CN105598466A - Synthesizing method for fluorescent copper nano cluster - Google Patents

Synthesizing method for fluorescent copper nano cluster Download PDF

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Publication number
CN105598466A
CN105598466A CN201610032140.6A CN201610032140A CN105598466A CN 105598466 A CN105598466 A CN 105598466A CN 201610032140 A CN201610032140 A CN 201610032140A CN 105598466 A CN105598466 A CN 105598466A
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China
Prior art keywords
copper nano
cluster
fluorescence
synthesizing method
lysozyme
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Pending
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CN201610032140.6A
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Chinese (zh)
Inventor
韩冰雁
许杰
侯绪芬
相荣超
李莹
彭婷婷
于明波
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Dalian University of Technology
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Dalian University of Technology
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Priority to CN201610032140.6A priority Critical patent/CN105598466A/en
Publication of CN105598466A publication Critical patent/CN105598466A/en
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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
    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • 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
    • 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

Abstract

The invention relates to a synthesizing method for a fluorescent copper nano cluster and belongs to the field of biochemistry technologies. According to the synthesizing method, first, a solution containing Cu+2 and a lysozyme solution are mixed evenly, then hydroxylammonium chloride is added into the mixture, the pH value is adjusted to be 10-13, reaction is performed for 6-24 h, and the mole ratio of Cu+2 to lysozyme to hydroxylammonium chloride is 1:1-8:40-400. The synthesizing method has the advantages that the synthesized fluorescent copper nano cluster emits bright fluorescence and is good in water solubility, high in stability, good in biocompatibility and low in toxicity.

Description

A kind of synthetic method of fluorescence copper nano-cluster
Technical field
The synthetic method that the present invention relates to a kind of fluorescence copper nano-cluster, belongs to technological field of biochemistry.
Background technology
In recent years, the extra small fluorescence metal nano-cluster that comprises several to dozens of metallic atoms, by atom and large-sizedNano particle couples together, and due to its physics and chemistry character that depends on size uniqueness, causes extensive concern. Due toThe size of metal nanometre cluster is similar to Fermi's wavelength of electronics, the property that it presents discrete energy level and is similar to moleculeMatter, for example: the transition of electron state that size is adjustable and strong photoluminescent property. That metal nanometre cluster is considered to is novel,Potential and practical nano material, have actual application, for example: cell imaging, ion sensor in a lot of fieldsAnd catalysis. Compared with traditional fluorescence quantum, metal nanometre cluster has much superior character, for example: low toxicity, superSmall size, good biocompatibility and multi-functional surface chemical property make it obtain more and more at biochemical fieldMany concerns.
In more than ten years in the past, the broad research of fluorescence metal nano-cluster mainly concentrates on synthetic fluorescence Au, Ag and PtNano-cluster, applies various types of templates, for example: polypeptide, protein, DNA, polymer, dendritic macromoleThe little molecule of polymer and biological thiol. But Au, Ag and Pt are noble metals, therefore, Au, Ag and Pt nano-clusterSynthetic is very expensive. As everyone knows, base metal element Cu rich content on earth, in daily lifeCheap and easy to get especially. Copper nano-cluster, as a kind of potential nano material, can be used in catalysis, sensing, cell markMultiple research fields such as note and cell imaging. But, because synthetic super undersized copper nano-cluster is very difficult,Even if the copper nano-cluster synthesizing is also easily oxidized in air, prepare the copper nano-cluster of extra small size and high stabilityRemain a current significant challenge, therefore, compare with the synthetic method of Ag nano-cluster with Au, the closing of copper nano-clusterBecome still in an elementary step.
Summary of the invention
The present invention synthesizes a kind of new fluorescence copper nano-cluster, and it is bright, water-soluble that this fluorescence copper nano-cluster has emitting fluorescenceGood, stability is high, good biocompatibility and low toxin.
The invention provides a kind of synthetic method of fluorescence copper nano-cluster, described synthetic method is for first will be containing Cu2+SolutionMix with lysozyme soln, then hydroxylamine hydrochloride is added wherein, regulate pH to 10～13, reaction 6～24h, described inCu2+, lysozyme and hydroxylamine hydrochloride mol ratio be 1:1～8:40～400.
Reaction temperature of the present invention is preferably 20～45 DEG C.
Beneficial effect of the present invention is: synthetic fluorescence copper nano-cluster has that emitting fluorescence is bright, good water solubility, stabilityHeight, good biocompatibility and low toxin.
Brief description of the drawings
Accompanying drawing 9 width of the present invention,
Fig. 1 is the fluorescence intensity of the synthetic fluorescence copper nano-cluster of embodiment 2～5;
Fig. 2 is the fluorescence intensity of the synthetic fluorescence copper nano-cluster of embodiment 6～12;
Fig. 3 is the fluorescence intensity of the synthetic fluorescence copper nano-cluster of embodiment 13～17;
Fig. 4 is the fluorescence intensity of the synthetic fluorescence copper nano-cluster of embodiment 18～21;
Fig. 5 is the fluorescence intensity of the synthetic fluorescence copper nano-cluster of embodiment 22～27;
Fig. 6 is the UV-vis abosrption spectrogram of the synthetic fluorescence copper nano-cluster of embodiment 10 and lysozyme;
Fig. 7 is fluorescence excitation and the utilizing emitted light spectrogram of the synthetic fluorescence copper nano-cluster of embodiment 10;
Fig. 8 is the H of different molar concentrations2O2On the impact of the synthetic fluorescence copper nano-cluster fluorescence intensity of embodiment 10;
Fig. 9 is 4 DEG C of fluorescence copper nano-clusters and the reality of reacting after 16h that the embodiment 10 keeping in Dark Place after 2 months is syntheticExecute the fluorescence emission spectrogram of example 10 fluorescence copper nano-clusters.
Detailed description of the invention
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but not withAny mode limits the present invention.
In following embodiment, if no special instructions, the experimental technique using is conventional method, the reagent usingDeng all can buying from chemistry or biological reagent company.
Describe the specific embodiment of the present invention in detail below in conjunction with technical scheme.
Embodiment 1～5
A synthetic method for fluorescence copper nano-cluster, described synthetic method is first by the Cu (NO of 5mL variable concentrations3)225 DEG C of stirring 10min of lysozyme soln that solution and 5mL concentration are 20mg/mL, then be 8M by 1mL concentrationHydroxylamine hydrochloride adds wherein, and with NaOH adjusting pH to 12,25 DEG C of stirring reaction 16h, obtain fluorescence copper nano-cluster;
Described embodiment 1～5Cu (NO3)2The concentration of solution is in table 1.
Table 1 embodiment 1～5Cu (NO3)2The concentration of solution
Embodiment 6～12
A synthetic method for fluorescence copper nano-cluster, described synthetic method is is first 5mM by 5mL concentrationCu(NO3)225 DEG C of stirring 10min of lysozyme soln that solution and 5mL concentration are 20mg/mL, then by 1mL differenceThe hydroxylamine hydrochloride of concentration adds wherein, and with NaOH adjusting pH to 12,25 DEG C of stirring reaction 16h, obtain fluorescence copperNano-cluster;
The concentration of described embodiment 6～12 hydroxylamine hydrochlorides is in table 2.
The concentration of table 2 embodiment 6～12 hydroxylamine hydrochlorides
Embodiment 13～17
A synthetic method for fluorescence copper nano-cluster, described synthetic method is is first 5mM by 5mL concentrationCu(NO3)225 DEG C of stirring 10min of lysozyme soln that solution and 5mL concentration are 20mg/mL, then by 1mL concentrationFor the hydroxylamine hydrochloride of 8M adds wherein, regulate different pH values, 25 DEG C of stirring reaction 16h, obtain fluorescence copper nanometerBunch;
The pH value of described embodiment 13～17 is in table 3.
The pH value of table 3 embodiment 13～17
Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17
PH value 4 6 8 10 12
Embodiment 18～21
A synthetic method for fluorescence copper nano-cluster, described synthetic method is is first 5mM by 5mL concentrationCu(NO3)225 DEG C of stirring 10min of lysozyme soln that solution and 5mL concentration are 20mg/mL, then by 1mL concentrationFor the hydroxylamine hydrochloride of 8M adds wherein, with NaOH adjusting pH to 12, different temperatures stirring reaction 16h, obtainsFluorescence copper nano-cluster;
The reaction temperature of described embodiment 18～21 is in table 4.
The reaction temperature of table 4 embodiment 18～21
Embodiment 22～27
A synthetic method for fluorescence copper nano-cluster, described synthetic method is is first 5mM by 5mL concentrationCu(NO3)225 DEG C of stirring 10min of lysozyme soln that solution and 5mL concentration are 20mg/mL, then by 1mL concentrationFor the hydroxylamine hydrochloride of 8M adds wherein, with NaOH adjusting pH to 12,25 DEG C of times that stirring reaction is different,To fluorescence copper nano-cluster;
The reaction time of described embodiment 22～27 is in table 5.
The reaction time of table 5 embodiment 22～27
Effect example 1
By fluorescence copper nano-cluster solution synthetic embodiment 10 and lysozyme soln test UV-vis abosrption spectrogram, knotFruit sees that Fig. 6, a are the UV-vis abosrption spectrogram of the synthetic fluorescence copper nano-cluster of embodiment 10, and b is lysozymeUV-vis abosrption spectrogram, is obtained by Fig. 6, compared with the obvious absworption peak of lysozyme at 280nm place, and embodiment 10Synthetic fluorescence copper nano-cluster does not have obvious absworption peak in whole UV-vis light district, and what near 280nm, occur is micro-Little hump is because unreacted lysozyme causes. In addition, there is no obvious surface plasma at 560～600nmResonance body absorption band, proves not have large-sized copper nano-particle to generate.
Effect example 2
By synthetic embodiment 10 fluorescence copper nano-cluster solution testing fluorescence excitation and utilizing emitted light spectrogram, the results are shown in Figure 7,A is fluorescence excitation spectrum, and b is fluorescence emission spectrum, is obtained by Fig. 7, and Stokes displacement is 262nm, proves utilizing emitted lightSpectrum can effectively be avoided the interference from excitation source. Compared with organic dyestuff, the Stokes displacement of large scale can haveEffect is avoided the intersection between excitation spectrum and emission spectrum.
Effect example 3
Be 0nM, 10nM, 100nM, 500nM, 1 μ M, 10 μ M, 100 μ M, 500 μ M, 1mM by concentrationH2O2The fluorescence copper nano-cluster obtaining with isopyknic embodiment 10 mixes, and 25 DEG C of reaction 12h survey respectively that it is glimmeringLight intensity value, investigates the H of different molar concentrations2O2The shadow of the fluorescence copper nano-cluster fluorescence intensity that embodiment 10 is obtainedRing, the results are shown in Figure 8, obtained H by Fig. 82O2The fluorescence intensity level of the fluorescence copper nano-cluster that embodiment 10 is obtained almostWithout impact, prove that the fluorescence copper nano-cluster that embodiment 10 obtains has strong anti-oxidation.
Effect example 4
4 DEG C of fluorescence copper nano-clusters and the embodiment 10 reacting after 16h that the embodiment 10 keeping in Dark Place after 2 months is syntheticThe fluorescence emission spectrum of fluorescence copper nano-cluster compare, the results are shown in Figure 9, a and be the glimmering of embodiment 10 after reaction 16hThe fluorescence emission spectrum of light copper nano-cluster, b is that 4 DEG C of synthetic fluorescence copper of the embodiment 10 keeping in Dark Place after 2 months are receivedThe fluorescence emission spectrum of rice bunch, is obtained by Fig. 9, and both almost do not change by fluorescence intensity level, prove that embodiment 10 synthesizesFluorescence copper nano-cluster there is high stability.

Claims (2)

1. a synthetic method for fluorescence copper nano-cluster, is characterized in that: described synthetic method is for first will be containing Cu2+'sSolution and lysozyme soln mix, then hydroxylamine hydrochloride is added wherein, regulate pH to 10～13, reaction 6～24h,Described Cu2+, lysozyme and hydroxylamine hydrochloride mol ratio be 1:1～8:40～400.
2. synthetic method according to claim 1, is characterized in that: described reaction temperature is 20～45 DEG C.
CN201610032140.6A 2016-01-18 2016-01-18 Synthesizing method for fluorescent copper nano cluster Pending CN105598466A (en)

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CN107159899A (en) * 2017-04-26 2017-09-15 大连理工大学 A kind of method that overstable copper nano-cluster is synthesized by protective agent of proline
CN107498068A (en) * 2017-09-22 2017-12-22 大连理工大学 A kind of preparation method of flower-like nanometer copper
CN108907221A (en) * 2018-06-10 2018-11-30 江苏经贸职业技术学院 A kind of synthetic method of copper nano-cluster
CN115365494A (en) * 2022-09-13 2022-11-22 嘉兴学院 Preparation method of silver-coated copper powder and application of silver-coated copper powder in conductive paste

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107159899A (en) * 2017-04-26 2017-09-15 大连理工大学 A kind of method that overstable copper nano-cluster is synthesized by protective agent of proline
CN107498068A (en) * 2017-09-22 2017-12-22 大连理工大学 A kind of preparation method of flower-like nanometer copper
CN108907221A (en) * 2018-06-10 2018-11-30 江苏经贸职业技术学院 A kind of synthetic method of copper nano-cluster
CN115365494A (en) * 2022-09-13 2022-11-22 嘉兴学院 Preparation method of silver-coated copper powder and application of silver-coated copper powder in conductive paste

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Application publication date: 20160525