
The content of copper ion ion into sample to be tested.
In order to further probe into Ratiometric fluorescent probe of the present invention in the detection to Cu2+Selectivity, we take more
The dispersion liquid of group probe, has been separately added into a series of metal ion, including K+,Fe3+,Na+,Mg2+,Ca2+,Zn2+,Cu2+,Ni2 +,Cr3+,Pb2+,Al3+,Ba2+, and fluorescence detection is carried out, and in contrast, only Cu2+It will cause being quenched for fluorescence.Therefore, we
The Ratiometric fluorescent probe of synthesis can selectively detect Cu well2+。
Compared with the prior art, the advantages of the present invention are as follows:
Compared to other Ratiometric fluorescent probes, this probe when detecting, has quite outstanding specificity, stability
Good, preparation it is simple this, it is cheap, and the reaction time is substantially reduced, to the detection of copper ion down to 0.83 μM.By right
Than it can be found that this probe is more wider than the detection range of single blue quantum dot fluorescence probe, detection limit is lower, to rapid visual
Change detection to provide convenience.
Detailed description of the invention
Fig. 1 is the flow chart of preparation method of the invention;
Fig. 2 is the TEM of the nano SiO 2 particle of the blue quantum dot of cladding of amination modification in the embodiment of the present invention 1
Figure;
Fig. 3 is the TEM figure of the Ratiometric fluorescent probe in the embodiment of the present invention 1;
Fig. 4 is the blue quantum dot prepared in the embodiment of the present invention 1, the titanium dioxide of the blue quantum dot of the cladding of amination modification
Nano silicon particles, the fluorescence spectra of Ratiometric fluorescent probe;
Fig. 5 is Ratiometric fluorescent probe made from case study on implementation 1 of the invention under the copper ion concentration of various concentration
Fluorescence emission spectrum and relative intensity of fluorescence ratio F0/FAWith the relationship of copper ion concentration;
Fig. 6 is corresponding fluorescence photo under the ultraviolet light irradiation of 365nm in the embodiment of the present invention 2, from left to right copper ion
Concentration be followed successively by 0,0.5,1,1.5,2,4,6,8,10 μM;
Fig. 7 is that fluorescence of Ratiometric fluorescent probe in the case where different ions made from case study on implementation 1 of the invention is strong
Degree.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
Embodiment 1: the preparation of Ratiometric fluorescent probe
Referring to Fig. 1, a kind of preparation method of Ratiometric fluorescent probe, comprising the following steps:
1, the preparation of blue quantum dot
It weighs 0.5g citric acid and is dissolved in 10ml N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane (AEAPMS)
In, solution is transferred in 50mL polytetrafluoroethyllining lining reaction kettle after stirring, 2h is reacted at 240 DEG C, certainly by reaction kettle later
So it is cooled to room temperature.To remove the impurity and small molecule in reaction solution, first by the solution through 0.22 μm of organic membrane filter, then
With petroleum ether extraction 3-5 times.Reaction product is dissolved in dehydrated alcohol and is stored in spare in 4 DEG C of refrigerators.
2, the preparation of the nano SiO 2 particle of blue quantum dot is embedded
7.7ml hexamethylene, 1.42g triton x-100 and 1.8ml n-hexyl alcohol are sequentially added in 100ml round-bottomed flask,
380 μ l are added thereto after being uniformly mixed and remove ultrapure water, which is vigorously stirred 10min and forms stable reverse micro emulsion
System.50 μ l ethyl orthosilicates, 20 μ l brand-new indigo plant quantum dots and 200 μ l ammonium hydroxide, room are sequentially added into flask after reaction
The lower reaction of temperature is for 24 hours.It is demulsified after reaction to the isopropanol that 36ml is added in the reaction system, obtains flocky precipitate.It will
Reactant centrifugation alcohol is washed repeatedly, until the centrifuged supernatant unstressed configuration signal of last time.The product is lyophilized, is used for
Subsequent reactions.Its TEM figure is as shown in Figure 1.As shown in Figure 2, nano particle particle spherical in shape, particle size is between 30-40nm
Between.
3, the preparation of Ratiometric fluorescent probe
It embeds the amination modification of the nano SiO 2 particle of blue quantum dot: 4mg being taken to embed the titanium dioxide of blue quantum dot
Nano silicon particles are dispersed in 40mL dehydrated alcohol, and 250 μ L 3- aminopropyl-triethoxy silicon are added dropwise rapidly to the reaction solution
Alkane, magnetic agitation are heated to 90 DEG C, and reaction is for 24 hours.The top connection of serpentine condenser is equipped with the drying of U-Ramin MC desiccant
Pipe prevents the vapor in air from entering the reaction system.After reaction, cooled to room temperature, with 12000r/min's
Revolving speed is centrifugated the product, is scattered in 4ml and goes to be used for subsequent experimental in ultrapure water.
The building of Ratiometric fluorescent probe: 80mg 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride is weighed
It is dissolved in 1ml respectively with 190mg n-hydroxysuccinimide to go in ultrapure water, is mixed later with 1ml cadmium telluride quantum dot solution,
30min is stirred under dark condition.Then to the nano SiO 2 particle that the blue quantum dot of 1ml embedding is added in above-mentioned reaction solution
Dispersion liquid reacts 12h at room temperature.After the reaction was completed, be centrifugated the product, and be scattered in 8ml go it is spare in ultrapure water.
The fluorescence spectra of its TEM figure and above-mentioned three are as shown in Figure 4.
Fig. 3 is the TEM image of Ratiometric fluorescent probe, it can be seen from this figure that its particle diameter distribution is in 35-45nm, dioxy
The surface of SiClx nano particle is able to observe that red quantum dot, illustrates that red quantum dot has been already connected to the surface of silica.With
And Fig. 4 is that Ratiometric fluorescent probe has fluorescent absorption at 462nm and 643nm under the excitation wavelength of 380nm, is respectively represented
It is the fluorescence peak of blue quantum dot and red quantum dot.
Embodiment 2: the detection of copper ions in sample concentration
It takes multiple groups Ratiometric fluorescent probe solution in quartz colorimetric utensil, is separately added into the different Cu of 10 μ L concentration2+, room temperature
Lower standing 10min reacts it completely.Using 380nm as excitation wavelength, 400-750nm is scanning range, is in slit width
Its fluorescence emission spectrum is measured under conditions of 2.5nm.Its fluorescence spectrum is as shown in Figure 5.As seen from Figure 4, with addition
Copper ion constantly increases, and fluorescence intensity of the Ratiometric fluorescent probe at 643nm constantly reduces, and the fluorescence intensity at 462nm
It is held essentially constant.Further investigate the range of linearity and detection limit when the Ratiometric fluorescent probe is measured copper ion.
Ratio (the F of Ratiometric fluorescent probe fluorescence intensityA/F0) and Cu2+Concentration showed between 0.82-25 μM it is good linear
Relationship (R2=0.992), detection is limited to 0.053 μM.
It takes one group of Ratiometric fluorescent probe solution in quartz colorimetric utensil, the Cu of unknown concentration is added2+, stand at room temperature
10min reacts it completely.Using 380nm as excitation wavelength, 400-750nm is scanning range, is 2.5nm's in slit width
Under the conditions of measure its fluorescence emission spectrum.Cu is calculated according to linear relationship2+Concentration is 1.84, the result and ICP testing result
It is identical.
Embodiment 3: actual water sample detection
Actual water sample used is collected in a plurality of river respectively in the experiment (labeled as 1,2,3,4,5,6,7,8,9).First
Collected water sample is removed into the insoluble granule in solution by 0.22 μm of water film filtering, then takes multiple groups Ratio-type fluorescence
Probe solution is separately added into the sample of 10 μ L difference groups in adaptation cuvette, and standing 10min at room temperature reacts it completely.
Using 380nm as excitation wavelength, 400-750nm is scanning range, its fluorescence hair is measured under conditions of slit width is 2.5nm
Penetrate spectrum.Its fluorescence photo is as shown in Figure 6.
Embodiment 4: the selectivity of ratio fluorescent probe
In order to prove that Ratiometric fluorescent probe has specificity for copper ion recognition detection, choose some relatively common
Metal ion carries out interference measurement.The 10mM that same volume is added into the aqueous solution of multiple groups Ratiometric fluorescent probe respectively is dry
Disturb substance: K+,Na+, Ba2, Ca2+, Mg2+, Al3+, Zn2+, Ni2+, Mn2+Deng, with Cu2+Fluorescence is carried out under identical testing conditions
Measurement.Experimental result is it can be proved that the other interfering substances removed except Cu2+ will not all cause Ratiometric fluorescent probe fluorescence
The variation of intensity ratio, illustrates that Ratiometric fluorescent probe can be realized to Cu2+Selective recognition.Its fluorescence intensity is as shown in Figure 7.
Claims (4)
1. a kind of preparation method of Ratiometric fluorescent probe, it is characterized in that steps are as follows:
S1 prepares blue quantum dot dispersion liquid:
Citric acid is dissolved in N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, solution is transferred to reaction after stirring
In kettle, 1.5-2.5h is reacted at 230 DEG C -250 DEG C, and later by reaction kettle cooled to room temperature, the solution after reaction is filtered,
It uses petroleum ether extraction 3-5 times again, later disperses obtained solution in dehydrated alcohol, obtain blue quantum dot dispersion liquid, and store up
There are 4 DEG C of refrigerators are spare,
Wherein, the amount of the citric acid and N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane substance be respectively 45~
50mmol and 9~11mmol;The organic film is the organic film that aperture is 0.22.
S2, the nano SiO 2 particle dispersion liquid of the blue quantum dot of cladding of preparation amination modification:
Triton x-100, n-hexyl alcohol and ultrapure water are added sequentially into hexamethylene, 8 are vigorously stirred after being uniformly mixed~
12min minutes, form microemulsion system;Then to blue quantum dot, ethyl orthosilicate and ammonium hydroxide are added in above-mentioned microemulsion system,
20-30h is reacted at 20~30 DEG C;Isopropanol is added to the reaction system after reaction, centrifugation precipitates successively with anhydrous second
Alcohol, milli-Q water 1~2 time obtain the nano SiO 2 particle for embedding blue quantum dot;
The nano SiO 2 particle for embedding blue quantum dot is dispersed in dehydrated alcohol, rapidly joins 3- to the reaction solution
Aminopropyl triethoxysilane uses serpentine condenser oil bath heating to 88-92 DEG C of reflux;After the reaction was completed, keep it naturally cold
But to room temperature, it is centrifugated the product, is scattered in ultrapure water later, obtain the blue quantum dot of cladding of amination modification
Nano SiO 2 particle dispersion liquid,
Wherein, the triton x-100 quality dosage is calculated as 70~80mg/1 μ l with blue quantum dot volume;The n-hexyl alcohol volume
Dosage is calculated as 80~100 μ l/1 μ l with blue quantum dot volume;The hexamethylene volumetric usage is calculated as 350 with blue quantum dot volume~
400μl/1μl;The ultrapure water volumetric usage is calculated as 18~20 μ l/1 μ l with blue quantum dot volume;The ethyl orthosilicate volume
Dosage is calculated as 2~3 μ l/1 μ l with blue quantum dot volume;The ammonium hydroxide quality dosage is calculated as 10 μ l/1 μ l with blue quantum dot volume;
The isopropanol volumetric usage is calculated as 3~4ml/1ml with reaction system volume;
The dehydrated alcohol quality dosage is calculated as 8~12ml/1mg with the nano SiO 2 particle quality for coating blue quantum dot;
The 3- aminopropyl triethoxysilane volumetric usage is calculated as 50 with the nano SiO 2 particle quality for being wrapped by blue quantum dot
~75 μ l/1mg,
S3, the preparation of Ratiometric fluorescent probe solution:
Weigh 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and n-hydroxysuccinimide be dissolved separately in it is super
It in pure water, is mixed later with red quantum dot solution, 27~33min of reaction stirring under dark condition;Then in above-mentioned reaction solution
The nano SiO 2 particle dispersion liquid of the blue quantum dot of cladding of amination modification is added, and reacts 11-13h at room temperature;Instead
After answering, it is centrifugated the product, and be scattered in ultrapure water and obtain Ratiometric fluorescent probe,
Wherein, 1- (3- the dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride quality dosage is with red quantum dot solution body
Product is calculated as 80mg/1ml;N-hydroxysuccinimide quality dosage is calculated as 190mg/1ml with red quantum dot volume;Red quantum dot is molten
Liquid volumetric usage is embedded in silicon dioxide nanosphere with blue quantum dot and carries out amination on silicon dioxide microsphere surface and repaired
The dispersion liquid volume of decorations is calculated as 1ml/1ml.
S4, Ratiometric fluorescent probe detect copper ion
Standard solution containing various concentration copper ion is entered into the resulting Ratiometric fluorescent probe solution of step S2, utilization is glimmering
Photothermal spectroscopic analyzer measures fluorescence emission spectrum, records the fluorescence photo of Ratiometric fluorescent probe solution under different content of copper ion, together
When according to the colors and copper ion concentration of double transmitting fluorescence probes establish standard curve, contrast standard curve obtains in solution to be measured
The concentration of copper ion.
2. the preparation method of Ratiometric fluorescent probe according to claim 1, it is characterised in that: the red quantum dot is tellurium
Cadmium quantum dot, the indigo plant quantum dot is carbon quantum dot.
3. the application of Ratiometric fluorescent probe prepared by the method for any one of claim 1-2 a kind of in detection copper ion,
Characterized by the following steps:
1) it goes the Ratiometric fluorescent probe of multiple groups same volume to be respectively placed in quartz colorimetric utensil, it is different to be separately added into 10 μ L concentration
Copper chloride solution, at room temperature stand 15min react it completely;
2) using 380nm as excitation wavelength, 400-750nm is scanning range, and step is measured under conditions of slit width is 2.5nm
It is rapid 1) in each sample fluorescence emission spectrum, with the fluorescence intensity ratio (F of Ratiometric fluorescent probe0/FA) and copper ion ion concentration
Standard curve is drawn for coordinate, wherein F0And FARespectively fluorescence intensity of the Ratiometric fluorescent probe at 462nm and 643nm.
3) fluorescence intensity change of 50 μ L samples to be tested and Ratiometric fluorescent probe reaction front and back, meter are measured using Fluorescence Spectrometer
The fluorescence intensity ratio for calculating Ratiometric fluorescent probe, the standard curve obtained with step 2) compare, and obtain copper ion in sample to be tested
The content of ion.
4. application according to claim 3, it is characterised in that: the step 1), 3) in, the volume of Ratiometric fluorescent probe
For 0.5~1ml.
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CN111795958A (en) * | 2020-07-14 | 2020-10-20 | 南宁师范大学 | Specific detection of Ag+Preparation of CdSe quantum dot, detection method and application thereof |
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CN111795958A (en) * | 2020-07-14 | 2020-10-20 | 南宁师范大学 | Specific detection of Ag+Preparation of CdSe quantum dot, detection method and application thereof |
CN111795958B (en) * | 2020-07-14 | 2022-09-09 | 南宁师范大学 | Specific detection of Ag + Preparation of CdSe quantum dot, detection method and application thereof |
CN112362629A (en) * | 2020-11-19 | 2021-02-12 | 中南大学 | Method for quantitatively detecting hydroxyl functional groups on surface of diamond micropowder by fluorescence |
CN112362629B (en) * | 2020-11-19 | 2021-11-02 | 中南大学 | Method for quantitatively detecting hydroxyl functional groups on surface of diamond micropowder by fluorescence |
CN112608324A (en) * | 2020-12-24 | 2021-04-06 | 衡阳师范学院 | Ultra-small fluorescent nano porous organic cage and preparation method and application thereof |
CN112608324B (en) * | 2020-12-24 | 2023-08-18 | 衡阳师范学院 | Fluorescent nano porous organic cage with ultra-small size and preparation method and application thereof |
CN112961669A (en) * | 2021-02-01 | 2021-06-15 | 苏州星烁纳米科技有限公司 | Preparation method of solid-phase carbon quantum dot, solid-phase carbon quantum dot prepared by same and light-emitting device |
CN113340862A (en) * | 2021-05-24 | 2021-09-03 | 中国工程物理研究院材料研究所 | Fluorescent molecular sensor, preparation method thereof and detection method of trace uranyl ions in water |
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