CN115290614A - Copper nanocluster-coumarin ratio fluorescence sensor for amplifying bimetallic ion signal and application thereof - Google Patents

Copper nanocluster-coumarin ratio fluorescence sensor for amplifying bimetallic ion signal and application thereof Download PDF

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CN115290614A
CN115290614A CN202210054589.8A CN202210054589A CN115290614A CN 115290614 A CN115290614 A CN 115290614A CN 202210054589 A CN202210054589 A CN 202210054589A CN 115290614 A CN115290614 A CN 115290614A
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solution
coumarin
copper
hydrogen peroxide
fluorescence
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梅鹤
王学东
周佩佩
朱晓磊
汪剑萍
汪清
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Wenzhou Medical University
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    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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    • G01N21/6408—Fluorescence; Phosphorescence with measurement of decay time, time resolved fluorescence
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Abstract

The invention belongs to the technical field of fluorescence sensing, and particularly relates to a copper nanocluster-coumarin ratio fluorescence sensor for amplifying bimetallic ion signals and application thereof. The invention uses Ce 3+ Inducing aggregation induction effect of glutathione-stabilized copper nanoclusters, remarkably enhancing fluorescence of the copper nanoclusters and remarkably improving fluorescence quenching efficiency of hydrogen peroxide on the copper nanoclusters, and applying the method to the treatment of the copper nanoclusters 2+ By Fe under catalysis of 2+ The Fenton reaction between the coumarin and the hydrogen peroxide promotes the conversion of the non-fluorescent coumarin into the strong-fluorescent 7-hydroxycoumarin, so that a ratiometric fluorescent sensor taking the copper nanocluster and the coumarin as fluorescent probes is constructed and used for sensitive detection of the hydrogen peroxide and the glucose. The preparation method of the fluorescence sensor is simple, short in time consumption and used for peroxideThe detection of hydrogen peroxide and glucose has high sensitivity, and the in-situ visual detection of hydrogen peroxide and glucose can be realized.

Description

Copper nanocluster-coumarin ratio fluorescence sensor for amplifying bimetallic ion signal and application thereof
Technical Field
The invention belongs to the technical field of fluorescence sensing, and particularly relates to a copper nanocluster-coumarin ratio fluorescence sensor for amplifying bimetallic ion signals and application thereof.
Background
Hydrogen peroxide is one of the important active oxygen species, and the disturbance or accumulation of intracellular hydrogen peroxide can lead to alzheimer's disease, parkinson's disease, and even cancer. Diabetes mellitus is a disease caused by defective insulin secretion or impaired insulin action and is characterized clinically by persistent hyperglycemia. Due to the lack of therapeutic methods to cure diabetes, for diabetic patients, complications (heart attack, hypertension, stroke, etc.) can only be reduced if the blood glucose concentration is monitored in real time and tightly controlled. Therefore, the development of highly sensitive, highly selective, rapid, and efficient hydrogen peroxide and glucose detection methods is crucial for the prevention, diagnosis, and monitoring of diseases. Fluorescent sensors have attracted the interest of researchers because of their advantages of high sensitivity, good selectivity, simplicity of operation, and the like.
The metal nanocluster has excellent fluorescence performance, particularly the metal nanocluster with stable sulfydryl has an aggregation-induced emission effect, and is commonly used for constructing fluorescence sensors of metal ions, environmental pollutants, biomolecules and the like. The present inventors have reported that cerium (III) induces aggregation-induced emission effect of glutathione-stabilized copper nanoclusters to enhance fluorescence quantum yield and stability of the copper nanoclusters, and cerium (III) as a fluorescent probe to construct hydrogen peroxide and glucose sensors (Analytical and biochemical Chemistry 413 (2021) 2135-2146). Although single-emission fluorescent sensors based on copper nanoclusters-cerium (III) have excellent detection performance for the detection of hydrogen peroxide and glucose, environmental factors unrelated to the analyte (probe concentration, excitation light intensity, temperature) cause false positive signals and visual detection is difficult to achieve.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a copper nanocluster-coumarin ratio fluorescence sensor for amplifying bimetallic ion signals and application thereof.
The technical scheme adopted by the invention is as follows: a copper nanocluster-coumarin ratio type fluorescence sensor for amplifying bimetallic ion signals is prepared by the following steps: adding the copper nanoclusters into acetic acid-sodium acetate buffer solution, uniformly mixing by vortex, and then adding Ce into the mixed solution 3+ Ion solution, after reaction, adding coumarin solution and Fe into the reaction solution in turn 2+ And (3) uniformly mixing the ionic solution in a vortex manner to obtain the copper nanocluster-coumarin ratio type fluorescence sensor with the double metal ion signal amplification function.
The preparation process of the copper nanocluster comprises the following steps of: dissolving glutathione in deionized water to obtain a solution A; dissolving copper sulfate in deionized water to obtain a solution B; dropwise adding the solution A into the solution B, and reacting under stirring; and then slowly dropwise adding an NaOH solution into the reaction solution, adjusting the pH value of the system to be between 4.5 and 5.5, and continuously reacting to obtain a light yellow copper nano-cluster solution.
And adding the copper nanocluster into an acetic acid-sodium acetate buffer solution in the form of a light yellow copper nanocluster solution.
The pH value of the acetic acid-sodium acetate buffer solution is 3-7.
Ce 3+ Ions, coumarin and Fe 2+ The molar concentration ratio of the ions is as follows: 0.5-6: 0.025-2.5: 0.015-1.25.
A visual detection method of hydrogen peroxide concentration comprises the following steps: adding the copper nanocluster-coumarin ratio type fluorescence sensor with the bimetallic ion signal amplified into a solution to be detected, uniformly mixing, reacting for a certain time, and determining the concentration of hydrogen peroxide in the solution to be detected according to the fluorescence intensity and/or color change of a system after reaction.
The reaction time of the solution to be detected and the copper nanocluster-coumarin ratio type fluorescence sensor is 3-30 min.
The detection range of the concentration of the hydrogen peroxide is 0-400 mu M, and the detection limit is 0.6 mu M. Under the irradiation of 365 nm ultraviolet lamp, the color of the reaction solution changes from red to blue as the concentration of hydrogen peroxide increases.
A visual detection method of glucose concentration comprises the following steps: reacting the solution to be tested with glucose oxidase to obtain a test system after reaction; the copper nanocluster-coumarin ratio type fluorescence sensor with the double metal ion signal amplification function is added into a test system, uniformly mixed and reacted for a certain time, and the concentration of glucose in a solution to be tested is determined according to the fluorescence intensity and/or color change of the reacted system.
The detection range of the glucose is 3.2-160 mu M, and the lowest detection limit is 0.96 mu M. Under the irradiation of 365 nm ultraviolet lamp, the color of the reaction solution was visually observed to change from red to blue as the glucose concentration increased.
The invention has the following beneficial effects: in the invention with Ce 3+ Inducing aggregation induction effect of glutathione-stabilized copper nanoclusters, remarkably enhancing fluorescence of the copper nanoclusters and remarkably improving fluorescence quenching efficiency of hydrogen peroxide on the copper nanoclusters, and applying the method to the treatment of the copper nanoclusters 2+ By Fe under catalysis of 2+ The Fenton reaction between the coumarin and the hydrogen peroxide promotes the conversion of the non-fluorescent coumarin into the strong-fluorescent 7-hydroxycoumarin, so that a ratiometric fluorescent sensor taking the copper nanocluster and the coumarin as fluorescent probes is constructed and used for sensitive detection of the hydrogen peroxide and the glucose. The preparation method of the fluorescence sensor is simple, short in time consumption, high in sensitivity when used for detecting hydrogen peroxide and glucose, and capable of realizing in-situ visual detection of the hydrogen peroxide and the glucose.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive labor.
FIG. 1, a fluorescence spectrum of copper nanoclusters;
FIG. 2, ce 3+ Influence of ion concentration on fluorescence of 7-hydroxycoumarin (460 nm)/fluorescence of copper nanocluster (625 nm);
FIG. 3, effect of buffer solution system pH on fluorescence of 7-hydroxycoumarin (460 nm)/fluorescence of copper nanoclusters (625 nm);
FIG. 4, effect of coumarin concentration on fluorescence of 7-hydroxycoumarin (460 nm)/copper nanocluster (625 nm);
FIG. 5, fe 2+ Influence of ion concentration on fluorescence of 7-hydroxycoumarin (460 nm)/fluorescence of copper nanocluster (625 nm);
FIG. 6, ce used for detection of Hydrogen peroxide 3+ An action verification diagram; in the figure, a is copper nanocluster-coumarin, and a' is copper nanocluster-coumarin/H 2 O 2 B is copper nanocluster-Ce 3+ Coumarin, b' is copper nanocluster-Ce 3+ coumarin/H 2 O 2 ；
FIG. 7 shows Fe in the detection of hydrogen peroxide 2+ An action verification diagram; in the figure, a is copper nanocluster-Ce 3+ Coumarin, a' is copper nanocluster-Ce 3+ coumarin/H 2 O 2 B is copper nanocluster-Fe 2+ /Ce 3+ Coumarin, b' is copper nanocluster-Fe 2+ /Ce 3 + coumarin/H 2 O 2 ；
FIG. 8, copper nanoclusters-Fe at different concentrations of hydrogen peroxide 2+ /Ce 3+ -a fluorescence response map of a coumarin fluorescence sensor;
FIG. 9, copper nanoclusters-Fe at different concentrations of hydrogen peroxide 2+ /Ce 3+ -a photograph of a coumarin fluorescence sensor under the 365 nm uv;
FIG. 10, validation graph for glucose assay; in the figure, a is copper nanocluster-Fe 2+ /Ce 3+ Coumarin, b is copper nanocluster-Fe 2+ /Ce 3+ Coumarin/glucose, c is copper nanocluster-Fe 2+ /Ce 3+ Coumarin/grape oxidationEnzyme, d is copper nanocluster-Fe 2+ /Ce 3+ Coumarin/glucose oxidase, e is copper nanocluster-Fe 2+ /Ce 3+ coumarin/H 2 O 2 ；
FIG. 11, effect of glucose oxidase and glucose reaction time on fluorescence of 7-hydroxycoumarin (460 nm)/fluorescence of copper nanoclusters (625 nm);
FIG. 12, copper nanoclusters-Fe at different concentrations of glucose 2+ /Ce 3+ -a fluorescence response plot of a coumarin fluorescence sensor;
FIG. 13, copper nanoclusters-Fe at different concentrations of glucose 2+ /Ce 3+ Photographs of coumarin fluorescence sensors under the 365 nm uv.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
(1) The preparation method of the copper nanocluster comprises the following steps: 1 g glutathione was weighed and dissolved in 20 mL deionized water to give solution A. 0.0499 g copper sulfate pentahydrate was weighed and dissolved in 20 mL deionized water to give solution B. The solution A was added dropwise to the solution B, and reacted at 37 ℃ for 1 hour under magnetic stirring. And then slowly dropwise adding an NaOH solution into the obtained reaction solution, adjusting the pH value of the system to 5, and continuously reacting for 2 hours to obtain a light yellow copper nano-cluster solution. As can be seen from FIG. 1, the excitation wavelength of the prepared copper nanoclusters is 350 nm, and the emission wavelength is 650 nm.
(2) The preparation method of the copper nanocluster-coumarin ratio type fluorescence sensor with the double metal ion signal amplification comprises the following steps: adding 12.5 mu L of the copper nanocluster prepared in the step (1) into 637.5 mu L of acetic acid-sodium acetate buffer solution (pH 3-7), uniformly mixing by vortex, and then adding 50 mu L of Ce into the mixed solution 3+ Reacting the ionic solution (final concentration of 0-4.5 mM) for 10 min, and sequentially adding 50 μ L coumarin solution (final concentration of 0-2.5 mM) and 50 μ L Fe into the reaction solution 2+ The ionic solution (0-1.2 mM) was vortexed and mixed.
As shown in FIG. 2, when Ce is added under the same conditions 3+ When the ion concentration is increased to 1 mM, the fluorescence intensity ratio (fluorescence of 7-hydroxycoumarin (460 nm)/fluorescence of copper nanocluster (625 nm)) is remarkably reduced, and the Ce continues to be increased 3+ The ion concentration and the fluorescence intensity ratio tend to be balanced, so 1 mM is selected as Ce 3+ Optimum concentration of ions and the selection was applied in the following experiments.
As shown in fig. 3, under the same conditions, the fluorescence intensity ratio (fluorescence of 7-hydroxycoumarin (460 nm)/fluorescence of copper nanocluster (625 nm)) gradually increased when the pH of the buffer solution increased from 3 to 6, and decreased when the pH of the system continued to increase to 7, so that the system pH of 6 was selected as the optimum pH of the system and the selection was applied in the following experiment.
As shown in fig. 4, the fluorescence intensity ratio (fluorescence of 7-hydroxycoumarin (460 nm)/fluorescence of copper nanocluster (625 nm)) increased with the increase of the concentration of coumarin, and when the concentration of coumarin exceeded 2.5 mM, the coumarin precipitated from the solution due to its limited solubility in the aqueous phase system, so 2.5 mM was selected as the optimum reaction concentration of coumarin and this choice was applied to the following experiment.
As shown in FIG. 5, when Fe 2+ When the ion concentration is increased to 0.5 mM, the fluorescence intensity ratio (fluorescence of 7-hydroxycoumarin (460 nm)/fluorescence of copper nanocluster (625 nm)) reaches the plateau, therefore, 1 mM is selected as Fe 2+ The optimum concentration of ions.
In summary, the optimal scheme for preparing the copper nanocluster-coumarin ratio type fluorescence sensor with bimetallic ion signal amplification is as follows: 1 mM Ce 3+ Ionic, pH 6 acetate-sodium acetate buffer solution, 2.5 mM coumarin, 1 mM Fe 2+ Ions. The copper nanocluster-coumarin ratio type fluorescence sensor mixed solution with the double metal ion signal amplified and prepared by the optimal scheme is used for hydrogen peroxide detection and glucose detection.
Example 2:
feasibility verification of hydrogen peroxide detection: amplification of the bimetallic ion Signal prepared in example 1200 mu L of hydrogen peroxide (2 mM) is added into the mixed solution of the copper nanocluster-coumarin ratio type fluorescence sensor and reacted for 10 min. The fluorescence intensity of the system was tested by setting the excitation wavelength to 345 nm and the emission wavelength to 460 nm, in the range of 350-850 nm. As shown in fig. 6, when Ce was added to the copper nanocluster-coumarin system 3+ In the process, the fluorescence of the copper nanocluster is obviously improved, and the fluorescence peak has an obvious blue shift phenomenon. However, when hydrogen peroxide is added into the system, the copper nanocluster-Ce 3+ The coumarin system is positioned at 625 nm, the fluorescence intensity is remarkably reduced, and the fluorescence change of the copper nanocluster coumarin is not obvious. As shown in fig. 7, when copper nanocluster-Ce is oriented 3+ When hydrogen peroxide is added to the coumarin system, only Fe is present in the system 2+ Then, the fluorescence of 7-hydroxycoumarin generated by coumarin oxidation appears at 460 nm, and the fluorescence intensity of copper nanoclusters decreases at 625 nm. Showing that only Ce is present in the system 3+ And Fe 2+ When the system exists at the same time, the system has a good hydrogen peroxide response signal, and the detection of the hydrogen peroxide can be realized.
Example 3:
detection of hydrogen peroxide: to the mixed solution of the bi-metal ion signal amplified copper nanocluster-coumarin ratio type fluorescence sensor prepared in example 1, 200. Mu.L of hydrogen peroxide (0, 0.02,0.05,0.1,0.2,0.5,1,2 mM) was added at various concentrations and reacted for 10 min. The fluorescence intensity of the system was tested in the range of 350-850 nm by setting the excitation wavelength to 345 nm and the emission wavelength to 460 nm. As shown in fig. 8, the fluorescence of copper nanoclusters (at about 625 nm) gradually decreased with increasing hydrogen peroxide concentration, while the fluorescence of 7-hydroxycoumarin generated by coumarin oxidation (460 nm) increased with increasing hydrogen peroxide concentration. The fluorescence intensity ratio (fluorescence of 7-hydroxycoumarin (460 nm)/fluorescence of copper nanocluster (625 nm)) is in a linear relationship with the hydrogen peroxide concentration, the linear range is 0 μ M to 400 μ M, and the detection limit is 0.6 μ M. As shown in FIG. 9, as the hydrogen peroxide is increased, the color of the reaction solution changes from red to blue when the system solution is irradiated by 365 nm ultraviolet lamp.
Example 4:
160. mu.L of glucose solution (2 mM) was reacted with 40. Mu.L of glucose oxidase (0-160. Mu.g/mL) for 0-30 minutes at 37 ℃. Then, the obtained reaction solution was added to the mixed solution of the bimetallic ion signal amplified copper nanocluster-coumarin ratio type fluorescent sensor prepared in example 1, and the reaction was continued for 10 min. The fluorescence intensity of the system was tested by setting the excitation wavelength to 345 nm and the emission wavelength to 460 nm, in the range of 350-850 nm.
As shown in FIG. 10, it is shown that when glucose and glucose oxidase coexist, the fluorescence of 7-hydroxycoumarin at 460 nm is enhanced, and the fluorescence of copper nanocluster at 625 nm is reduced, consistent with the change of fluorescence generated by hydrogen peroxide, and can be used for quantitative detection of glucose. When the concentration of the glucose oxidase is increased to 120 mug/mL, the fluorescence intensity ratio tends to reach the balance, the concentration of the glucose oxidase is continuously increased, and the fluorescence intensity ratio is kept unchanged, so that 120 mug/mL is selected as the optimal concentration of the glucose oxidase.
As shown in fig. 11, the fluorescence intensity ratio (fluorescence of 7-hydroxycoumarin (460 nm)/fluorescence of copper nanocluster (625 nm)) gradually decreased with increasing reaction time and reached a plateau at 30 minutes, and therefore, 30 minutes was selected as the optimal reaction time for glucose oxidase and glucose.
In summary, the optimal scheme for glucose detection is as follows: 120. μ g/mL glucose oxidase concentration, 30 minutes reaction time. The glucose assay was performed in the optimal protocol for glucose assay described above.
Example 5:
and (3) detection of glucose: 160. mu.L of glucose (0, 0.02,0.05,0.1,0.2,0.5,1,2 mM) at various concentrations was reacted with 40. Mu.L of glucose oxidase (120. Mu.g/mL) for 30 minutes at 37 ℃. Then, the obtained reaction solution was added to the mixed solution of the copper nanocluster-coumarin ratio type fluorescence sensor prepared in example 1, which is subjected to bimetallic ion signal amplification, and the reaction was carried out for 10 min. The fluorescence intensity of the system was tested by setting the excitation wavelength to 345 nm and the emission wavelength to 460 nm, in the range of 350-850 nm. As shown in fig. 12, the fluorescence of copper nanoclusters (625 nm) gradually decreased as the glucose concentration increased, while the fluorescence of 7-hydroxycoumarin (460 nm) was sequentially increased. The fluorescence intensity ratio (fluorescence of 7-hydroxycoumarin (460 nm)/fluorescence of copper nanocluster (625 nm)) is linear with the concentration of glucose, the linear range is 3.2 μ M to 480 μ M, and the detection limit is 0.96 μ M. As shown in FIG. 13, as the glucose concentration increased, the solution was visually observed to change from red to blue under the 365 nm UV lamp.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.

Claims (10)

1. A copper nanocluster-coumarin ratio type fluorescence sensor for amplifying bimetallic ion signals is characterized in that a preparation method of the sensor comprises the following steps: adding the copper nanoclusters into an acetic acid-sodium acetate buffer solution, uniformly mixing by vortex, and then adding Ce into the mixed solution 3+ Ion solution, after reaction, adding coumarin solution and Fe into the reaction solution in turn 2+ And (3) uniformly mixing the ionic solution in a vortex manner to obtain the copper nanocluster-coumarin ratio type fluorescence sensor with the double metal ion signal amplification function.
2. The bi-metal ion signal amplified copper nanocluster-coumarin ratio type fluorescent sensor according to claim 1, characterized in that: the preparation process of the copper nanocluster comprises the following steps: dissolving glutathione in deionized water to obtain a solution A; dissolving copper sulfate in deionized water to obtain a solution B; dropwise adding the solution A into the solution B, and reacting under stirring; and then slowly dropwise adding an NaOH solution into the reaction solution, adjusting the pH value of the system to be between 4.5 and 5.5, and continuously reacting to obtain a light yellow copper nano-cluster solution.
3. The bi-metal ion signal amplified copper nanocluster-coumarin ratio type fluorescent sensor according to claim 2, characterized in that: and adding the copper nanoclusters into an acetic acid-sodium acetate buffer solution in the form of a light yellow copper nanocluster solution.
4. The bi-metal ion signal amplified copper nanocluster-coumarin ratio type fluorescent sensor according to claim 1, characterized in that: the pH value of the acetic acid-sodium acetate buffer solution is 3-7.
5. The bi-metal ion signal amplified copper nanocluster-coumarin ratio type fluorescent sensor according to claim 1, characterized in that: ce 3+ Ions, coumarin and Fe 2+ The molar concentration ratio of the ions is as follows: 0.5-6: 0.025-2.5: 0.015-1.25.
6. A visual detection method for hydrogen peroxide concentration is characterized by comprising the following steps: the copper nanocluster-coumarin ratio type fluorescence sensor with the double metal ion signal amplification function as claimed in any one of claims 1 to 5 is added into a solution to be detected, uniformly mixed, reacted for a certain time, and the hydrogen peroxide concentration in the solution to be detected is determined according to the fluorescence intensity and/or color of a system after the reaction.
7. The method for visually detecting a concentration of hydrogen peroxide according to claim 6, wherein: the reaction time of the solution to be detected and the copper nanocluster-coumarin ratio type fluorescence sensor is 3-30 min.
8. The method for visually detecting a concentration of hydrogen peroxide according to claim 6, wherein: the detection range of the concentration of the hydrogen peroxide is 0-400 mu M, and the detection limit is 0.6 mu M; under the irradiation of 365 nm ultraviolet lamp, the color of the reaction solution changes from red to blue as the concentration of hydrogen peroxide increases.
9. A visual detection method of glucose concentration is characterized by comprising the following steps: reacting the solution to be tested with glucose oxidase to obtain a test system after reaction; the copper nanocluster-coumarin ratio type fluorescence sensor with the double metal ion signal amplification function as claimed in any one of claims 1 to 5 is added into a test system, uniformly mixed, reacted for a certain time, and the concentration of glucose in a solution to be tested is determined according to the change of fluorescence intensity and/or color of the reacted system.
10. The method for visually detecting a glucose concentration according to claim 9, wherein: the detection range of the glucose is 3.2-160 mu M, and the lowest detection limit is 0.96 mu M; under the irradiation of 365 nm ultraviolet lamp, the color of the reaction solution was visually observed to change from red to blue as the glucose concentration increased.
CN202210054589.8A 2022-01-18 2022-01-18 Copper nanocluster-coumarin ratio fluorescence sensor for amplifying bimetallic ion signal and application thereof Pending CN115290614A (en)

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