CN105441069B - A kind of method using small molecule as the high fluorescence alloy nanocluster of templated synthesis - Google Patents
A kind of method using small molecule as the high fluorescence alloy nanocluster of templated synthesis Download PDFInfo
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- CN105441069B CN105441069B CN201510794258.8A CN201510794258A CN105441069B CN 105441069 B CN105441069 B CN 105441069B CN 201510794258 A CN201510794258 A CN 201510794258A CN 105441069 B CN105441069 B CN 105441069B
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- copper
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- 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
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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Abstract
The present invention relates to a kind of using small molecule as the method for the high fluorescence alloy nanocluster of templated synthesis, belong to technical field of bioengineering, methods described comprises the following steps：1. glutathione solution and copper ion solution are mixed, regulation pH is 4~5；The mol ratio of the glutathione and copper ion is 4~8：1；2. silver ion solution is added into step 1. to mix in products obtained therefrom；The mol ratio of the glutathione, copper ion and silver ion is 20~40：5：4~6, the present invention has the beneficial effect that the present invention synthesizes alloyed copper silver nanoclusters by introducing silver ion, strengthens the fluorescence intensity of copper nano-cluster, improves its stability, and provide a kind of new nano-cluster.In addition, synthetic method of the present invention is easily-controllable, simple, quick.
Description
Technical field
The present invention relates to a kind of using small molecule as the method for the high fluorescence alloy nanocluster of templated synthesis, belong to bioengineering skill
Art field.
Background technology
Metal nanometre cluster is made up of several to more than ten atom, have that toxicity is low, size is small due to it, photostability by force with
And the advantages of good water solubility so that metal nanometre cluster is increasingly becoming a kind of wide variety of nanometer in many fields of nanosecond science and technology
Material.
The synthesis of metal nanometre cluster mainly uses template synthesis method, and the template often used has polymer, DNA, polypeptide and egg
White matter, and synthesize metal nanometre cluster using biological micromolecule recently and cause extensive concern.Because biological micromolecule
Synthesis metal nanometer cluster has its superior condition, including reaction condition mitigations, good biocompatibility, it is simple in construction clearly, divide
Son is measured small etc..
Glutathione (GSH) is a kind of tripeptides containing γ-amido link and sulfydryl, is by glutamic acid, cysteine and sweet ammonia
Acid is combined, with antioxidation and integration detoxication.Glutathione is widely present in animals and plants, is had in vivo
Important effect.Using the sulfydryl on glutathione can and the special combination of metal, synthesis metal nanometre cluster by extensively should
With.
At present, research of the people to nano-cluster has gradually been transferred to cheap copper by expensive gold, silver, platinum
On, but synthesis copper nano-cluster have the shortcomings that it is very big, stability difference with fluorescence intensity it is low.
The content of the invention
The present invention on the basis of synthesis copper nano-cluster by using small molecule glutathione as template, adding silver ion synthesis
Copper-silver alloy nano-cluster, solves above mentioned problem.
The invention provides a kind of method using small molecule as the high fluorescence alloy nanocluster of templated synthesis, methods described includes
Following steps：
1. glutathione solution and copper ion solution are mixed, regulation pH is 4~5；
The mol ratio of the glutathione and copper ion is 4~8：1；
2. silver ion solution is added into step 1. to mix in products obtained therefrom；
The mol ratio of the glutathione, copper ion and silver ion is 20~40：5：4~6.
The concentration of glutathione solution of the present invention is preferably 20~80mM.
The concentration of copper ion solution of the present invention is preferably 2.5~20mM.
The concentration of silver ion solution of the present invention is preferably 80~120mM.
The present invention is preferably that ethanol is added into step 2. to mix in products obtained therefrom.
The addition of ethanol of the present invention be preferably step 2. products obtained therefrom volume 10~60%.
The present invention has the beneficial effect that：
The present invention synthesizes alloyed copper-silver nanoclusters by introducing silver ion, strengthens the fluorescence intensity of copper nano-cluster, improves it
Stability, and a kind of new nano-cluster is provided.In addition, synthetic method of the present invention is easily-controllable, simple, quick.
Brief description of the drawings
The width of accompanying drawing 5 of the present invention,
Fig. 1 is influence of the glutathione of different mol ratio with copper nitrate to synthesis copper nanocluster fluorescence intensity；
Fig. 2 is influence of the silver nitrate of various concentrations to synthesis alloyed copper-silver nanoclusters fluorescence intensity；
Fig. 3 is the fluorescence spectrum of copper nano-cluster and alloyed copper-silver nanoclusters；
Fig. 4 is copper nano-cluster and illuminated diagram of the alloyed copper-silver nanoclusters under visible ray and ultraviolet light；
Fig. 5 is alloyed copper-fluorescence spectrum of the silver nanoclusters system in the ethanol of different volumes percentage.
Embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
In following embodiments, unless otherwise specified, used experimental method is conventional method, agents useful for same etc.
Chemically or biological reagent company purchase.
Describe the embodiment of the present invention in detail below in conjunction with technical scheme.
Embodiment 1
The synthesis of copper nano-cluster
The 5mL copper nitrate solutions of various concentrations are added in 5mL 80mM reduced glutathione solution respectively, made also
The mol ratio of prototype glutathione and copper ion is respectively 8：1、6：1、4：1、2：1, pH is adjusted to 5 with 1M NaOH solutions respectively,
Room temperature is mixed；
The fluoroscopic examination under 350nm excitation wavelengths, is obtained by Fig. 1, and glutathione is 4 with copper nitrate mol ratio：1 is better than other
Ratio, when glutathione is excessive, due to the interaction between glutathione and copper nitrate, produces a kind of compound to draw
Play Quenching of fluorescence.
Embodiment 2
The synthesis of alloyed copper-silver nanoclusters
1. 5mL 20mM copper nitrate solutions are added in 5mL 80mM reduced glutathione solution, it is molten with 1M NaOH
Liquid adjusts pH to 5, and room temperature is mixed；
2. the 1mL silver nitrate solutiones of various concentrations are added to step 1. in products obtained therefrom respectively, make copper ion and silver from
The mol ratio of son is respectively 5：2、5：3、5：4、1：1、5：6, mix；
Fluoroscopic examination under ultraviolet light, is obtained by Fig. 2, when the mol ratio of copper ion and silver ion is 5：When 4, fluorescence intensity is most
It is high.Silver nitrate solution is added, the fluorescence intensity of copper nano-cluster is not only improved, also improves its stability.Fig. 3 is copper nano-cluster with closing
The fluorescence spectrum of golden copper-silver nanoclusters.Fig. 4 is copper nano-cluster and hair of the alloyed copper-silver nanoclusters under visible ray and ultraviolet light
Light figure, 1 and 2 be respectively copper nano-cluster and the illuminated diagram of alloyed copper-silver nanoclusters under visible light, 1 color be it is faint yellow, 2
Color be yellow, 3 and 4 be respectively copper nano-cluster and the illuminated diagram of alloyed copper-silver nanoclusters under ultraviolet light, and 3 color is
Red, 4 color is orange-yellow.
Embodiment 3
The synthesis of alloyed copper-silver nanoclusters
1. 5mL 80mM reduced glutathiones solution is mixed with 5mL 20mM copper nitrate solutions, uses 1M NaOH solutions
PH to 5 is adjusted, room temperature is mixed；
2. 1mL 80mM silver nitrate solutiones are added into step 1. to mix in products obtained therefrom；
3. the ethanol of step 2. products obtained therefrom volume 10%, 20%, 40%, 60% being added into step respectively, 2. gained is produced
Mixed in product；
By step, 3. products obtained therefrom presses 2 times of volume dilution respectively, and fluoroscopic examination is obtained by Fig. 5, and ethanol assembles system
Inducing phenomena, so as to further improve the fluorescence intensity of system.
Claims (6)
1. a kind of method using small molecule as the high fluorescence alloy nanocluster of templated synthesis, it is characterised in that：Methods described is included such as
Lower step：
1. glutathione solution and copper ion solution are mixed, regulation pH is 4~5；
The mol ratio of the glutathione and copper ion is 4：1；
2. silver ion solution is added into step 1. to mix in products obtained therefrom；
The mol ratio of the glutathione, copper ion and silver ion is 20：5：4.
2. according to the method described in claim 1, it is characterised in that：The concentration of the glutathione solution is 20~80mM.
3. according to the method described in claim 1, it is characterised in that：The concentration of the copper ion solution is 2.5~20mM.
4. according to the method described in claim 1, it is characterised in that：The concentration of the silver ion solution is 80~120mM.
5. according to the method described in claim 1, it is characterised in that：Ethanol is added into step 2. to mix in products obtained therefrom.
6. method according to claim 5, it is characterised in that：The addition of the ethanol is step 2. products obtained therefrom volume
10~60%.
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| CN105602554B (en) * | 2016-03-09 | 2018-01-05 | 吉林大学 | Copper nano-cluster self assembly fluorescent material, preparation method and its application in LED encapsulation of gold doping |
| CN107552807B (en) * | 2016-06-30 | 2020-01-17 | 郑州科斗科技有限公司 | Preparation method capable of preparing gold nanorods with controllable size and dispersibility on large scale |
| CN107290313A (en) * | 2017-06-12 | 2017-10-24 | 湖南科技大学 | A kind of preparation method and application of the golden copper composite Nano cluster of Two Colour Fluorescence |
| CN107987827B (en) * | 2017-12-11 | 2020-10-23 | 无锡市疾病预防控制中心 | Preparation method of copper/silver alloy nanocluster with aggregation-induced luminescence and adjustable luminescence |
| CN108420748B (en) * | 2018-04-25 | 2021-11-30 | 上海谦懋纺织科技有限公司 | Processing technology of blue copper peptide combined with nano gold and nano diamond structure |
| 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 |
| CN111253936B (en) * | 2020-03-30 | 2021-03-16 | 吉林大学 | Metal nano-cluster fluorescent powder, preparation method thereof and LED |
| CN111570820B (en) * | 2020-04-21 | 2022-01-11 | 武汉理工大学 | Preparation method and application of copper nanocluster |
| CN111440343B (en) * | 2020-06-03 | 2022-10-04 | 齐鲁工业大学 | Preparation method of fluorescence-enhanced copper cluster and nano-cellulose composite film |
| CN113061261A (en) * | 2021-03-30 | 2021-07-02 | 深圳第三代半导体研究院 | Copper nano-cluster fluorescent powder and preparation method thereof |
| CN114523123B (en) * | 2022-02-24 | 2023-10-20 | 华南理工大学 | Nanocellulose-based fluorescent silver nanocluster and preparation method and application thereof |
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| CN104749151A (en) * | 2015-04-08 | 2015-07-01 | 东南大学 | Application of glutathione-based stable gold nano cluster particles to detection of sulfhydryl compound |
| CN104865229A (en) * | 2015-01-23 | 2015-08-26 | 江南大学 | Preparation method of copper nano-cluster fluorescence probe for detecting tiny amount of lead ions in water through ultrasonic technology |
| CN104985193A (en) * | 2015-07-24 | 2015-10-21 | 天津大学 | Alloy nano-particle preparation method based on protein reduction method |
| CN105038771A (en) * | 2015-05-18 | 2015-11-11 | 汕头大学 | Glutathione-Au/Ag alloy nano material, preparation method and application thereof |
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| CN104865229A (en) * | 2015-01-23 | 2015-08-26 | 江南大学 | Preparation method of copper nano-cluster fluorescence probe for detecting tiny amount of lead ions in water through ultrasonic technology |
| CN104749151A (en) * | 2015-04-08 | 2015-07-01 | 东南大学 | Application of glutathione-based stable gold nano cluster particles to detection of sulfhydryl compound |
| CN105038771A (en) * | 2015-05-18 | 2015-11-11 | 汕头大学 | Glutathione-Au/Ag alloy nano material, preparation method and application thereof |
| CN104985193A (en) * | 2015-07-24 | 2015-10-21 | 天津大学 | Alloy nano-particle preparation method based on protein reduction method |
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