CN108971511A - A method of using polymer film as the high fluorescence copper nano-cluster of carrier rapid synthesis - Google Patents
A method of using polymer film as the high fluorescence copper nano-cluster of carrier rapid synthesis Download PDFInfo
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- CN108971511A CN108971511A CN201810834689.6A CN201810834689A CN108971511A CN 108971511 A CN108971511 A CN 108971511A CN 201810834689 A CN201810834689 A CN 201810834689A CN 108971511 A CN108971511 A CN 108971511A
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- cluster
- copper nano
- chitosan
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- polymer film
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
Abstract
The invention belongs to the preparation technical fields of fluorescent nano material, it provides a kind of using polymer film as the method for the high fluorescence copper nano-cluster of carrier rapid synthesis, steps are as follows: (1) weighing the chitosan of certain mass, glacial acetic acid is added dropwise to make it completely dissolved, configuration quality percent concentration is the chitosan solution of 1.5%-2.5%；(2) at room temperature, glutathione solution and Gerhardite solution are added in step (1) resulting chitosan solution, gained mixed solution stirs evenly；The molar ratio for controlling glutathione and Gerhardite is 0.5:1~10:1；(3) step (2) resulting mixed solution is reacted into 5-7h in 35-45 DEG C of air blast bellows.For the present invention by one-step method using chitosan film as the copper nano-cluster of the high fluorescence of carrier rapid synthesis, chitosan film can protect copper nano-cluster as good nano-reactor, reduce the energy of nonradiative transition loss, and then improve fluorescence intensity.
Description
Technical field
The present invention relates to a kind of using polymer film as the method for the high fluorescence copper nano-cluster of carrier rapid synthesis, belongs to fluorescence and receives
The preparation technical field of rice material.
Background technique
Metal nanometre cluster is that a kind of molecular level for being made of several to dozens of metallic atoms, having " core-shell structure copolymer " structure is poly-
Collective.There is dimensional effect since size is less than Fermi's wavelength of electronics, there is excellent physical/chemical and optical property.
Compared with biggish metal nanoparticle, photoluminescence is its critical nature in UV, visible light region.In addition to noble metal
Outside gold, silver, cheap, nontoxic, rich content copper nano-cluster has also been widely studied.However, since copper is relatively vivaciously easily oxidized
And in the synthesis process therefore uniform partial size difficult to control is mesh by copper nano-cluster of the straightforward procedure synthesis with high fluorescence
Preceding research hotspot and difficult point.In addition, synthesis copper nano-cluster generally requires longer time at present, in order to save time and energy
Source, rapid synthesis have the copper nanocluster of high fluorescence significant.
Polymer molecule film, since polymer is easily connected by intermolecular force, can prepare has good extend
The polymer molecule film of property.Chitosan, is a kind of edible polymer material, nontoxic, good biocompatibility, biodegradable,
With bacteriostasis property and there is good film forming.Chitosan film can generate different size of hole in film forming procedure, can make
For the reactor of copper nanocluster growth.On the one hand copper nano-cluster nucleating growth in chitosan film can provide for copper nano-cluster
" confinement protection " reduces nonradiative transition and improves fluorescence intensity；On the other hand, chitosan is in film forming procedure, with solvent
Volatilization enhances intermolecular collision probability, accelerates reaction speed.
The chitosan solution of debita spissitudo is mixed at room temperature with the raw material of synthesis copper nano-cluster, is then being suitable for
At a temperature of form a film growth.The fluorescence intensity for the fluorescence copper nano-cluster that one-step method generates after reaction obtains larger raising and contracting
Short reaction time.This method is easy to operate, environmentally protective.
Summary of the invention
The present invention is realized by one-step method using chitosan film as the high fluorescence copper nano-cluster of carrier rapid synthesis, and copper is overcome
The disadvantages of nanocluster fluorescence intensity is low, synthesis step is complicated, the reaction time is longer.
Technical solution of the present invention:
A method of using polymer film as the high fluorescence copper nano-cluster of carrier rapid synthesis, steps are as follows:
(1) chitosan of certain mass is weighed, glacial acetic acid is added dropwise and makes it completely dissolved, configuration quality percent concentration is
The chitosan solution of 1.5%-2.5%；
(2) at room temperature, that glutathione solution and Gerhardite solution are added to step (1) resulting chitosan is molten
In liquid, gained mixed solution is stirred evenly；The molar ratio for controlling glutathione and Gerhardite is 0.5:1~10:1.
(3) step (2) resulting mixed solution is reacted into 5-7h in 35-45 DEG C of air blast bellows.
The mass percent concentration of the chitosan solution is 2%.
The molar ratio of the glutathione and Gerhardite is preferably 5:1.
The reaction temperature is preferably 40 DEG C.
The reaction time is preferably 6h.
Beneficial effects of the present invention: the present invention is received by one-step method by the copper of the high fluorescence of carrier rapid synthesis of chitosan film
Rice cluster, chitosan film can protect copper nano-cluster as good nano-reactor, reduce the energy of nonradiative transition loss, into
And improve fluorescence intensity.On the other hand, chitosan can accelerate the life of copper nano-cluster in film forming procedure as the solvent evaporates
Long rate shortens the reaction time.
Detailed description of the invention
Fig. 1 is chitosan film/copper nano-cluster complex fluorescence excitation and the transmitting spectrogram of synthesis.
Fig. 2 is chitosan film/copper nano-cluster compound ultra-violet absorption spectrum.
Fig. 3 is the different mol ratio of embodiment 1 glutathione and Gerhardite.
Fig. 4 is chitosan film/copper nano-cluster compound transmission electron microscope figure.
Fig. 5 is chitosan film/copper nano-cluster compound x-ray photoelectron spectroscopy figure.
Fig. 6 is the atomic force microscopy diagram of chitosan film.
Fig. 7 is chitosan film/copper nano-cluster compound atomic force microscopy diagram.
Specific embodiment
Below in conjunction with attached drawing and technical solution, a specific embodiment of the invention is further illustrated.
Examples 1 to 5
It is a kind of using polymer film as the synthetic method of the high fluorescence copper nano-cluster of carrier rapid synthesis, the method includes as follows
Step:
(1) chitosan of certain mass is weighed, glacial acetic acid is added dropwise and makes it completely dissolved, the chitosan that configuration concentration is 2%
Solution.
(2) at room temperature, glutathione solution (2.5mL, 0.1M) and Gerhardite solution are added to step (1) institute
In the chitosan solution obtained, gained mixed solution is stirred evenly；The molar ratio of control control glutathione and Gerhardite
For 5:1.The different mol ratio value of the Examples 1 to 5 is shown in Table 1.
(3) step (2) resulting mixed solution is reacted into 6h in 40 DEG C of air blast bellows.
Chitosan film/copper nano-cluster compound maximum excitation and launch wavelength are respectively 345nm and 366nm (Fig. 1).It is purple
Outer absorption spectrum (Fig. 2) no apparent absorption peak at 500~600nm, shows fluorescence copper nano-cluster rather than copper nano-particle
Success synthesizes in chitosan film.Glycan film/copper nano-cluster compound transmission electron microscope figure (Fig. 4) shows to exist simultaneously
Chitosan film and copper nano-cluster, and copper nano-cluster is uniformly distributed in film.In addition, x-ray photoelectron spectroscopy figure (Fig. 5) exists
There is not the peak of bivalent cupric ion in 942eV, shows that bivalent cupric ion is reduced completely, in 932.2eV (Cu in figure
2P3/2) and 952.2eV (Cu 2P1/2) peak that occurs, show the copper in copper nano-cluster containing zeroth order, it was demonstrated that copper nano-cluster is in shell
Successful synthesis in glycan film.The atomic force microscope (Fig. 6) of chitosan film shows that chitosan has less hole, when copper nanometer
After cluster is grown in chitosan film, the quantity in hole increases and aperture increases.
1 Examples 1 to 5 different mol ratio value of table
Claims (8)
1. a kind of using polymer film as the method for the high fluorescence copper nano-cluster of carrier rapid synthesis, which is characterized in that steps are as follows:
(1) chitosan of certain mass is weighed, glacial acetic acid is added dropwise and makes it completely dissolved, configuration quality percent concentration is 1.5%-
2.5% chitosan solution；
(2) at room temperature, glutathione solution and Gerhardite solution are added to step (1) resulting chitosan solution
In, gained mixed solution stirs evenly；The molar ratio for controlling glutathione and Gerhardite is 0.5:1~10:1；
(3) step (2) resulting mixed solution is reacted into 5-7h in 35-45 DEG C of air blast bellows.
2. according to claim 1 using polymer film as the method for the high fluorescence copper nano-cluster of carrier rapid synthesis, feature
It is, the mass percent concentration of the chitosan solution is 2%.
3. it is according to claim 1 or 2 using polymer film as the method for the high fluorescence copper nano-cluster of carrier rapid synthesis, it is special
Sign is that the molar ratio of the glutathione and Gerhardite is 5:1.
4. it is according to claim 1 or 2 using polymer film as the method for the high fluorescence copper nano-cluster of carrier rapid synthesis, it is special
Sign is that the reaction temperature is 40 DEG C.
5. according to claim 3 using polymer film as the method for the high fluorescence copper nano-cluster of carrier rapid synthesis, feature
It is, the reaction temperature is 40 DEG C.
6. according to claim 1, using polymer film as the method for the high fluorescence copper nano-cluster of carrier rapid synthesis described in 2 or 5,
It is characterized in that, the reaction time is 6h.
7. according to claim 3 using polymer film as the method for the high fluorescence copper nano-cluster of carrier rapid synthesis, feature
It is, the reaction time is 6h.
8. according to claim 4 using polymer film as the method for the high fluorescence copper nano-cluster of carrier rapid synthesis, feature
It is, the reaction time is 6h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109613266A (en) * | 2018-12-30 | 2019-04-12 | 吉林大学 | It is a kind of detection glycosylated albumin and its concentration method, detection glycated amino acid oxidizing ferment -one amine oxidase and its concentration method |
| CN111440343A (en) * | 2020-06-03 | 2020-07-24 | 齐鲁工业大学 | Preparation method of fluorescence-enhanced copper cluster and nano-cellulose composite film |
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Cited By (4)
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| CN111440343A (en) * | 2020-06-03 | 2020-07-24 | 齐鲁工业大学 | Preparation method of fluorescence-enhanced copper cluster and nano-cellulose composite film |
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