CN111548792B - Fluorescent copper nanocluster and preparation method and application thereof - Google Patents
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Abstract
The invention provides a fluorescent copper nanocluster and a preparation method and application thereof, wherein the preparation method comprises the following steps of mixing, by volume, 2-20 parts of 0.01-0.1 mol.L ‑1 2 to 20 portions of 0.01 to 0.1 mol.L of 3, 4-dihydroxyphenylalanine aqueous solution ‑1 And mixing the copper salt aqueous solution, stirring the mixed solution uniformly, and then carrying out microwave heating to obtain the fluorescent copper nano-cluster solution. The method has the advantages of simple preparation process, low instrument requirement, controllable reaction condition, short treatment time, low cost and the like, avoids adding reducing agents such as hydrazine hydrate, ascorbic acid and the like, and the prepared copper nano cluster has the advantages of small size, good water solubility, strong photobleaching resistance and the like, can generate fluorescence, has a fluorescence emission peak of about 514nm, has a fluorescence copper nano cluster quantum yield of up to 0.58 percent, has higher sensitivity and selectivity on bulk iron ions, and can be used for constructing a sensing system of the iron ions.
Description
Technical Field
The invention belongs to the technical field of fluorescent nano materials, and particularly relates to a fluorescent copper nanocluster and a preparation method and application thereof.
Background
Metal Nanoclusters (NCs) are generally composed of several to tens of atoms, the properties of which are controlled by the sub-nanometer size thereof, and as a fluorescent material, have the advantages of good biocompatibility, large stokes shift, easy functionalization and the like. Therefore, the method attracts the attention of many researchers, so that the method is successfully applied to the fields of biosensing, catalysis, imaging and the like. Common metal nanoclusters mainly comprise metal nanoclusters of gold, silver, platinum, copper and the like and alloy nanoclusters containing two or more metal elements. The synthesis of gold, silver and platinum noble metal nanoclusters is high in cost and complicated in procedure, while copper is low in price and belongs to the same main group with gold and silver, and has similar properties. Therefore, the copper nano cluster has good research prospect.
To date, various functionalized copper nanoclusters have been successfully prepared and applied to the sensory detection of adenosine 5' -triphosphate (ATP), glucose, ascorbic acid, Picric Acid (PA), and the like. For example, Wang et al, in conjunction with Target Cycle Strand Displacement Amplification (TCSDA), synthesized strong red fluorescent copper nanoclusters (CuNCs) using double stranded DNA (dsDNA) as a template and applied to quantitative detection of adenosine 5' -triphosphate (ATP) by target induction (Microchimica Acta,2017,184(10), 4183-4188). Gou et al report that a glucose sensing detection method (ACS Applied Materials) is established based on fluorescence enhancement of GSH protected Cu Nanoclusters (NCs)&Interfaces,2019,11(6),6561 and 6567). CuNCs stabilized with tannic acid were developed by Rao et al and used to detect ascorbic acid AA (Microchimica Acta,2016,183(5), 1651) -1657). Patel et al used Pyrilamine (PM) and Glutathione (GSH) to synthesize PM-GSH-CuNCs for the selective detection of Picric Acid (PA) (Biosensors and Bioelectronics,2018,102, 196-. Luo et al reported GSH-terminated CuNCs, which have been successfully applied to pH sensing and VB 1 The aggregation-induced emission property of Glutathione (GSH) -stabilized CuNCs is detected and explored, and a new opportunity is provided for the construction of copper nanoclusters in light-emitting diodes, chemical sensors and biological imaging systems (Talanta,2015,144, 488-495). However, research on CuNCs is still in the preliminary stage, and a new strategy for rapidly and efficiently synthesizing stable and highly fluorescent CuNCs by using other protective agents needs to be explored, and the application field of the CuNCs is further widened.
3, 4-Dihydroxyphenylalanine (DOPA) is a neurotransmitter generally used for the treatment of neurological diseases (e.g., Parkinson's syndrome), and in addition, DOPA plays an important role in the organism, producing dopaquinone under the action of tyrosinase, which is then spontaneously converted into melanin, or producing dopamine under the action of aromatic amino acid decarboxylase, which is then formed into norepinephrine and epinephrineAdrenalin and the like. DOPA is an oxidation product generated by hydroxylation of tyrosine under the action of tyrosine hydroxylase, has catechol hydroxyl and can further generate other substances with biological activity. The invention selects DOPA as a reducing agent and a stabilizing agent, and successfully synthesizes DOPA stable CuNCs and Fe by a microwave heating method 3+ Can enhance the fluorescence of DOPA-CuNCs, establishes the detection of Fe based on the enhancement 3+ Sensing method and application to Fe in actual sample 3+ Detection of (3).
Disclosure of Invention
In view of this, the invention aims to provide a fluorescent copper nanocluster, and a preparation method and an application thereof, wherein the method is short in preparation time, free of additional reducing agent addition, simple in preparation process, and capable of being used for constructing a sensing system of iron ions, and the prepared copper nanocluster has high sensitivity and selectivity on bulk iron ions.
In order to achieve the purpose of the invention, the following technical scheme is adopted:
a fluorescent copper nano-cluster is prepared by taking 3, 4-dihydroxyphenylalanine as a protective agent and a reducing agent and a soluble copper salt solution as a substrate through a microwave-assisted method.
A preparation method of a fluorescent copper nanocluster comprises the following steps: 2 to 20 portions of 0.01 to 0.1 mol.L according to the volume portion -1 2 to 20 portions of 0.01 to 0.1 mol.L of 3, 4-dihydroxyphenylalanine aqueous solution -1 And mixing the copper salt aqueous solution, stirring the mixed solution uniformly, and then carrying out microwave heating to obtain the fluorescent copper nano-cluster solution.
Further, the copper salt aqueous solution in the above method comprises copper nitrate, copper chloride, copper sulfate aqueous solution; preferably, the aqueous copper salt solution is an aqueous copper nitrate solution.
Preferably, the concentration of the aqueous copper salt solution in the above method is 0.05 mol. L -1 The concentration of the 3, 4-dihydroxyphenylalanine aqueous solution is 0.05 mol.L -1 。
Further, in the method, the molar ratio of the copper salt to the 3, 4-dihydroxyphenylalanine is 3:5-10: 1; preferably, the molar ratio of the copper salt to the 3, 4-dihydroxyphenylalanine is 5: 3.
Further, in the method, the heating power of the microwave heating is 53-385W, and the heating time is 3-18 min; preferably, the heating power of the microwave heating is 119W, and the heating time is 12 min.
Further, the method also comprises the steps of cooling the mixed solution after microwave heating, and then carrying out centrifugal purification to remove large-particle copper nanoclusters; further, the centrifugation condition is 5000-; preferably, the centrifugation conditions are 9000rpm centrifugation for 10 min.
The fluorescent copper nanocluster is applied to iron ion detection.
Further, the iron ion detection method comprises the following steps: and adding 100 mu L of the fluorescent copper nanocluster aqueous solution and different concentrations of iron ion standard solutions into a fluorescent cuvette, measuring the fluorescence spectrum of the fluorescent copper nanocluster aqueous solution by taking 394nm as an excitation wavelength to obtain a linear relation between a fluorescence intensity logarithm and an iron ion concentration logarithm, adding a sample to be detected, and quantitatively detecting the concentration of the iron ions in the sample to be detected through the change of fluorescence intensity.
Compared with the prior art, the invention has the advantages that:
(1) the invention adopts a microwave-assisted method to synthesize the fluorescent copper nanoclusters in one step by taking 3, 4-dihydroxyphenylalanine as a protective agent and a reducing agent, has the advantages of simple preparation process, low instrument requirement, controllable reaction conditions, short treatment time, low cost and the like, avoids adding the reducing agents such as hydrazine hydrate, ascorbic acid and the like, and the prepared copper nanoclusters have the advantages of small size, good water solubility, strong photobleaching resistance and the like, can generate fluorescence, have a fluorescence emission peak of about 514nm and have the quantum yield of the fluorescent copper nanoclusters as high as 0.58 percent;
(2)3, 4-dihydroxyphenylalanine is a neurotransmitter, has two ligands of amino and hydroxyl, can form a strong bond with metal copper, and 3, 4-dihydroxyphenylalanine has oxidability and can reduce divalent copper ions into Cu + And Cu 0 Further generating other substances with biological activity;
(3) the iron ions have a fluorescence enhancement effect on the prepared fluorescent copper nanoclusters, and the prepared fluorescent copper nanoclusters can be applied to detection of the iron ions.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. In the drawings:
FIG. 1 is a schematic diagram of the synthesis of fluorescent copper nanoclusters;
FIG. 2 is an ultraviolet absorption spectrum, a fluorescence excitation spectrum and a fluorescence emission spectrum of a fluorescent copper nanocluster of example 3; in the figure: line a: uv-vis absorption spectrum, line b: excitation spectrum, line c: an emission spectrum;
FIG. 3 is a graph of the photodynamic stability of fluorescent copper nanoclusters of example 3 under excitation of 394 nm;
FIG. 4 is the effect of different sodium chloride concentrations on the fluorescence intensity of fluorescent copper nanoclusters of example 3;
FIG. 5 is the effect of different pH environments on the fluorescence intensity of fluorescent copper nanoclusters of example 3;
FIG. 6 is a fluorescence spectrum of fluorescent copper nanoclusters after different anions and cations are added in example 3;
FIG. 7 is a bar graph of fluorescence of the fluorescent copper nanoclusters of example 3 after interaction with various anions and cations;
FIG. 8 is a fluorescence spectrum of fluorescent copper nanoclusters of example 3 after adding iron ions of different concentrations;
fig. 9 is a linear relationship between the logarithm of the fluorescence intensity and the logarithm of the iron ion concentration of the fluorescent copper nanoclusters of example 3.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make the technical solutions of the present application better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
As shown in fig. 1, the formation process of the fluorescent copper nanocluster of the present invention is: irradiating with microwave power of 53-385W for 3-18min, 3, 4-dihydroxyphenylalanine and Cu 2+ Reaction takes place, Cu 2+ Is reduced to Cu + And Cu 0 And the core is aggregated to form the fluorescent copper nano-cluster, the 3, 4-dihydroxyphenylalanine is oxidized into dopaquinone, and the amino in the 3, 4-dihydroxyphenylalanine is coordinated and bonded with the copper and is associated with the surface of the fluorescent copper nano-cluster to form the shell of the fluorescent copper nano-cluster.
Example 1
A preparation method of a fluorescent copper nanocluster comprises the following steps: 2 portions of 0.01 mol.L -1 20 parts of 0.1 mol. L of 3, 4-dihydroxyphenylalanine aqueous solution -1 And (2) mixing the copper nitrate aqueous solution, uniformly stirring the mixed solution, controlling the microwave heating power to be 53W, heating for 18min, taking out the solution after cooling, centrifuging the obtained solution at 12000rpm for 2min, and removing large-particle copper nano clusters to obtain the fluorescent copper nano cluster aqueous solution, wherein the fluorescent emission peak of the fluorescent copper nano clusters is about 514nm, and the quantum yield is 0.08%.
Example 2
A preparation method of a fluorescent copper nanocluster comprises the following steps: 4 parts of 0.03 mol/L -1 An aqueous solution of 3, 4-dihydroxyphenylalanine and 16 parts of 0.08 mol. L -1 And (2) mixing the copper chloride aqueous solution, uniformly stirring the mixed solution, controlling the microwave heating power to be 85W, heating for 15min, taking out after the solution is cooled, centrifuging the obtained solution at 6500rpm for 12min, purifying, and removing large-particle copper nano-clusters to obtain the fluorescent copper nano-cluster aqueous solution, wherein the fluorescent emission peak of the fluorescent copper nano-clusters is about 514nm, and the quantum yield is 0.11%.
Example 3:
a preparation method of a fluorescent copper nanocluster comprises the following steps: 6 portions of 0.05 mol.L -1 10 parts of 0.05 mol. L.of an aqueous solution of 3, 4-dihydroxyphenylalanine -1 And (2) mixing the copper nitrate aqueous solution, uniformly stirring the mixed solution, controlling the microwave heating power to be 119W, heating for 12min, taking out the solution after cooling, centrifuging the obtained solution at 9000rpm for 10min, and removing large-particle copper nano clusters to obtain the fluorescent copper nano cluster aqueous solution, wherein the fluorescent emission peak of the fluorescent copper nano clusters is about 514nm, and the quantum yield is 0.58%.
And adding 100 mu L of fluorescent copper nanocluster aqueous solution into an ultraviolet cuvette and a fluorescent cuvette, and measuring an ultraviolet-visible absorption spectrum and a fluorescence excitation and emission spectrogram of the aqueous solution. As shown in FIG. 2, the fluorescent copper nanoclusters show maximum excitation and emission peaks at 394nm and 514nm respectively, and the ultraviolet-visible absorption peak signals of the fluorescent copper nanoclusters at 394nm are consistent with the fluorescence excitation spectrum.
The aqueous solution of the fluorescent copper nanocluster is subjected to a photodynamic stability experiment, as shown in fig. 3, the aqueous solution of the red fluorescent copper nanocluster can keep good luminescence performance within 60min, which shows that the photodynamic stability is good.
The influence of sodium chloride solutions with different concentrations on the fluorescence intensity of the fluorescent copper nanoclusters is explored for the prepared fluorescent copper nanocluster aqueous solution. Fig. 4 shows that the fluorescence intensity of the fluorescent copper nanocluster does not substantially change with the change of the sodium chloride concentration, which indicates that the decrease of the fluorescence intensity after the iron plasma is added into the fluorescent copper nanocluster in the subsequent experiment is not caused by the increase of the ion intensity, and the influence of the ion intensity on the fluorescence intensity is eliminated. Finally, the influence of the change of the pH environment on the fluorescence intensity of the fluorescent copper nanoclusters is studied, as shown in FIG. 5, the fluorescence intensity of the fluorescent copper nanoclusters is not changed greatly within the range of pH 2-12, and the fact that the fluorescent copper nanoclusters can still maintain a stable structure in acidic and alkaline environments is proved.
Example 4
A preparation method of a fluorescent copper nanocluster comprises the following steps: 14 parts of 0.08 mol.L -1 And 6 parts of 0.03 mol/l aqueous 3, 4-dihydroxyphenylalanine solutionL -1 And (2) mixing the copper sulfate aqueous solution, uniformly stirring the mixed solution, controlling the microwave heating power 372W to heat for 9min, taking out the solution after cooling, centrifuging the obtained solution at 11000rpm for 5min to purify, and removing large-particle copper nano-clusters to obtain the fluorescent copper nano-cluster aqueous solution, wherein the fluorescence emission peak of the fluorescent copper nano-clusters is about 514nm, and the quantum yield is 0.21%.
Example 5
A preparation method of a fluorescent copper nano-cluster comprises the following steps: 20 portions of 0.1 mol.L -1 2 parts of 0.01 mol. L.of an aqueous solution of 3, 4-dihydroxyphenylalanine -1 And (2) mixing the copper nitrate aqueous solution, uniformly stirring the mixed solution, controlling the microwave heating power to 385W, heating for 3min, taking out the solution after cooling, centrifuging the obtained solution at 5000rpm for 20min, and removing large-particle copper nano-clusters to obtain the fluorescent copper nano-cluster aqueous solution, wherein the fluorescent emission peak of the fluorescent copper nano-clusters is about 514nm, and the quantum yield is 0.12%.
Example 6
The application of the fluorescent copper nanocluster prepared by the invention in iron ion detection is as follows:
1) influence of different anions and cations on fluorescence intensity of fluorescent copper nanocluster
Transferring 100 mu L of the aqueous solution of the fluorescent copper nanoclusters prepared in the example 3, adding the aqueous solution of the fluorescent copper nanoclusters into a fluorescence cuvette, and measuring the fluorescence intensity of the fluorescent copper nanoclusters after 11 anions and cations are added under the excitation wavelength of 394nm, as shown in fig. 6, the addition of iron ions can enhance the fluorescence of the fluorescent copper nanoclusters, and other potential interferents have almost no influence on the fluorescence intensity, which indicates that the fluorescent copper nanoclusters have good selectivity on the iron ions. This is due to the electron configuration of the iron ion being 3d, as shown in FIG. 6 5 4s 0 And the half-filled 3d multi-site state causes iron ions to have a high positive charge density, thereby having a stronger electron withdrawing property than other metal ions. In the iron ion sensing system, fluorescent copper nanoclusters induce fluorescence enhancement through the interaction of iron ions and ligands, resulting in aggregation of the fluorescent copper nanoclusters.
Other methods were investigated using the above-mentioned iron ionsThe influence of various possible substances on the fluorescence intensity of the red fluorescent copper nanocluster is as follows: ni 2+ ，Cu 2+ ，Al 3+ ，Mg 2+ ，Mn 2+ ，Ba 2+ ，Zn 2+ ，IO 3 - ，ClO 3 - ，F - ，Pb 2+ . The fluorescence intensity F after only adding the copper nanocluster and 11 kinds of anions and cations in the system was measured, and the fluorescence intensity (F) after only adding the fluorescent copper nanocluster was measured 0 ) As a blank control group. The concentration of other coexisting ions was 20 times that of iron ions, and a bar graph of the fluorescence intensity at 494nm for different anions and cations was plotted, as shown in FIG. 7.
2) Detection of iron ion concentration by fluorescent copper nanocluster
And transferring 100 mu L of the fluorescent copper nanocluster aqueous solution prepared in the example 3, adding the aqueous solution into a sample cell, adding the aqueous solution into a fluorescent cuvette together, adding iron ion standard solutions with different concentrations respectively, and measuring the fluorescence spectrum of the solution by taking 394nm as an excitation wavelength. As shown in fig. 8, the fluorescence of the fluorescent copper nanoclusters gradually increased as the concentration of the iron ion standard solution increased. As shown in FIG. 9, the logarithm of the fluorescence intensity of the fluorescent copper nanocluster is linearly related to the logarithm of the concentration of iron ions, and the change of the logarithm of the fluorescence intensity is represented by logF, wherein F represents the fluorescence intensity of the copper nanocluster in the presence of iron ions, and the linear range of the fluorescence intensity is 1.49X 10 -12 To 1.9X 10 -9 mol·L -1 The linear regression equation is 0.03736X +4.67675, the linear correlation coefficient is 0.99, and the detection limit is 9.15 × 10 -13 mol·L -1 . The fluorescent copper nanocluster is successfully applied to detection of an actual sample water sample, provides important reference significance for water quality detection, and is expected to be applied to detection of biological samples.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement or combination made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (5)
1. The application of the fluorescent copper nanocluster in iron ion detection is characterized in that the preparation process of the fluorescent copper nanocluster comprises the following steps: mixing 3, 4-dihydroxyphenylalanine aqueous solution with copper salt aqueous solution, wherein the concentration of the copper salt aqueous solution is 0.05 mol.L -1 The concentration of the 3, 4-dihydroxyphenylalanine aqueous solution is 0.05 mol.L -1 (ii) a The molar ratio of the copper salt to the 3, 4-dihydroxyphenylalanine is 3:5-10:1, the mixed solution is stirred uniformly and then is subjected to microwave heating, the radiation is carried out for 3-18min under the microwave power of 53-385W, and the 3, 4-dihydroxyphenylalanine and Cu are mixed 2+ Reaction takes place, Cu 2+ Is reduced to Cu + And Cu 0 And the core is aggregated to form a fluorescent copper nano-cluster, the 3, 4-dihydroxyphenylalanine is oxidized to dopaquinone, the amino group in the 3, 4-dihydroxyphenylalanine is in coordination bonding with copper and is associated on the surface of the fluorescent copper nano-cluster to form a shell of the fluorescent copper nano-cluster, and a fluorescent copper nano-cluster solution is obtained; and the fluorescent copper nano-cluster solution can keep good luminous performance within 60 min.
2. The use of the fluorescent copper nanoclusters of claim 1 in iron ion detection, wherein the aqueous copper salt solution comprises an aqueous copper nitrate solution, an aqueous copper chloride solution, and an aqueous copper sulfate solution.
3. The use of the fluorescent copper nanocluster of claim 1 in iron ion detection, wherein the molar ratio of the copper salt to the 3, 4-dihydroxyphenylalanine is 5: 3.
4. The application of the fluorescent copper nanocluster in iron ion detection as claimed in claim 1, wherein the heating power of the microwave heating is 119W, and the heating time is 12 min.
5. The application of the fluorescent copper nanocluster in iron ion detection as claimed in claim 1, further comprising cooling the mixed solution after microwave heating and then centrifugally purifying at 12000rpm of 5000-20 min.
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