CN104139188A - Method for preparing polymer protected fluorescent copper nanoclusters - Google Patents
Method for preparing polymer protected fluorescent copper nanoclusters Download PDFInfo
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- CN104139188A CN104139188A CN201410335952.9A CN201410335952A CN104139188A CN 104139188 A CN104139188 A CN 104139188A CN 201410335952 A CN201410335952 A CN 201410335952A CN 104139188 A CN104139188 A CN 104139188A
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Abstract
The invention discloses a method for preparing polymer protected fluorescent copper nanoclusters. The method is characterized by comprising the following steps of 1, dissolving a polymer solution and a 4-(2-hydroxyerhyl) piperazine-1-erhaesulfonic acid solution in a proper amount of pure water, and stirring to blend uniformly; 2, adding a cupric nitrate solution into the solution in the step 1, and continuously stirring; 3, adding a proper amount of methanol into the solution in the step 2 and heating at the temperature of between 50 and 90DEG C for 10 to 100 minutes to obtain a blue polymer protected fluorescent copper nanocluster solution. According to the method, a polymer is taken as a stabilizer, the methanol is taken as a reducing agent, 4-(2-hydroxyerhyl) piperazine-1-erhaesulfonic acid is taken as an auxiliary, cupric nitrate is taken as a Cu source, and reaction conditions are mild. The copper nanoclusters synthesized by the method have the advantages of low price, stable performance, no toxicity and the like, serve as a potential fluorescent label to be expectedly applied to the fields such as optical imaging, biomarkers and chemical sensors, and have wide application prospect in the fields such as environment analysis, biochemical analysis and food safety.
Description
Technical field
The invention belongs to field of nano material preparation, relate to new method prepared by a kind of polymer protection fluorescence copper nanocluster of high stability.
Background technology
Cluster forms metastable aggregation by physics and chemistry adhesion by several to several thousand atoms, molecule, ions, its bulk at several dusts to the scope of hundreds of dust.Because nanocluster has the surface atom of larger proportion, there is significant difference in the environment of the inner atom of this part of atoms and cluster, make nanocluster there are a series of single atom, molecules of being different from, also be different from physical property and the chemical property of bulk solid material, there is the quantum size effect of abnormal high chemism and catalytic performance, light and physical dimension effect that nonlinear effect, electricity are led, adulterate and mix the electric conductivity etc. of the electric conductivity of bag atom and superconductivity, carbon pipe, carbon green onion as great specific surface makes it.
Along with reducing of metal nanoparticle yardstick, its level structure can occur sharply to change, and near electron energy level fermi level is transitioned into discrete energy levels from quasicontinuum state.The variation of level structure has metal nanometer cluster to be different from the special performance of base metal, obtains broad research and application in recent years at aspects such as catalysis, fluorescence analysis and biomarkers.
But, at present transition metal nanocluster research on sub-nanoscale is mainly concentrated on to noble metal Au and Ag, and relatively less to the Cu nanocluster research in (IB) of the same clan.And the Cu nano-particles size that adopts conventional method to obtain is larger, and more oxidizable.Therefore, the simple method for synthesizing of stable Cu nanocluster is one of challenging problem in metal cluster research.
Summary of the invention
For the existing problem and shortage of prior art, the present invention aims to provide a kind of preparation method of simple stable polymer protection fluorescence copper nanocluster.The method has simple to operate, raw materials used low price, reaction condition gentleness, the advantage such as nontoxic, the copper nanocluster stable performance of preparation, be easy to preserve, and instrument equipment is conventional equipment, as: magnetic stirring apparatus, round-bottomed flask etc.
The preparation method of polymer protection fluorescence copper nanocluster, is characterized in that comprising the following steps:
4-HEPES (HEPES) solution that step 1, the polymer solution that is 0.1g/mL by the concentration of 300-900 μ L and 300-600 μ L concentration are 10mmol/l is dissolved in appropriate pure water, stirs 2-20min;
Step 2, the copper nitrate solution that is 100mmol/l to the concentration that adds 100-300 μ L in step 1 solution, stir 2-20min;
Step 3, under strong magnetic agitation, in step 2 solution, add appropriate formaldehyde, at 50-90 DEG C, heat 10-100min, obtain blue solution, be polymer protection fluorescence copper nanocluster.
Polymer in described step 1 is polymine, shitosan or polylysine.
In step 1, the amount of pure water is at 1390-2680 μ L.
In step 3, the amount of formaldehyde is at 10-30 μ L.
The polymer protection fluorescence copper nanocluster of the synthetic high stability of the present invention has low price, stable performance, reaction condition gentleness, the advantage such as nontoxic; be expected to be applied to the fields such as photoimaging, biomarker, chemical sensor as a kind of potential fluorescent marker, and it also has comparatively wide application prospect in fields such as environmental analysis, biochemical analysis, food securities.
Brief description of the drawings
Fig. 1 is the synthetic polymer protection fluorescence copper nanocluster Electronic Speculum collection of illustrative plates of the present invention.
Fig. 2 is the synthetic polymer protection fluorescence copper nanocluster fluorescence pattern of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1:
The preparation method of polymer protection fluorescence copper nanocluster, comprises the steps:
(1) 4-HEPES (HEPES) solution that polymine (PEI) solution that is 0.1g/mL by the concentration of 500 μ L and 300 μ L concentration are 10mmol/l is dissolved in the pure water of 2020 μ L, stirs 5min;
(2) copper nitrate solution that is 100mmol/l to the concentration that adds 150 μ L in step (1) solution, stirs 20min;
(3) under magnetic agitation to the formaldehyde that adds 30 μ L in step (2) solution, at 50 DEG C, heat 20min, obtain blue solution, be polymer protection fluorescence copper nanocluster.Make the Electronic Speculum collection of illustrative plates of polymer protection fluorescence copper nanocluster as shown in Figure 1, fluorescence pattern as shown in Figure 2.
Embodiment 2:
The preparation method of polymer protection fluorescence copper nanocluster, comprises the steps:
(1) 4-HEPES (HEPES) solution that the chitosan solution that is 0.1g/mL by the concentration of 800 μ L and 500 μ L concentration are 10mmol/l is dissolved in the pure water of 1390 μ L, stirs 20min;
(2), to the copper nitrate solution that adds the 100mmol/l of 300 μ L in step (1) solution, stir 5min;
(3) under magnetic agitation to the formaldehyde that adds 10 μ L in step (2) solution, at 70 DEG C, heat 50min, obtain blue solution, be polymer protection fluorescence copper nanocluster.
Embodiment 3:
The preparation method of polymer protection fluorescence copper nanocluster, comprises the steps:
(1) 4-HEPES (HEPES) solution that the lysine solution that is 0.1g/mL by the concentration of 300 μ L and 600 μ L concentration are 10mmol/l is dissolved in the pure water of 1980 μ L, stirs 10min;
(2) copper nitrate solution that is 100mmol/l to the concentration that adds 100 μ L in step (1) solution, stirs 15min;
(3) under magnetic agitation to the formaldehyde that adds 20 μ L in step (2) solution, at 80 DEG C, heat 80min, obtain blue solution, be polymer protection fluorescence copper nanocluster.
Embodiment 4:
The preparation method of polymer protection fluorescence copper nanocluster, comprises the steps:
(1) 4-HEPES (HEPES) solution that polymine (PEI) solution that is 0.1g/mL by the concentration of 900 μ L and 500 μ L concentration are 10mmol/l is dissolved in the pure water of 2680 μ L, stirs 2min;
(2) copper nitrate solution that is 100mmol/l to the concentration that adds 100 μ L in step (1) solution, stirs 15min;
(3) under magnetic agitation to the formaldehyde that adds 20 μ L in step (2) solution, at 90 DEG C, heat 10min, obtain blue solution, be polymer protection fluorescence copper nanocluster.
Embodiment 5:
The preparation method of polymer protection fluorescence copper nanocluster, comprises the steps:
(1) 4-HEPES (HEPES) solution that the lysine solution that is 0.1g/mL by the concentration of 600 μ L and 400 μ L concentration are 10mmol/l is dissolved in the pure water of 1980 μ L, stirs 10min;
(2) copper nitrate solution that is 100mmol/l to the concentration that adds 250 μ L in step (1) solution, stirs 2min;
(3) under magnetic agitation to the formaldehyde that adds 10 μ L in step (2) solution, at 60 DEG C, heat 60min, obtain blue solution, be polymer protection fluorescence copper nanocluster.
Claims (4)
1. the preparation method of polymer protection fluorescence copper nanocluster, is characterized in that comprising the following steps:
4-HEPES (HEPES) solution that step 1, the polymer solution that is 0.1g/mL by the concentration of 300-900 μ L and 300-600 μ L concentration are 10mmol/l is dissolved in appropriate pure water, stirs 2-20min;
Step 2, the copper nitrate solution that is 100mmol/l to the concentration that adds 100-300 μ L in step 1 solution, stir 2-20min;
Step 3, under strong magnetic agitation, in step 2 solution, add appropriate formaldehyde, at 50-90 DEG C, heat 10-100min, obtain blue solution, be polymer protection fluorescence copper nanocluster.
2. the preparation method of polymer protection fluorescence copper nanocluster according to claim 1, is characterized in that: the polymer in described step 1 is polymine, shitosan or polylysine.
3. the preparation method of polymer protection fluorescence copper nanocluster according to claim 1, is characterized in that: in step 1, the amount of pure water is at 1390-2680 μ L.
4. the preparation method of polymer protection fluorescence copper nanocluster according to claim 1, is characterized in that: in step 3, the amount of formaldehyde is at 10-30 μ L.
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| CN201410335952.9A CN104139188B (en) | 2014-07-15 | The preparation method of polymer protection fluorescence copper nanocluster |
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| CN201410335952.9A CN104139188B (en) | 2014-07-15 | The preparation method of polymer protection fluorescence copper nanocluster |
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| CN104139188A true CN104139188A (en) | 2014-11-12 |
| CN104139188B CN104139188B (en) | 2017-01-04 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607652A (en) * | 2015-01-17 | 2015-05-13 | 南京师范大学 | Controllable precious metal nanocatalyst synthesis method with amino acid as soft templates |
| CN104865230A (en) * | 2015-05-25 | 2015-08-26 | 西南大学 | PVP (polyvinylpyrrolidone) protected copper nano cluster and method for detecting free chlorine in tap water |
| CN108372311A (en) * | 2018-03-21 | 2018-08-07 | 北京科技大学 | A method of preparing copper nano-particle using modification of polysaccharides |
| CN108971511A (en) * | 2018-07-26 | 2018-12-11 | 大连理工大学 | A method of using polymer film as the high fluorescence copper nano-cluster of carrier rapid synthesis |
| CN117025210A (en) * | 2023-08-09 | 2023-11-10 | 湖北大学 | Blue copper fluorescent probe for detecting tetracycline antibiotics and preparation method thereof |
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| WO2010091529A1 (en) * | 2009-02-10 | 2010-08-19 | Mingfen Tsai | A composition comprising silver nanoparticles and extracts of polygonum multiflorum thunb and the use thereof |
| CN101576548A (en) * | 2009-05-05 | 2009-11-11 | 中国科学院长春应用化学研究所 | Method for detecting Al<3+> in drinking water or cells based on functionalized gold nanoprobe colour comparison |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607652A (en) * | 2015-01-17 | 2015-05-13 | 南京师范大学 | Controllable precious metal nanocatalyst synthesis method with amino acid as soft templates |
| CN104865230A (en) * | 2015-05-25 | 2015-08-26 | 西南大学 | PVP (polyvinylpyrrolidone) protected copper nano cluster and method for detecting free chlorine in tap water |
| CN104865230B (en) * | 2015-05-25 | 2018-05-11 | 西南大学 | The method of free chlorine in the copper nano-cluster and detection tap water of polyvinylpyrrolidone protection |
| CN108372311A (en) * | 2018-03-21 | 2018-08-07 | 北京科技大学 | A method of preparing copper nano-particle using modification of polysaccharides |
| CN108372311B (en) * | 2018-03-21 | 2019-07-16 | 北京科技大学 | A method of copper nano-particle is prepared using modification of polysaccharides |
| CN108971511A (en) * | 2018-07-26 | 2018-12-11 | 大连理工大学 | A method of using polymer film as the high fluorescence copper nano-cluster of carrier rapid synthesis |
| CN117025210A (en) * | 2023-08-09 | 2023-11-10 | 湖北大学 | Blue copper fluorescent probe for detecting tetracycline antibiotics and preparation method thereof |
| CN117025210B (en) * | 2023-08-09 | 2024-03-19 | 湖北大学 | Blue copper fluorescent probe for detecting tetracycline antibiotics and preparation method thereof |
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