CN107903891A - A kind of preparation method and application of copper nanocluster self-assembly - Google Patents
A kind of preparation method and application of copper nanocluster self-assembly Download PDFInfo
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- CN107903891A CN107903891A CN201711245696.4A CN201711245696A CN107903891A CN 107903891 A CN107903891 A CN 107903891A CN 201711245696 A CN201711245696 A CN 201711245696A CN 107903891 A CN107903891 A CN 107903891A
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- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The present invention discloses a kind of preparation method of copper nanocluster self-assembly and its application as fluorescence probe in histamine is detected.The present invention is with 2,3,5,6 tetrafluoro benzenethiols are as ligand and reducing agent, one-step synthesis banding, there is the copper nanocluster self-assembly of fluorescent orange, this method is a kind of preparation method of new copper nanocluster self-assembly, have the advantages that it is easy to operate, prepare quickly, cost it is low etc..Synthesized copper nanocluster self-assembly has the advantages that exciting light spectrum width, emission spectrum are narrow, fluorescence quantum yield is high, fluorescent stability is strong, in addition, the copper nanocluster self-assembly can be used for the detection of histamine.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of preparation method of copper nanocluster self-assembly,
And application of the nanocluster self-assembly in histamine detection.
Background technology
Metal nanometer cluster be a kind of size between metallic atom and nano-particle, diameter is generally below 2nm's
Nano material.As a kind of new fluorescent material, metal nanometer cluster has been applied to biomarker, bio-imaging, structure
The each side such as fluorescent optical sensor, but metal nanometer cluster still suffers from some shortcomings, such as：Product fluorescence intensity is weak, fluorescent quantum
Low yield, stability difference etc., significantly limit its application in analysis detects.Reported in existing document, with monodispersed gold
Belong to cluster to compare, the metal cluster of state of aggregation or the fluorescence intensity height of metal cluster assembly, stability are good and close orderly
Self-assembled structures have the fluorescence intensity and stability of higher, so, metal nanometer cluster assembly is more suitable for analysis detection.
Ion induction, high boiling solvent high temperature prepare be the metal cluster or metal cluster assembly that prepare state of aggregation common side
Method, there are the shortcomings of preparation process is cumbersome, preparation time is long, cost is higher.
Biogenic amine is widely present in varieties of food items, and content is relatively more especially in the food rich in protein and amino acid
More, from a structural point, biogenic amine is divided into aromatic amine, fatty amine and heterocyclic amine three classes, and the biogenic amine in food mainly includes junket
Amine, histamine, putrescine, cadaverine, β-phenyl ethylamine, tryptamines, spermine and spermidine etc..Histamine is one of biogenic amine main in food,
Fish food histamine poisoning event happens occasionally, and international and various countries' health organization is all further expanding the food of histamine detection at present
Kind class and reduce histamine content standard, existing histamine detection method have thin-layer chromatography, gas-chromatography, high performance liquid chromatography,
The methods of Capillary Electrophoresis, electrochemical sensing, enzyme linked immunological, the sample pretreatment process of these methods is relatively complicated, Er Qiedou
It is related to the operation of some special instruments, so real-time, quick, the sensitive histamine detection method of development energy is very necessary.
The content of the invention
It is an object of the invention to provide a kind of preparation method of copper nanocluster self-assembly, and it is applied to histamine
Detection.
To achieve these goals, the preparation method of a kind of copper nanocluster self-assembly provided by the invention, be with 2,
3,5,6- tetrafluoro benzenethiols are as ligand and reducing agent, and the copper nanocluster with fluorescent orange of one-step synthesis banding is from group
Fill body.
A kind of preparation method of copper nanocluster self-assembly of the present invention, its step are：
(1) 12mg copper nitrates are weighed, add the solvent dissolving of 5mL, solvent for use includes acetone, tetrahydrofuran, ethanol, two
Methyl sulfoxide or dimethylformamide；
(2) the 2,3,5,6- tetrafluoros benzenethiol that 0.05~0.25mmol is added in copper nitrate solution stirs at 0-80 DEG C
15min~5h；
(3) reaction system obtained to step (2) centrifuges, and removes supernatant, retains sediment；
(4) sediment for obtaining step (3) adds ethanol centrifuge washing three times, is made lurid after nitrogen drying
2,3,5,6- tetrafluoros benzenethiol-copper nanocluster powder.
Solvent used is ethanol in the step (1).
2,3,5,6- tetrafluoro benzenethiol additions are 0.15mmol in the step (2), and reaction temperature is 25 DEG C of room temperature, instead
It is 30min between seasonable.
Centrifugation is to centrifuge 10min with the rotating speed of 8000r/min in the step (3).
A kind of copper nanocluster self-assembly powder is light yellow, and fluorescent orange is sent under 365nm ultraviolet lamps.
In the synthesis process, which has carried out self assembly, is in banded structure after self assembly.
A kind of uv-vis spectra of the copper nanocluster self-assembly have 255nm, 283nm, 330nm and
Tetra- characteristic absorption peaks of 435nm.
A kind of copper nanocluster self-assembly, excitation spectrum has and has at 330nm and 435nm in fluorescence spectrum
Two excitation wave crests, transmitted wave peak is located at 590nm in emission spectrum.The ethanol dispersion soln of the assembly is under 330nm excitations
Absolute fluorescence quantum yield be 43%.
A kind of copper nanocluster self-assembly, it is main through Energy Dispersive X energy spectrum analysis, the copper nanocluster
Contain tetra- kinds of elements of Cu, C, F, S.
It can be used for the detection of histamine according to copper nanocluster self-assembly described made from the method for the present invention.
Relative to the prior art, the advantage of the invention is that：
(1) present invention with 2,3,5,6- tetrafluoro benzenethiols as ligand and reducing agent, one-step synthesis banding at room temperature
Copper nanocluster self-assembly, have the advantages that it is easy to operate, prepare quick, cost is low etc..
(2) banding copper nanocluster assembly prepared by the present invention can send fluorescent orange under excitation, have exciting light
The advantages that spectrum width, emission spectrum are narrow, fluorescent stability is strong.
(3) the ethanol dispersion soln of banding copper nanocluster assembly prepared by the present invention is absolute under 330nm excitations
Quantum yield is up to 43%.
(4) the copper nanocluster assembly for preparing of the present invention histamine, tryptamines, tyrasamine, β-phenyl ethylamine, spermine, putrescine this
Can specific recognition histamine in common biogenic amine in six kinds of food.
(5) copper nanocluster assembly prepared by the present invention can be used for the detection of histamine, and detection is limited to 60nM, the range of linearity
For 0.1~10 μM, there is response is fast, the range of linearity is wide, detection limit is low etc..
Brief description of the drawings
Fig. 1 is the banding copper nanocluster self-assembly powder of the invention prepared in visible ray (a) and 365nm ultraviolet lamps
(b) photo under irradiating.
Fig. 2 is the transmission electron microscope phenogram of banding copper nanocluster self-assembly prepared by the present invention.
Fig. 3 is banding copper nanocluster self-assembly and ligand 2,3,5,6- tetrafluoros benzenethiol (TFTP) prepared by the present invention
Ultraviolet-visible absorption spectroscopy.
Fig. 4 is the fluorescence excitation spectrum and emission spectrum of banding copper nanocluster self-assembly prepared by the present invention.
Fig. 5 is the Energy Dispersive X energy spectrum diagram of banding copper nanocluster self-assembly prepared by the present invention.
Fig. 6 is six kinds of common biogenic amines (histamine, tryptamines, tyrasamine, β-phenyl ethylamine, putrescine, spermine) in food to banding copper
The influence figure of the fluorescence intensity of nanocluster self-assembly ethanol dispersion soln.
Fig. 7 is shadow of the histamine to the fluorescence intensity of banding copper nanocluster self-assembly ethanol dispersion soln of various concentrations
Ring figure
Fig. 8 is histamine to copper nanocluster self-assembly ethanol dispersion soln Quenching of fluorescence degree (F0/ F) it is dense with histamine
The linear fit curve of degree.
Embodiment
Embodiment 1：
The preparation process of banding copper nanocluster self-assembly：The ethanol that 12mg copper nitrates are dissolved in 5mL is weighed, is added
The 2 of 0.15mmol, 3,5,6- tetrafluoro benzenethiols, 1h is stirred at 25 DEG C；Then centrifuged, remove supernatant, retain precipitation
Thing；Again by sediment with ethanol centrifuge washing three times, nitrogen drying after lurid powder is made, 365nm ultraviolet lamps shine
Penetrate down and send fluorescent orange (see Fig. 1).
Embodiment 2：
The morphology characterization step of copper nanocluster self-assembly：It is molten that copper nanocluster self-assembly powder is scattered in ethanol
In liquid, take 2 μ L to drop on the copper mesh of ultrathin carbon films covering, transmission electron microscope sample is made after naturally dry, is placed on by sample
In the lens barrel of JEM-1011 transmission electron microscopes, its pattern is observed under suitable amplification factor.As seen from Figure 2, exist
Copper nanocluster has carried out self assembly in building-up process, is in banded structure after self assembly.
Embodiment 3：
The ultraviolet-visible absorption spectroscopy characterization step of copper nanocluster self-assembly：By copper nanocluster self-assembly powder
It is scattered in ethanol solution, its ultraviolet-visible absorption spectroscopy is measured with ultraviolet-uisible spectrophotometer, as shown in figure 3, its is ultraviolet
Visible spectrum has tetra- characteristic absorption peaks of 255nm, 283nm, 330nm and 435nm, the absworption peak wherein at 255nm, 283nm
Corresponding to the ultraviolet characteristic absorption of 2,3,5,6- tetrafluoro benzenethiol (TFTP) of ligand, the characteristic absorption peak at 330nm, 435nm is
The characteristic absorption of 2,3,5,6- tetrafluoros benzenethiol-copper nanocluster.
Embodiment 4：
The spectral characterization step of copper nanocluster self-assembly：It is molten that copper nanocluster self-assembly powder is scattered in ethanol
In liquid, with fluorescent spectrophotometer assay fluorescence spectrum.As shown in figure 4, have in fluorescence excitation spectrum positioned at 330nm and 435nm
Two excitation wave crests at place, corresponding to its ultraviolet characteristic absorption, emission peak is located at 590nm in emission spectrum.
Embodiment 5：
The component characterization step of copper nanocluster self-assembly：Amount of copper nanocluster self-assembly powder is taken to be placed in
On conductive tape, the EDAX energy disperse spectroscopies being equipped with after metal spraying with field emission scanning electron microscope gather its Energy Dispersive X energy spectrum diagram, by
Fig. 5 is understood, tetra- kinds of elements of Cu, C, F, S are mainly contained in copper nanocluster self-assembly.
Embodiment 6：
In fatty amine, aromatic amine, respectively selects biogenic amine common in two kinds of food in heterocyclic amine three classes, is respectively histamine, color
Amine, tyrasamine, β-phenyl ethylamine, spermine, putrescine, study fluorescence shadow of these amine to copper nanocluster self-assembly ethanol dispersion soln
Ring.Concentration is molten for the ethanol dispersion soln of the copper nanocluster self-assembly of 0.2mg/mL and the histamine standard items of respective concentration
Liquid mixes in equal volume, sepectrophotofluorometer spectra re-recorded is used after question response 5min, by the ratio of fluorescence intensity before and after reaction
F0/ F maps biological amine concentration, special in 6 kinds of biogenic amines that copper nanocluster self-assembly can be common in food as shown in Figure 6
Opposite sex identification histamine.
Embodiment 7：
Copper nanocluster self-assembly is used to detect histamine step：By the copper nanocluster self assembly that concentration is 0.2mg/mL
The ethanol dispersion soln of body mixes in equal volume with the histamine standard solution of respective concentration, and fluorescence spectrophotometer is used after question response 5min
Photometer spectra re-recorded, the result is shown in Fig. 7, Fig. 8.This method detection, which is obtained, by three times signal-to-noise ratio is limited to 60nM, will be glimmering before and after reaction
The ratio F of luminous intensity0/ F maps Histamine concentrations, and the range of linearity for obtaining copper nanocluster self-assembly detection histamine is 0.01
~10 μM.
The foregoing is merely the preferred embodiment of the invention, is not intended to limit the invention creation, all at this
Within the spirit and principle of innovation and creation, any modification, equivalent replacement, improvement and so on, should be included in the invention
Protection domain within.
Claims (10)
1. a kind of preparation method of copper nanocluster self-assembly, it is characterised in that be used as and matched somebody with somebody with 2,3,5,6- tetrafluoro benzenethiols
Body and reducing agent, the one-step synthesis copper nanocluster self-assembly with fluorescent orange of banding.
2. a kind of copper nanocluster self-assembly preparation method according to claim 1, it is characterised in that including following step
Suddenly：
(1) 12mg copper nitrates are weighed, add the solvent dissolving of 5mL, solvent for use includes acetone, tetrahydrofuran, ethanol, dimethyl
Sulfoxide or dimethylformamide；
(2) 2,3,5, the 6- tetrafluoro benzenethiols of 0.05~0.25mmol are added in the copper nitrate solution that step (1) obtains, in 0-
15min~5h is stirred at 80 DEG C；
(3) reaction system obtained to step (2) centrifuges, and removes supernatant, retains sediment；
(4) sediment for obtaining step (3) adds ethanol centrifuge washing three times, and lurid powder is made after nitrogen drying.
3. a kind of copper nanocluster self-assembly preparation method according to claim 2, it is characterised in that in step (1)
Solvent used is ethanol.
4. a kind of copper nanocluster self-assembly preparation method according to claim 2, it is characterised in that in step (2)
2,3,5,6- tetrafluoro benzenethiol additions are 0.15mmol, and reaction temperature is 25 DEG C of room temperature, reaction time 30min.
5. a kind of copper nanocluster self-assembly preparation method according to claim 2, it is characterised in that in step (3)
Centrifugation is to centrifuge 10min with the rotating speed of 8000r/min.
6. a kind of copper nanocluster self-assembly preparation method according to claim 1-5 any claims, its feature
It is, obtained copper nanocluster self-assembly is buff powder, sends fluorescent orange under 365nm ultraviolet lamps, is synthesizing
During, which has carried out self assembly, is in banded structure after self assembly.
7. a kind of copper nanocluster self-assembly preparation method according to claim 6, it is characterised in that obtained copper is received
Rice cluster self-assembly ultraviolet-visible absorption spectroscopy has tetra- characteristic absorption peaks of 255nm, 283nm, 330nm and 435nm.
8. a kind of copper nanocluster self-assembly preparation method according to claim 6, it is characterised in that obtained copper is received
There is at 330nm and 435nm excitation spectrum in rice cluster self-assembly fluorescence spectrum has two excitation wave crests, in emission spectrum
Transmitted wave peak is located at 590nm, the absolute fluorescence of the ethanol dispersion soln of the copper nanocluster self-assembly under 330nm excitations
Quantum yield is 43%.
9. a kind of copper nanocluster self-assembly preparation method according to claim 6, it is characterised in that through energy dispersive
X-ray energy spectrum is analyzed, and obtained copper nanocluster self-assembly mainly contains tetra- kinds of elements of Cu, C, F, S.
10. it can be used for group according to copper nanocluster self-assembly made from the method described in claim 1-9 any claims
The detection of amine.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724156A (en) * | 2019-10-22 | 2020-01-24 | 安徽大学 | Method for enhancing fluorescence intensity of copper nanocluster |
| CN111687408A (en) * | 2020-06-29 | 2020-09-22 | 太原师范学院 | Fluorescent copper nanocluster, preparation method and application thereof |
| CN112110955A (en) * | 2020-09-28 | 2020-12-22 | 安徽医科大学 | AuCu with high phosphorescence quantum yield in air atmosphere14Nanocluster and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106590635A (en) * | 2016-12-07 | 2017-04-26 | 吉林大学 | Yellow-light or red-light copper cluster assembly fluorescent material, and preparation method and application thereof in preparation of pure copper cluster white-light LED device |
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2017
- 2017-12-01 CN CN201711245696.4A patent/CN107903891B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106590635A (en) * | 2016-12-07 | 2017-04-26 | 吉林大学 | Yellow-light or red-light copper cluster assembly fluorescent material, and preparation method and application thereof in preparation of pure copper cluster white-light LED device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724156A (en) * | 2019-10-22 | 2020-01-24 | 安徽大学 | Method for enhancing fluorescence intensity of copper nanocluster |
| CN111687408A (en) * | 2020-06-29 | 2020-09-22 | 太原师范学院 | Fluorescent copper nanocluster, preparation method and application thereof |
| CN112110955A (en) * | 2020-09-28 | 2020-12-22 | 安徽医科大学 | AuCu with high phosphorescence quantum yield in air atmosphere14Nanocluster and method for preparing same |
| CN112110955B (en) * | 2020-09-28 | 2023-05-30 | 安徽医科大学 | Aucu with high phosphorescence quantum yield in air atmosphere 14 Nanoclusters and methods of making the same |
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