CN108489951A - Double fluorescent emission copper nano-cluster/carbon dots colorimetric probes, preparation method and the application in trace water context of detection - Google Patents
Double fluorescent emission copper nano-cluster/carbon dots colorimetric probes, preparation method and the application in trace water context of detection Download PDFInfo
- Publication number
- CN108489951A CN108489951A CN201810360138.0A CN201810360138A CN108489951A CN 108489951 A CN108489951 A CN 108489951A CN 201810360138 A CN201810360138 A CN 201810360138A CN 108489951 A CN108489951 A CN 108489951A
- Authority
- CN
- China
- Prior art keywords
- fluorescent emission
- cds
- double fluorescent
- cluster
- carbon dots
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
Landscapes
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The in-situ preparation method of copper nano-cluster/carbon dots (Cu NCs/CDs) the double fluorescent emission colorimetric probes of one kind based on aggregation inducing Fluorescence Increasing (AIEE) and its application in detecting organic solvent in terms of trace water, belong to colorimetric sensing technical field.The present invention includes three steps such as the preparation of the synthesis of blue-fluorescence carbon dots (CDs), the surface modification of CDs and double fluorescent emission Cu NCs/CDs probes.Double fluorescent emission effects of visible region 450nm blue lights and 596nm feux rouges are presented under 365nm ultraviolet excitations in the obtained double fluorescent emission probe Cu NCs/CDs of the present invention.There is using double fluorescence for different water contents in organic solvent the result of different responses; different composite fluorescence color changes is presented; this double fluorescent emission test paper can be used for the water of trace in bore hole colorimetric detection organic solvent; and detect limit can down to 0.02% (v/v), this is environmental protection, in food security and organic reaction the water detection of trace provide it is convenient.
Description
Technical field
The invention belongs to colorimetric sensing technical fields, and in particular to a kind of double transmitting colorimetrics based on copper nano-cluster/carbon dots
The preparation of probe and its application in the detection of organic solvent trace water.
Background technology
Water content in organic solvent can largely influence the progress of chemical reaction, or even can determine the production of reaction
Object, so sensitive in organic solvent and rapidly detect minor amount of water for drug manufacture, environmental monitoring and food inspection especially
It is that organic synthesis is of great significance.Therefore the water detection method of development convenient and efficient causes the great interest of people.It measures
The common chemical analysis method of Water in Organic Solvents content is the Karl_Fischer method of classics, which proposes in nineteen thirty-five, although
By significant improvement, but still have the shortcomings that reaction rate is slow, be easily disturbed, precision is poor, toxicity is big.Measure water content
Other methods have spectrophotometry, gas chromatography, liquid chromatography, infra-red sepectrometry and fluorescence method etc..Fluorescence method is due to it
The advantages that fast response time, high sensitivity, method are easy, instrument and equipment is simple and be concerned.Currently, common fluorescence sense
Material includes mainly fluorescent organic molecule, containing rare earth compounding, metal nanometre cluster and semiconductor-quantum-point etc..
In recent years, metal nanometre cluster (NCs) due to its special physics, chemistry and optical property and is being catalyzed, biology
Imaging and the various applications of chemical sensitisation etc. and be widely studied.Wherein, copper nano-cluster (Cu NCs) is due to excellent
Fluorescence property and more and more concerns are more inexpensively caused than gold, silver nano-cluster.In addition, Cu NCs have special gather
Collection induction transmitting enhancing (AIEE) property, it means that coherent condition shows the photoluminescent property of enhancing.Therefore, Cu NCs are utilized
AIEE properties, be prepared for many fluorescence probes be used for detect metal ion and solvent.However, being visited in the fluorescence invented
It is largely all based on single-shot in needle and penetrates detection, it means that including concentration and probe concentration, instrumental sensitivity and environmental condition etc. are all
It is multifactor all to influence testing result.Therefore, it there is an urgent need for preparing the fluorescence probe of more convenient, more acurrate, more stable double transmittings, uses
In detecting the minor amount of water in organic solvent.
The probe of double fluorescent emissions refers to that two different emission peaks are shown under single excited state, a kind of when detecting
The intensity of fluorescence emission peak changes with the variation of target detection thing, and the intensity of another fluorescence emission peak hardly happens change
Change, you can think to implant correction factor in detection architecture, it can be to avoid the shadow of concentration and probe concentration, instrument state and ambient condition
It rings, and double fluorescent emissions easily can directly use bore hole colorimetric detection.Based on above analysis, we devise based on tool
There is water of the double emitting probes of the Cu NCs of AIEE for trace in colorimetric detection organic solvent.
Invention content
The technical problem to be solved by the present invention is to：Cu NCs are constructed by the method for fabricated in situ and carbon dots (CDs) are compound
Double fluorescent emission probes, the probe have stable structure, it is environmental-friendly, it is easy to operate the features such as.
The preparation side of the double fluorescent emission colorimetric probes of copper nano-cluster/carbon dots of the present invention for trace water detection
Method, its step are as follows：
(1), the synthesis of blue-fluorescence CDs：By carbon source (phenol, m-phenylene diamine (MPD), terephthalic acid (TPA), melamine, lemon
Acid, glucose, chitosan, fructose, sucrose, lactic acid, cellulose, polyvinyl alcohol, polyacrylic acid, polyvinyl, pomelo peel)
With nitrogen source (urea, thiocarbamide, semicarbazides, diphenylcarbazide, ethylenediamine, triethylene tetramine, tryptophan, histidine, arginine, it is sweet
Propylhomoserin, cysteine, glutathione) it is 1~5 in molar ratio:1 is dissolved in the deionized water of 5~10 times of carbon source quality.So
Mixed solution is added in Teflon reaction kettle afterwards, be heated to 60~300 DEG C react 1~10h hour, after reaction, oneself
So it is cooled to room temperature.The product is brownish black clear solution, and yellow solution is obtained after dialysis, is obtained after freeze-drying faint yellow
CDs powder.
(2), the synthesis of glutathione modification CDs：0.1~0.5g glutathione (GSH) is added to 3~15 mL PBS
(pH=6.86) in buffer solution, thereto be added 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides (EDC) (0.1~
0.5g) and n-hydroxysuccinimide (NHS) (0.5~0.4g), 20~120min is stirred at room temperature in mixed solution, be protected from light to
CDs solution prepared by the step of 0.5~10mL concentration ranges are 1~20mg/mL (1) is wherein added, subsequent room temperature is protected from light stirring 6
~20h activates the CDs (GSH-CDs) that GSH modifications are prepared in coupling reaction by a simple imines in this way.It will be above-mentioned
The dialysis bag dialysis of 3500 molecular weight of solution 3~5 days, gets rid of EDC, NHS and excessive GSH, will finally obtain after purification
GSH-CDs solution low-temperature darks store for future use.
(3), the preparation of double fluorescent emission nanocomposite Cu NCs/CDs：30~500 μ that will be obtained in step (2)
L GSH-CDs are distributed to 0.2~5mL organic solvents, and (Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide (DMF), dimethyl are sub-
(DMSO), acetonitrile (CH3CN), tetrahydrofuran (THF), dichloromethane (CH2Cl2), chloroform (CHCl3)) in, fully stir
It mixes, copper source (basic copper carbonate Cu is added thereto2(OH)2CO3, basic copper sulfate Cu2(OH)2SO4, copper chloride CuCl2, sulfuric acid
Copper CuSO4, copper nitrate Cu (NO3)2, copper acetate Cu (Ac)2) (a concentration of 0.05~0.5 μM, volume is 10~250 μ L), stirring 1
~30min occurs a large amount of white insoluble matters in solution, fluorescent red-orange is presented under being irradiated under 365nm ultraviolet lamps, rotating speed is
5~30min is centrifuged under 3000~12000rpm, with DMF or DMSO and water volume ratio is 2~10 by solid product:1 mixing
Solution is washed 2~6 times, and product obtains double fluorescent emission Cu NCs/CDs composite materials after 30~80 DEG C are dried in vacuo 3~10h,
4 DEG C are stored at, in case further using.
It is preferably in the above scheme, the carbon source is phenol, m-phenylene diamine (MPD), terephthalic acid (TPA), melamine, lemon
Acid, glucose, chitosan, fructose, sucrose, lactic acid, cellulose, polyvinyl alcohol, polyacrylic acid, polyvinyl and pomelo peel
One or more of.
In any of the above-described scheme preferably, the nitrogen source is water-soluble level-one amine, general structure R-NH2。
In any of the above-described scheme preferably, the nitrogen source is urea, thiocarbamide, semicarbazides, diphenylcarbazide, second two
Amine, triethylene tetramine, tryptophan, histidine, arginine, glycine, one or more of cysteine and glutathione.
In any of the above-described scheme preferably, the organic solvent is Isosorbide-5-Nitrae-dioxane, N, N- dimethyl formyls
Amine (DMF), dimethyl sub- (DMSO), acetonitrile (CH3CN), tetrahydrofuran (THF), dichloromethane (CH2Cl2) and chloroform
(CHCl3One or more of).
In any of the above-described scheme preferably, copper source is basic copper carbonate Cu2(OH)2CO3, basic copper sulfate
Cu2(OH)2SO4, copper chloride CuCl2, copper sulphate CuSO4, copper nitrate Cu (NO3)2With copper acetate Cu (Ac)2One or more of.
It is described the present invention also provides a kind of double fluorescent emission colorimetric probes of copper nano-cluster/carbon dots for trace water detection
The double fluorescent emission colorimetric probes of copper nano-cluster/carbon dots are double fluorescent emission Cu NCs/CDs.
It is described the present invention also provides a kind of double fluorescent emission colorimetric probes of copper nano-cluster/carbon dots for trace water detection
The double fluorescent emission colorimetric probes of copper nano-cluster/carbon dots are double fluorescent emission Cu NCs/CDs, are by any of the above-described the method
It is prepared.
It is preferably in the above scheme, double fluorescent emission Cu NCs/CDs, can in the case where an exciting light irradiates
Two different fluorescence emission peaks are sent out, particle size is less than 20nm.
The double fluorescent emission colorimetric probes of copper nano-cluster/carbon dots of the present invention are used to detect the water of trace in organic solvent,
Its detection is limited to 0.02% (v/v).
For the obtained double fluorescent emission Cu NCs/CDs probes of the present invention, under 365nm ultraviolet excitations, presentation can
Double fluorescent emission effects of light-exposed area 450nm blue lights and 596nm feux rouges.Using the AIEE properties of Cu NCs, in organic solvent
The state that aggregation is presented emits the stronger red fluorescence of fluorescence intensity, and when encountering water, the state gradually disperseed is presented in it, red
Fluorescence intensity gradually weakens, and the blue-fluorescence of CDs is almost without changing in this process, therefore double fluorescence probes pair
In organic solvent the water of different content have different responses as a result, different composite fluorescence color change is presented, with this
Double fluorescent emissive materials are detected as colorimetric probe.It is organic that this double fluorescent emission probes can be used for bore hole colorimetric detection
The water of trace in solvent, and detecting limit can be down to 0.02% (v/v), and this is environmental monitoring, food inspection and organic reaction
It is convenient that middle trace water detection provides.
The remarkable advantage of the present invention is：
1. preparation method is simple, it is short to take, raw material is cheap, easily realizes industrialization production.
2. obtained double fluorescent emission probes are novel, have the characteristics that the transmitting of red blue Two Colour Fluorescence, be very beneficial for carrying out
Colorimetric detection.
3. being learnt by test experience result, which may be implemented the specific hypersensitive colorimetric detection to water, detection limit
It can be down to 0.02% (v/v), and to the detection result of water in different organic solvents all it is obvious that may be implemented to organic molten
Water content in agent is detected, thus the probe in organic solvent trace water context of detection have great potential.
Description of the drawings
Fig. 1：Fluorescence excitation (Ex), fluorescent emission (Em) and the UV absorption of 1 gained blue-fluorescence CDs of present example
(Abs) spectrogram；Show that a length of 338nm of the optimum excitation wave of CDs, best launch wavelength are 450nm；
Fig. 2：(a) fluorescence emission spectrogram of compound of the double fluorescent emission Cu NCs/CDs of 1 gained of present example, shows double fluorescence
Two fluorescence emission peaks of emitting probe are respectively in 450nm and 596nm；(b) when double fluorescent emissive materials Cu NCs/CDs dispersions
Transmission electron microscope photo；Show that Cu NCs are synthesized in the surface in situ of CDs, the grain size of the two is all in 2nm or so；
Fig. 3：Double fluorescent emission Cu NCs/CDs detect the fluorescence spectrum of different content water in DMSO in present example 2
Figure；Show to increase with the content of dampening, red fluorescence intensity reduces, blue-fluorescence being basically unchanged of intensity；
Fig. 4：In present example 2 in double fluorescent emission probe in detecting DMSO different content water fluorescence photo.Show with
The increase of water content, it is composite coloured that double fluorescent emission probes show different fluorescence.It is organic molten that fluorescence colorimetric detection may be implemented
Function containing trace water in agent DMSO；
Fig. 5：Double fluorescent emission Cu NCs/CDs detect the fluorescence spectrum of different content water in DMF in present example 3
Figure；Show that the increase with water content, red fluorescence intensity reduce, blue-fluorescence being basically unchanged of intensity.Fluorescence may be implemented
Function containing trace water in colorimetric detection organic solvent DMF.
Specific implementation mode
Embodiment 1
(1), the synthesis of blue-fluorescence CDs：1.0507g citric acids and 335 μ L ethylenediamines are dissolved in the deionization of 10mL
In water.Then mixed solution is added in Teflon reaction kettle, be heated to 200 DEG C react 5h hour, after reaction, oneself
So it is cooled to room temperature.The product is brownish black clear solution, and yellow solution is obtained after dialysis, is obtained after freeze-drying faint yellow
CDs powder.
(2), the synthesis of glutathione modification CDs：0.1995g glutathione (GSH) is added to the PBS (pH=of 10mL
6.86) in buffer solution, 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides (EDC) (0.125g) and N- are added thereto
HOSu NHS (NHS) (0.075g), 30min is stirred at room temperature in mixed solution, is protected from light addition 10mL concentration thereto
The CDs solution that the step of ranging from 10mg/mL (1) obtains, subsequent room temperature are protected from light stirring 10h, simple sub- by one in this way
The CDs (GSH-CDs) of GSH modifications is prepared in amine activation coupling reaction.Above-mentioned solution is oozed with the dialysis bag of 3500 molecular weight
Analysis 3~5 days, gets rid of EDC, NHS and excessive GSH, finally stores the GSH-CDs solution low-temperature darks obtained after purification
It is spare.
(3), the preparation of double fluorescent emission nanometer compound probe Cu NCs/CDs：The 300 μ L that will be obtained in step (2)
GSH-CDs is distributed in DMSO (0.65mL), is sufficiently stirred, and Cu (NO are added thereto3)2Solution (0.1 μM, 50 μ L), stirring
5min occurs a large amount of white insoluble matters in solution, fluorescent red-orange is presented under being irradiated under 365nm ultraviolet lamps, rotating speed is
6000rpm centrifuges 8min, with DMSO and water volume ratio is 5 by solid product:1 mixed solution is washed 3 times, and product is true through 40 DEG C
Double fluorescent emission Cu NCs/CDs probes are obtained after the dry 5h of sky, 4 DEG C are then stored at, in case further using.
Embodiment 2
(1), the synthesis of blue-fluorescence CDs：0.9603g citric acids and 300 μ L ethylenediamines are dissolved in the deionization of 8mL
In water.Then mixed solution is added in Teflon reaction kettle, be heated to 180 DEG C react 6.5 h hours, after reaction,
Cooled to room temperature.The product is brownish black clear solution, and yellow solution is obtained after dialysis, is obtained after freeze-drying faint yellow
CDs powder.
(2), the synthesis of glutathione modification CDs：0.1536g glutathione (GSH) is added to the PBS (pH=of 8mL
6.86) in buffer solution, 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides (EDC) (0.0904g) and N- are added thereto
HOSu NHS (NHS) (0.054g), 40min is stirred at room temperature in mixed solution, is protected from light addition 8mL concentration models thereto
Enclose for 9mg/mL the step of (1) obtained CDs solution, subsequent room temperature is protected from light stirring 12h, passes through a simple imines in this way
The CDs (GSH-CDs) of GSH modifications is prepared in activation coupling reaction.By the dialysis bag dialysis 3 of 3500 molecular weight of above-mentioned solution
~5 days, EDC, NHS and excessive GSH are got rid of, is finally stored the GSH-CDs solution low-temperature darks obtained after purification standby
With.
(3), the preparation of double fluorescent emission nanometer compound probe material Cu NCs/CDs：The 200 μ L that will be obtained in step (2)
GSH-CDs is distributed in DMSO (0.7mL), is sufficiently stirred, and Cu (NO are added thereto3)2Solution (0.1 μM, 40 μ L), stirring
4min occurs a large amount of white insoluble matters in solution, fluorescent red-orange is presented under being irradiated under 365nm ultraviolet lamps, rotating speed is
5000rpm centrifuges 10min, with DMSO and water volume ratio is 4 by solid product:1 mixed solution is washed 3 times, and product is true through 30 DEG C
Double fluorescent emission Cu NCs/CDs probes are obtained after the dry 6h of sky, 4 DEG C are then stored at, in case further using.
(4), in double fluorescent emission probe in detecting DMSO trace water：By double fluorescent emission Cu of 100 μ L (8.2mg/mL)
NCs/CDs, which is added in 3mL DMSO, does detection architecture (prepare 12 identical systems), then by the water of different volumes (0.6,
1.0,3.0,9.0,15.0,30.0,60.0,90.0,120.0,150.0, and 180.0 μ L) it is added separately in each system,
10s is shaken, response results are detected with Fluorescence Spectrometer, it can be found that：With the fluorescence intensity for increasing red fluorescence of water content
Gradually weaken, blue-fluorescence hardly happens variation；And different fluorescence face can be seen with bore hole with ultra violet lamp bottle
Good colorimetric effect is presented in color, therefore the probe can be used for detecting the water of trace in DMSO.
Embodiment 3
(1), the synthesis of blue-fluorescence CDs：1.2359g citric acids and 400 μ L ethylenediamines are dissolved in the deionization of 12mL
In water.Then mixed solution is added in Teflon reaction kettle, be heated to 160 DEG C react 8h hour, after reaction, oneself
So it is cooled to room temperature.The product is brownish black clear solution, and yellow solution is obtained after dialysis, is obtained after freeze-drying faint yellow
CDs powder.
(2), the synthesis of glutathione modification CDs：0.2033g glutathione (GSH) is added to the PBS (pH=of 12mL
6.86) in buffer solution, 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides (EDC) (0.1652g) and N- are added thereto
HOSu NHS (NHS) (0.947g), 60min is stirred at room temperature in mixed solution, is protected from light addition 12mL concentration thereto
The CDs solution that the step of ranging from 12mg/mL (1) obtains, subsequent room temperature are protected from light stirring 15h, simple sub- by one in this way
The CDs (GSH-CDs) of GSH modifications is prepared in amine activation coupling reaction.Above-mentioned solution is oozed with the dialysis bag of 3500 molecular weight
Analysis 3~5 days, gets rid of EDC, NHS and excessive GSH, finally stores the GSH-CDs solution low-temperature darks obtained after purification
It is spare.
(3), the preparation of double fluorescent emission nanometer compound probe material Cu NCs/CDs：400 μ that will be obtained in step (2)
LGSH-CDs is distributed in DMSO (0.9mL), is sufficiently stirred, and Cu (NO are added thereto3)2Solution (0.1 μM, 80 μ L), stirring
4min occurs a large amount of white insoluble matters in solution, fluorescent red-orange is presented under being irradiated under 365nm ultraviolet lamps, rotating speed is
7000rpm centrifuges 6min, and solid product is 6 with DMF and water volume ratio:1 mixed solution is washed 5 times, and product is dry through 50 DEG C of vacuum
Double fluorescent emission Cu NCs/CDs probes are obtained after dry 4h, 4 DEG C are then stored at, in case further using.
(4), in double fluorescent emission probe in detecting DMF trace water：By double fluorescent emission Cu of 100 μ L (8.2mg/mL)
NCs/CDs, which is added in 4mL DMF, does detection architecture (prepare 12 identical systems), then by the water of different volumes (0.6,
1.0,3.0,9.0,15.0,30.0,60.0,90.0,120.0,150.0, and 180.0 μ L) it is added separately in each system,
10s is shaken, response results are detected with Fluorescence Spectrometer, it can be found that：With the fluorescence intensity for increasing red fluorescence of water content
Gradually weaken, blue-fluorescence hardly happens variation；And different fluorescence face can be seen with bore hole with ultra violet lamp bottle
Good colorimetric effect is presented in color, therefore the probe can be used for detecting the water of trace in DMF.
Claims (10)
1. a kind of preparation method of the double fluorescent emission colorimetric probes of copper nano-cluster/carbon dots for trace water detection, including it is following
Each step：
(1), the synthesis of blue-fluorescence carbon dots (CDs)：It is 1~5 in molar ratio by carbon source and nitrogen source:1 be dissolved in carbon source quality 5~
In 10 times of deionized water, then mixed solution is added in Teflon reaction kettle, is heated to 60~300 DEG C of 1~10h of reaction
Hour, after reaction, cooled to room temperature, the product is brownish black clear solution, and yellow solution is obtained after dialysis, is freezed
Faint yellow CDs powder is obtained after drying；
(2), the synthesis of glutathione modification CDs：0.1~0.5g glutathione (GSH) is added to 3~15ml of pH=6.86
In PBS buffer solutions, 0.1~0.5g 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides (EDC) and 0.5 are added thereto
~0.4g n-hydroxysuccinimides (NHS), 20~120min is stirred at room temperature in mixed solution, is protected from light and 0.5 is added thereto
CDs solution prepared by the step of~10ml concentration ranges are 1~20mg/ml (1), subsequent room temperature are protected from light 6~20h of stirring, in this way
The CDs (GSH-CDs) that GSH modifications are prepared in coupling reaction is activated by a simple imines, by above-mentioned solution with 3500
The dialysis bag dialysis of molecular weight 3~5 days, gets rid of EDC, NHS and excessive GSH, the GSH-CDs that will finally obtain after purification
Solution low-temperature dark stores for future use；
(3), the preparation of double fluorescent emission nanocomposite Cu NCs/CDs：30~500 μ L that will be obtained in step (2)
GSH-CDs is distributed in 0.2~5mL organic solvents, is sufficiently stirred, and a concentration of 0.05~0.5 μM, volume 10 are added thereto
The copper source of~250 μ L stirs 1~30min, occurs a large amount of white insoluble matters in solution, is presented under being irradiated under 365nm ultraviolet lamps
Fluorescent red-orange, rotating speed is that 5~30min is centrifuged under 3000~12000rpm, by solid product DMF or DMSO and water volume ratio
It is 2~10:1 mixed solution is washed 2~6 times, and product obtains double fluorescent emission Cu after 30~80 DEG C are dried in vacuo 3~10h
NCs/CDs composite materials are stored at 4 DEG C, in case further using.
2. the double fluorescent emission colorimetric probes of a kind of copper nano-cluster/carbon dots for trace water detection as described in claim 1
Preparation method, it is characterised in that：The carbon source is phenol, m-phenylene diamine (MPD), terephthalic acid (TPA), melamine, citric acid, grape
One in sugar, chitosan, fructose, sucrose, lactic acid, cellulose, polyvinyl alcohol, polyacrylic acid, polyvinyl and pomelo peel
Kind is several.
3. the double fluorescent emission colorimetric probes of a kind of copper nano-cluster/carbon dots for trace water detection as described in claim 1
Preparation method, it is characterised in that：The nitrogen source is water-soluble level-one amine, general structure R-NH2。
4. the double fluorescent emission colorimetric probes of a kind of copper nano-cluster/carbon dots for trace water detection as described in claim 1 or 3
Preparation method, it is characterised in that：The nitrogen source is urea, thiocarbamide, semicarbazides, diphenylcarbazide, ethylenediamine, triethylene four
Amine, tryptophan, histidine, arginine, glycine, one or more of cysteine and glutathione.
5. the double fluorescent emission colorimetric probes of a kind of copper nano-cluster/carbon dots for trace water detection as described in claim 1
Preparation method, it is characterised in that：The organic solvent is Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide (DMF), dimethyl Asia
(DMSO), acetonitrile (CH3CN), tetrahydrofuran (THF), dichloromethane (CH2Cl2) and chloroform (CHCl3) in one kind or several
Kind.
6. the double fluorescent emission colorimetric probes of a kind of copper nano-cluster/carbon dots for trace water detection as described in claim 1
Preparation method, it is characterised in that：Copper source is basic copper carbonate Cu2(OH)2CO3, basic copper sulfate Cu2(OH)2SO4, chlorination
Copper CuCl2, copper sulphate CuSO4, copper nitrate Cu (NO3)2With copper acetate Cu (Ac)2One or more of.
7. a kind of double fluorescent emission colorimetric probes of copper nano-cluster/carbon dots for trace water detection, it is characterised in that：The copper is received
The double fluorescent emission colorimetric probes of rice cluster/carbon dots are double fluorescent emission Cu NCs/CDs.
8. a kind of double fluorescent emission colorimetric probes of copper nano-cluster/carbon dots for trace water detection, it is characterised in that：The copper is received
The double fluorescent emission colorimetric probes of rice cluster/carbon dots are double fluorescent emission Cu NCs/CDs, are by any one of claim 1~6 institute
The method stated is prepared.
9. the double fluorescent emission colorimetric probes of a kind of copper nano-cluster/carbon dots for trace water detection as claimed in claim 7, special
Sign is：Double fluorescent emission Cu NCs/CDs can send out two different fluorescent emissions in the case where an exciting light irradiates
Peak, particle size are less than 20nm.
10. a kind of copper nano-cluster/carbon dots for trace water detection prepared such as any one of claim 1~6 the method
Double fluorescent emission colorimetric probes, it is characterised in that：The double fluorescent emission colorimetric probes of the copper nano-cluster/carbon dots are organic for detecting
The water of trace in solvent, detection are limited to 0.02% (v/v).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810360138.0A CN108489951A (en) | 2018-04-20 | 2018-04-20 | Double fluorescent emission copper nano-cluster/carbon dots colorimetric probes, preparation method and the application in trace water context of detection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810360138.0A CN108489951A (en) | 2018-04-20 | 2018-04-20 | Double fluorescent emission copper nano-cluster/carbon dots colorimetric probes, preparation method and the application in trace water context of detection |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108489951A true CN108489951A (en) | 2018-09-04 |
Family
ID=63312794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810360138.0A Pending CN108489951A (en) | 2018-04-20 | 2018-04-20 | Double fluorescent emission copper nano-cluster/carbon dots colorimetric probes, preparation method and the application in trace water context of detection |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108489951A (en) |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109164083A (en) * | 2018-11-13 | 2019-01-08 | 青岛大学 | Based on copper nano-cluster/carbon dots/arginine complex paracetamol ratio fluorescent sensor preparation method |
| CN109211861A (en) * | 2018-10-10 | 2019-01-15 | 吉林化工学院 | A kind of polymerization object point/gold nanoclusters ratio fluorescent probe synthesis and its application to the detection of melamine ratio fluorescent |
| CN109283165A (en) * | 2018-10-31 | 2019-01-29 | 曲阜师范大学 | The preparation method and application of water microanalysis fluorescent test paper strip in a kind of organic reagent |
| CN109294569A (en) * | 2018-10-17 | 2019-02-01 | 河南大学 | A kind of preparation method of the adjustable carbon dots of fluorescence color |
| CN109324029A (en) * | 2018-12-14 | 2019-02-12 | 盐城工学院 | The method of gold nano cluster probe in detecting melamine concentration based on glutathione functionalization |
| CN109324028A (en) * | 2018-11-19 | 2019-02-12 | 湖南科技大学 | A method of Cr (VI) is detected using ethylenediamine and nitric acid as raw material microwave rapid synthesis carbon dots solution |
| CN109490269A (en) * | 2018-12-07 | 2019-03-19 | 吉林大学 | The application of double transmitting colorimetric fluorescent nanometer microsphere preparation methods and its Bacteria Detection |
| CN109557063A (en) * | 2018-12-30 | 2019-04-02 | 长春中医药大学 | A kind of method by the method for fluorescence copper nano-cluster probe in detecting catecholamine and its concentration, detection monoamine oxidase and its concentration |
| CN110108701A (en) * | 2019-04-22 | 2019-08-09 | 江苏大学 | A kind of lead ion rapid detection method based on fluorescence colorimetric and microflow control technique |
| CN110117492A (en) * | 2019-04-17 | 2019-08-13 | 长春工业大学 | A kind of fluorescent carbon point and the preparation method and application thereof |
| CN110125432A (en) * | 2019-04-22 | 2019-08-16 | 山西大学 | A kind of preparation method and application of green fluorescence copper nanocluster |
| CN110339357A (en) * | 2019-02-28 | 2019-10-18 | 安徽大学 | Copper ion doped carbon dots, preparation and its application as photosensitizer for photodynamic therapy |
| CN111122531A (en) * | 2020-01-06 | 2020-05-08 | 闽南师范大学 | Ratio fluorescence sensing method for visually identifying multiple organic solvents |
| CN111205862A (en) * | 2020-01-08 | 2020-05-29 | 辽宁大学 | Application of carbon quantum dot with multiple fluorescence emission centers as optical sensor in visual detection of trace water in organic solvent |
| CN111317706A (en) * | 2020-04-24 | 2020-06-23 | 云南伦扬科技有限公司 | Wet tissue with moisturizing, moistening and sterilizing functions and preparation method thereof |
| CN111394090A (en) * | 2020-02-24 | 2020-07-10 | 安徽大学 | Three-layer coated copper cluster ratio fluorescent probe and preparation method and application thereof |
| CN111518555A (en) * | 2020-04-30 | 2020-08-11 | 温州医科大学 | Trivalent cerium ion coupled graphite-phase carbon nitride and copper nanocluster ratio fluorescent probe and preparation method and application thereof |
| CN111591976A (en) * | 2020-06-04 | 2020-08-28 | 山东丰益泰和科技有限公司 | Fluorescent carbon quantum dot with scale inhibition performance and preparation method and application thereof |
| CN111909691A (en) * | 2020-06-23 | 2020-11-10 | 南京师范大学 | Preparation method of photo-thermal antibacterial near-infrared carbon quantum dots, product and application thereof |
| CN112285271A (en) * | 2020-10-22 | 2021-01-29 | 东来涂料技术（上海）股份有限公司 | Method for judging moisture content of organic solvent |
| WO2021035855A1 (en) * | 2019-08-26 | 2021-03-04 | 江苏大学 | Fluorescent test paper for measuring mercury ions and measurement method |
| CN113376129A (en) * | 2021-03-26 | 2021-09-10 | 中科院苏州医工所郑州工程技术研究院 | Preparation method and application of carbon dot-based nano composite for detecting iron ions |
| CN113916844A (en) * | 2020-07-08 | 2022-01-11 | 长春工业大学 | Preparation method of blue-red light dual-emission nano hybrid probe and application of blue-red light dual-emission nano hybrid probe in ion detection |
| WO2023103537A1 (en) * | 2022-08-16 | 2023-06-15 | 广东省科学院微生物研究所(广东省微生物分析检测中心) | Gsh-based fluorescent nanoprobe, and synthesis method therefor and use thereof |
| CN116656344A (en) * | 2023-05-12 | 2023-08-29 | 电子科技大学 | Preparation method of fluorescent nanocluster for humidity sensor |
| CN116814106A (en) * | 2023-07-05 | 2023-09-29 | 广东红海湾发电有限公司 | Fluorescent marking material for high-temperature-resistant flame-retardant photovoltaic cable and preparation method thereof |
| CN116836699A (en) * | 2023-04-25 | 2023-10-03 | 四川轻化工大学 | Carbon quantum dot based on shaddock peel and preparation method and application thereof |
-
2018
- 2018-04-20 CN CN201810360138.0A patent/CN108489951A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| SHANLIANG SONG等: "Ratiometric fluorescence detection of trace water in organic solvents based on aggregation-induced emission enhanced Cu nanoclusters", 《ANALYST》 * |
Cited By (42)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109211861A (en) * | 2018-10-10 | 2019-01-15 | 吉林化工学院 | A kind of polymerization object point/gold nanoclusters ratio fluorescent probe synthesis and its application to the detection of melamine ratio fluorescent |
| CN109294569B (en) * | 2018-10-17 | 2021-11-16 | 河南大学 | Preparation method of fluorescent color-adjustable carbon dots |
| CN109294569A (en) * | 2018-10-17 | 2019-02-01 | 河南大学 | A kind of preparation method of the adjustable carbon dots of fluorescence color |
| CN109283165A (en) * | 2018-10-31 | 2019-01-29 | 曲阜师范大学 | The preparation method and application of water microanalysis fluorescent test paper strip in a kind of organic reagent |
| CN109283165B (en) * | 2018-10-31 | 2020-11-06 | 曲阜师范大学 | Preparation method and application of fluorescent test strip for analyzing trace water in organic reagent |
| WO2020098182A1 (en) * | 2018-11-13 | 2020-05-22 | 青岛大学 | Preparation method of copper nanocluster/carbon dot/arginine complex-based ratiometric fluorescent sensor for paracetamol |
| CN109164083B (en) * | 2018-11-13 | 2019-06-14 | 青岛大学 | Based on copper nano-cluster/carbon dots/arginine complex paracetamol ratio fluorescent sensor preparation method |
| US10983057B2 (en) | 2018-11-13 | 2021-04-20 | Qingdao University | Method for preparing a ratiometric fluorescent sensor for paracetamol based on a copper nanoclusters-carbon dots-arginine composite |
| CN109164083A (en) * | 2018-11-13 | 2019-01-08 | 青岛大学 | Based on copper nano-cluster/carbon dots/arginine complex paracetamol ratio fluorescent sensor preparation method |
| CN109324028A (en) * | 2018-11-19 | 2019-02-12 | 湖南科技大学 | A method of Cr (VI) is detected using ethylenediamine and nitric acid as raw material microwave rapid synthesis carbon dots solution |
| CN109490269B (en) * | 2018-12-07 | 2020-07-24 | 吉林大学 | Preparation method of dual-emission colorimetric fluorescent nano-microsphere and application of dual-emission colorimetric fluorescent nano-microsphere in bacterial detection |
| CN109490269A (en) * | 2018-12-07 | 2019-03-19 | 吉林大学 | The application of double transmitting colorimetric fluorescent nanometer microsphere preparation methods and its Bacteria Detection |
| CN109324029B (en) * | 2018-12-14 | 2021-08-06 | 盐城工学院 | Method for detecting melamine concentration by gold nanocluster probe based on glutathione functionalization |
| CN109324029A (en) * | 2018-12-14 | 2019-02-12 | 盐城工学院 | The method of gold nano cluster probe in detecting melamine concentration based on glutathione functionalization |
| CN109557063A (en) * | 2018-12-30 | 2019-04-02 | 长春中医药大学 | A kind of method by the method for fluorescence copper nano-cluster probe in detecting catecholamine and its concentration, detection monoamine oxidase and its concentration |
| CN110339357A (en) * | 2019-02-28 | 2019-10-18 | 安徽大学 | Copper ion doped carbon dots, preparation and its application as photosensitizer for photodynamic therapy |
| CN110339357B (en) * | 2019-02-28 | 2021-04-13 | 安徽大学 | Copper ion doped carbon dot, preparation and application thereof as photodynamic therapy photosensitizer |
| CN110117492B (en) * | 2019-04-17 | 2021-12-10 | 长春工业大学 | Fluorescent carbon dot and preparation method and application thereof |
| CN110117492A (en) * | 2019-04-17 | 2019-08-13 | 长春工业大学 | A kind of fluorescent carbon point and the preparation method and application thereof |
| CN110125432A (en) * | 2019-04-22 | 2019-08-16 | 山西大学 | A kind of preparation method and application of green fluorescence copper nanocluster |
| CN110108701A (en) * | 2019-04-22 | 2019-08-09 | 江苏大学 | A kind of lead ion rapid detection method based on fluorescence colorimetric and microflow control technique |
| CN110125432B (en) * | 2019-04-22 | 2021-07-27 | 山西大学 | Preparation method and application of green fluorescent copper nanocluster |
| CN110108701B (en) * | 2019-04-22 | 2021-08-03 | 江苏大学 | Rapid lead ion detection method based on fluorescence colorimetry and microfluidic technology |
| US11378519B2 (en) | 2019-08-26 | 2022-07-05 | Jiangsu University | Fluorescent test paper for detecting mercury ions and detection method using the same |
| WO2021035855A1 (en) * | 2019-08-26 | 2021-03-04 | 江苏大学 | Fluorescent test paper for measuring mercury ions and measurement method |
| CN111122531A (en) * | 2020-01-06 | 2020-05-08 | 闽南师范大学 | Ratio fluorescence sensing method for visually identifying multiple organic solvents |
| CN111205862A (en) * | 2020-01-08 | 2020-05-29 | 辽宁大学 | Application of carbon quantum dot with multiple fluorescence emission centers as optical sensor in visual detection of trace water in organic solvent |
| CN111394090A (en) * | 2020-02-24 | 2020-07-10 | 安徽大学 | Three-layer coated copper cluster ratio fluorescent probe and preparation method and application thereof |
| CN111317706A (en) * | 2020-04-24 | 2020-06-23 | 云南伦扬科技有限公司 | Wet tissue with moisturizing, moistening and sterilizing functions and preparation method thereof |
| CN111518555A (en) * | 2020-04-30 | 2020-08-11 | 温州医科大学 | Trivalent cerium ion coupled graphite-phase carbon nitride and copper nanocluster ratio fluorescent probe and preparation method and application thereof |
| CN111518555B (en) * | 2020-04-30 | 2022-12-20 | 温州医科大学 | Trivalent cerium ion coupled graphite-phase carbon nitride and copper nanocluster ratio fluorescent probe and preparation method and application thereof |
| CN111591976A (en) * | 2020-06-04 | 2020-08-28 | 山东丰益泰和科技有限公司 | Fluorescent carbon quantum dot with scale inhibition performance and preparation method and application thereof |
| CN111909691A (en) * | 2020-06-23 | 2020-11-10 | 南京师范大学 | Preparation method of photo-thermal antibacterial near-infrared carbon quantum dots, product and application thereof |
| CN113916844A (en) * | 2020-07-08 | 2022-01-11 | 长春工业大学 | Preparation method of blue-red light dual-emission nano hybrid probe and application of blue-red light dual-emission nano hybrid probe in ion detection |
| CN112285271A (en) * | 2020-10-22 | 2021-01-29 | 东来涂料技术（上海）股份有限公司 | Method for judging moisture content of organic solvent |
| CN113376129A (en) * | 2021-03-26 | 2021-09-10 | 中科院苏州医工所郑州工程技术研究院 | Preparation method and application of carbon dot-based nano composite for detecting iron ions |
| WO2023103537A1 (en) * | 2022-08-16 | 2023-06-15 | 广东省科学院微生物研究所(广东省微生物分析检测中心) | Gsh-based fluorescent nanoprobe, and synthesis method therefor and use thereof |
| CN116836699A (en) * | 2023-04-25 | 2023-10-03 | 四川轻化工大学 | Carbon quantum dot based on shaddock peel and preparation method and application thereof |
| CN116836699B (en) * | 2023-04-25 | 2024-03-22 | 四川轻化工大学 | Carbon quantum dot based on shaddock peel and preparation method and application thereof |
| CN116656344A (en) * | 2023-05-12 | 2023-08-29 | 电子科技大学 | Preparation method of fluorescent nanocluster for humidity sensor |
| CN116656344B (en) * | 2023-05-12 | 2024-04-12 | 电子科技大学 | Preparation method of fluorescent nanocluster for humidity sensor |
| CN116814106A (en) * | 2023-07-05 | 2023-09-29 | 广东红海湾发电有限公司 | Fluorescent marking material for high-temperature-resistant flame-retardant photovoltaic cable and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108489951A (en) | Double fluorescent emission copper nano-cluster/carbon dots colorimetric probes, preparation method and the application in trace water context of detection | |
| Li et al. | Ratiometric fluorescence detection of tetracycline antibiotic based on a polynuclear lanthanide metal–organic framework | |
| Song et al. | Eu3+ doped bismuth metal-organic frameworks with ultrahigh fluorescence quantum yield and act as ratiometric turn-on sensor for histidine detection | |
| Suárez et al. | Functionalized phosphorescent nanoparticles in (bio) chemical sensing and imaging–a review | |
| Sun et al. | Recent advances in developing lanthanide metal–organic frameworks for ratiometric fluorescent sensing | |
| Zhang et al. | A volatile basic nitrogens-responsive tag based on aggregation-induced emission luminogen for real-time monitoring and in situ visualization of salmon freshness | |
| Fereja et al. | A recent review on chemiluminescence reaction, principle and application on pharmaceutical analysis | |
| Gan et al. | Collaborative compounding of metal-organic frameworks and lanthanide coordination polymers for ratiometric visual detection of tetracycline | |
| Bian et al. | A novel phosphorescence sensor for Co2+ ion based on Mn‐doped ZnS quantum dots | |
| Liu et al. | A sensitive metal–organic framework nanosensor with cation-introduced chirality for enantioselective recognition and determination of quinine and quinidine in human urine | |
| Rooj et al. | Green synthesized carbon quantum dots from polianthes tuberose L. Petals for Copper (II) and Iron (II) detection | |
| Sun et al. | Aggregation-induced emission of 4-formyl-3-hydroxybenzoic acid for the ratiometric fluorescence detection of tetracycline antibiotics | |
| Wang et al. | A hybrid of carbon dots with 4-chloro-7-nitro-2, 1, 3-benzoxadiazole for selective detection of p-phenylenediamine | |
| CN108752377B (en) | Fluorescent probe for detecting peroxynitrite anion, synthetic method and application | |
| CN107389636A (en) | A kind of preparation and application of the water soluble fluorescence sensor that endogenous glutathione can be detected in cancer cell | |
| CN101963581A (en) | Preparation method of Zns:Cu<2+>nanocrystalline fluorescence probe detecting trace TNT (trinitrotoluene) | |
| CN110862547B (en) | Rare earth supermolecule gel luminescent material, preparation and application thereof | |
| Zhang et al. | Nitrogen-doped carbon dots from rhizobium as fluorescence probes for chlortetracycline hydrochloride | |
| Li et al. | Sensitive detection of the antibiotic pollutants by a solvent-stable luminescent sensor based on a europium (III) metal-organic framework | |
| CN114656424B (en) | Up-conversion long-afterglow chemiluminescent imaging nano probe and preparation method and application thereof | |
| Ma et al. | A dual-emission Eu (Ⅲ) functionalized multi-ligand MOFs for wide range pH sensing | |
| Fang et al. | Research progress of fluorescent-substance@ MOFs | |
| Ma et al. | One high-nuclearity Eu 18 nanoring with rapid ratiometric fluorescence response to dipicolinic acid (an anthrax biomarker) | |
| Xu et al. | pH and solvent induced discoloration behavior of multicolor fluorescent carbon dots | |
| Su et al. | Rapid and high-selectivity detection of rifampicin based on upconversion luminescence core-shell structure composites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180904 |
|
| WD01 | Invention patent application deemed withdrawn after publication |