CN114806548A - Red fluorescent silver nanocluster, preparation method thereof and application of red fluorescent silver nanocluster in detection of copper ions - Google Patents
Red fluorescent silver nanocluster, preparation method thereof and application of red fluorescent silver nanocluster in detection of copper ions Download PDFInfo
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Abstract
The invention relates to a red fluorescent silver nanocluster, a preparation method thereof and application of the red fluorescent silver nanocluster in detection of copper ions. The red fluorescent silver nanocluster is prepared by a one-pot method by using 5-mercapto- (1H) -tetrazolyl sodium acetate as a protective agent, sodium borohydride as a reducing agent and a silver nitrate solution as a matrix. The preparation method has the advantages of simple preparation process, simple reaction conditions and convenient operation. The prepared red fluorescent silver nanocluster has the advantages of good water solubility, strong stability, large Stocks displacement, strong photobleaching resistance and the like, has response of ultrahigh sensitivity and high selectivity to copper ions, and can be applied to detection of the copper ions in the wine.
Description
Technical Field
The invention relates to preparation of silver nanoclusters, in particular to a red fluorescent silver nanocluster and a preparation method and application thereof.
Background
Copper, as an essential trace element in the human body, plays an important role in the development and maintenance of the central nervous system, the immune system, the bone tissue and the visceral system. However, human body to Cu 2+ Excessive intake of (b) may cause various diseases such as kidney, liver damage and nervous system damage, which may have adverse effects on the body. Therefore, a high-selectivity rapid trace Cu detection method is established 2+ The method has important significance.
In recent years, fluorescence analysis methods have been widely studied in the field of analytical detection due to the advantages of easy operation, high sensitivity, fast signal response, low cost, real-time detection, almost no damage to samples, and the like. Among the reported fluorescent materials, the metal nanoclusters are attracting attention due to their excellent optical properties such as large stokes shift, good photobleaching resistance, and stable light emitting properties. Silver nanoclusters are gradually becoming an important part of research in metal nanomaterials. In synthesis, thiol small molecules are widely used as a protective agent for metal nanoclusters because thiol groups have strong acting force with metals. Saifei Pan et al added a mixed solution of silver nitrate and thiosalicylic acid (TSA) to an ethanol solution, and after the mixture was heated under nitrogen protection at 80 ℃ and stirred vigorously for 2 hours, a silver nanocluster solution was obtained (Journal of Materials Chemistry B,2018,6: 3927-. Silver nitrate and Glutathione (GSH) synthesized into silver nanoclusters at a high temperature of 100 deg.C (Analytical Chemistry,2017,89(9): 4994-. Silver nitrate such as Mostafa Farrag and 2-phenethyl mercaptan (PhCH) 2 CH 2 SH) is dissolved in methanol, freshly prepared NaBH is added dropwise under ice-cold conditions 4 And centrifuging the solution, collecting precipitate, and repeatedly washing with methanol to obtain the silver nanocluster.
The above methods either need to be synthesized under a heating condition or need to be synthesized at a low temperature, and have relatively high requirements on reaction temperature; still other nanocluster syntheses require the addition of organic reagents.
Disclosure of Invention
The invention aims to provide a red fluorescent silver nanocluster and a preparation method and application thereof, and at least one red fluorescent silver nanocluster for sensitively detecting copper ions is obtained.
In order to achieve the above object, according to one aspect of the present invention, a method for preparing a red fluorescent silver nanocluster is provided, wherein a "one-pot method" is used to prepare a red fluorescent silver nanocluster solution by using 5-mercapto- (1H) -tetrazolyl sodium acetate as a protective agent, sodium borohydride as a reducing agent, and a silver nitrate solution as a matrix.
Further, the above method comprises the steps of:
step one, uniformly mixing a 5-mercapto- (1H) -tetrazolyl sodium acetate solution and a silver nitrate solution, adding a sodium borohydride solution, and uniformly stirring;
and step two, reacting at room temperature for 6-36 hours, and taking out after reaction to obtain the red fluorescent silver nanocluster aqueous solution.
Further, in the first step, 5-30 parts by volume of 5-mercapto- (1H) -tetrazolyl sodium acetate solution and 5 parts by volume of silver nitrate solution are uniformly mixed, and 0.1-0.5 part by volume of 0.5mol/L sodium borohydride solution is added and uniformly stirred.
Further, the molar ratio of the silver nitrate to the sodium borohydride is 1: 5; the molar ratio of the silver nitrate to the 5-mercapto- (1H) -tetrazolyl sodium acetate is 1: 3.
Further, in the second step, the reaction is carried out for 24 hours at room temperature under the condition of controlling the temperature.
The invention adopts a one-pot method to synthesize the red fluorescent silver nanocluster. The preparation process is simple and easy to operate, the instrument requirement is low, the cost is low, the preparation method is green and environment-friendly, the product aftertreatment is not needed, the reaction condition is mild, and the obtained nanocluster has good luminescence property.
The 5-mercapto- (1H) -tetrazolyl sodium acetate solution is a compound with a mercapto group and a heterocyclic ring, the mercapto group can have a strong bonding effect with noble metals, the heterocyclic ring can also have a coordination effect with silver, and the carboxylic group contained in the 5-mercapto- (1H) -tetrazolyl sodium acetate solution can enable the prepared red fluorescent silver nano-cluster to have good water solubility.
According to one aspect of the invention, the red fluorescent silver nanoclusters prepared by the method are provided.
According to another aspect of the present invention, there is provided the use of the red fluorescent silver nanoclusters described above for detection of copper ions.
The red luminescent silver nanocluster prepared by the invention has good optical properties, the fluorescence emission of the red luminescent silver nanocluster is about 650nm, and the red luminescent silver nanocluster shows red fluorescence when observed with a black background under ultraviolet light. The red luminous silver nanocluster prepared by the invention has the advantages of average particle size of 1.1nm, small size, uniform particle size distribution and good photobleaching resistance.
The prepared red fluorescent silver nanocluster can be applied to ultra-sensitive detection of copper ions, and the detection limit is 0.175 nmol/L.
According to another aspect of the present invention, a method for detecting copper ions is provided, wherein 100L of the above aqueous solution of red fluorescent silver nanoclusters and 1mL of PBS buffer solution with pH 6.0 and 20mmol/L are added into a fluorescence cuvette, copper ion solutions with different concentrations are added, and a fluorescence spectrum is measured with 400nm as an excitation wavelength to obtain a linear relationship between fluorescence intensity and copper ion concentration; and according to the linear relation, quantitatively detecting the concentration of the copper ions in the sample to be detected through the change of the fluorescence intensity.
The invention also provides a method for measuring copper ions in wine, which comprises the steps of adding 100 mu L of the aqueous solution of the red fluorescent silver nanocluster and 1mL of PBS buffer solution with the pH value of 6.0 being 20mmol/L into a fluorescent cuvette, adding different volumes of wine, measuring the fluorescence spectrum of the wine with the excitation wavelength of 400nm, and substituting the measured fluorescence intensity into a linear equation to calculate the concentration of the copper ions.
In conclusion, the preparation process is simple, the reaction conditions are simple, and the operation is convenient. The prepared red fluorescent silver nanocluster has the advantages of good water solubility, strong stability, large Stocks displacement, strong photobleaching resistance and the like, has response of ultrahigh sensitivity and high selectivity to copper ions, and can be applied to ultrasensitive detection of the copper ions.
Description of the figures and accompanying tables
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic diagram of the formation of red fluorescent silver nanoclusters and detection of copper ions;
fig. 2 is a fluorescence excitation and emission spectrum of red fluorescent silver nanoclusters;
fig. 3 is a graph of the photostability of red fluorescent silver nanoclusters;
fig. 4 is a transmission electron microscope image of red fluorescent silver nanoclusters;
FIG. 5 is a working curve of the response of red fluorescent silver nanoclusters to copper ions and a linear relationship between the fluorescence intensity of the red fluorescent silver nanoclusters and the concentration of copper ions;
FIG. 6 is a bar graph of fluorescence of red fluorescent silver nanoclusters after interaction with various interferents.
Detailed Description
Examples 1 to 6 are methods for preparing red fluorescent silver nanoclusters.
Example 1
Uniformly mixing 30mL of 5-mercapto- (1H) -tetrazolyl sodium acetate solution with 5mL of 5mmol/L silver nitrate solution, quickly adding 0.5mL of 0.5mol/L sodium borohydride solution which is freshly prepared, uniformly stirring, reacting at room temperature for 36H, and taking out after reaction to obtain the red fluorescent silver nanocluster aqueous solution. The fluorescence emission peak of the red fluorescent silver nanocluster is about 650nm, and under ultraviolet light, when the red fluorescent silver nanocluster is observed on a black background, red fluorescence is presented, and the quantum yield is 10.7%.
Example 2
5mL of 5-mercapto- (1H) -tetrazolyl sodium acetate solution with the concentration of 5mmol/L and 5mL of 5mmol/L silver nitrate solution are mixed uniformly, 0.1mL of 0.5mol/L sodium borohydride solution which is prepared freshly is added rapidly, the mixture is stirred uniformly and reacts at room temperature for 6 hours, and after the reaction, the mixture is taken out to obtain the red fluorescent silver nanocluster aqueous solution. The fluorescence emission peak of the red fluorescent silver nanocluster is about 650nm, and under ultraviolet light, when the red fluorescent silver nanocluster is observed on a black background, red fluorescence is presented, and the quantum yield is 10.3%.
Example 3
Uniformly mixing 10mL of 5-mercapto- (1H) -tetrazolyl sodium acetate solution with 5mL of 5mmol/L silver nitrate solution, quickly adding 0.2mL of 0.5mol/L sodium borohydride solution which is freshly prepared, uniformly stirring, reacting at room temperature for 12H, and taking out after reaction to obtain the red fluorescent silver nanocluster aqueous solution. The fluorescence emission peak of the red fluorescent silver nanocluster is about 650nm, and under ultraviolet light, when the red fluorescent silver nanocluster is observed on a black background, red fluorescence is presented, and the quantum yield is 11.6%.
Example 4
Uniformly mixing 20mL of 5-mercapto- (1H) -tetrazolyl sodium acetate solution with 5mL of 5mmol/L silver nitrate solution, quickly adding 0.3mL of 0.5mol/L sodium borohydride solution which is freshly prepared, uniformly stirring, reacting at room temperature for 28H, and taking out after reaction to obtain the red fluorescent silver nanocluster aqueous solution. The fluorescence emission peak of the red fluorescent silver nanocluster is about 650nm, and under ultraviolet light, when the red fluorescent silver nanocluster is observed on a black background, red fluorescence is presented, and the quantum yield is 11.8%.
Example 5:
uniformly mixing 25mL of 5-mercapto- (1H) -tetrazolyl sodium acetate solution with 5mL of 5mmol/L silver nitrate solution, quickly adding 0.4mL of 0.5mol/L sodium borohydride solution which is freshly prepared, uniformly stirring, reacting at room temperature for 32H, and taking out after reaction to obtain the red fluorescent silver nanocluster aqueous solution. The fluorescence emission peak of the red fluorescent silver nanocluster is about 650nm, and under ultraviolet light, when the red fluorescent silver nanocluster is observed on a black background, red fluorescence is presented, and the quantum yield is 11.4%.
Example 6
Uniformly mixing 15mL of 5-mercapto- (1H) -tetrazolyl sodium acetate solution with 5mL of 5mmol/L silver nitrate solution, quickly adding 0.25mL of 0.5mol/L sodium borohydride solution which is freshly prepared, uniformly stirring, reacting at room temperature for 24H, and taking out after reaction to obtain the red fluorescent silver nanocluster aqueous solution. The fluorescence emission peak of the red fluorescent silver nanocluster is about 650nm, and under ultraviolet light, when the red fluorescent silver nanocluster is observed on a black background, red fluorescence is presented, and the quantum yield is 12.2%.
The formation mechanism of the red fluorescent silver nanocluster and the detection of copper ions are schematically shown in fig. 1.
100 μ L of red fluorescent silver nanocluster aqueous solution and 1mL of phosphate buffer (NaH) 2 PO 4 -Na 2 HPO 4 PBS buffer, pH 6, 20mmol/L) was added to the fluorescence cuvette and fluorescence excitation and emission spectra were measured, as shown in fig. 2, the red fluorescent silver nanocluster has two fluorescence excitation peaks of 360nm and 400nm, the maximum fluorescence emission peak is around 650nm, and the larger stokes shift (290nm) can avoid overlapping of the excitation and emission peaks.
The prepared red fluorescent silver nanocluster is subjected to a photobleaching resistance experiment, as shown in fig. 3, good luminescence performance can still be kept after continuous ultraviolet irradiation for 50min, and fluorescence intensity can still be maintained above 98%, which indicates that the photobleaching resistance is good. The method provides a reliable premise for the application of the red fluorescent silver nanocluster in the detection of copper ions.
And analyzing the distribution form and the size of the prepared red fluorescent silver nanocluster by a transmission electron microscope. As shown in fig. 4, the synthesized red fluorescent silver nanoclusters had good dispersibility and an average particle diameter of 1.1 nm.
Example 7 application of the red fluorescent silver nanocluster of the present invention in ultra-sensitive detection of copper ions the red fluorescent silver nanocluster aqueous solution prepared in example 6 was mixed with 1mL of phosphate buffer (NaH) 2 PO 4 -Na 2 HPO 4 PBS buffer solution, pH 6, 20mmol/L) was added to the fluorescence cuvette, stirred until mixed well, copper ion solutions of different concentrations were added, and fluorescence spectra were measured separately with 400nm as excitation wavelength. As shown in fig. 5, the fluorescence of the silver nanoclusters is gradually quenched as the concentration of copper ions increases. Change in relative fluorescence intensity of solution (log (F) 0 /F)) andthe copper ion concentration presents a three-stage linear relationship: when the content of copper ions is in the range of 0.0018-0.057. mu.M, the formula log (F) 0 /F)＝0.00846+6.87[Cu 2+ ]To represent (R) 2 0.997); the concentration of copper ions is in the range of 0.059 μ M to 0.103 μ M, and the linear equation is log (F) 0 /F)＝0.146+3.973[Cu 2+ ]Linear correlation coefficient R 2 0.996; the concentration of copper ions is in the range of 0.110 μ M to 0.195 μ M, and the linear equation is log (F) 0 /F)＝0.196+3.297[Cu 2+ ]Linear correlation coefficient R 2 0.993, wherein F 0 Showing the fluorescence intensity of MTA @ Ag NCs in the absence of copper ions, F showing the fluorescence intensity of silver nanoclusters after copper ions of different concentrations were added, [ Cu ] 2+ ]Represents the concentration of copper ions in μ M. Further, the detection Limit (LOD) was calculated from the formula LOD of 3 σ/k to be 0.175 nmol/L. The regression equation of the silver nanoclusters obtained by linear fitting is: y is 0.160+1.912X, and the linear coefficient is R 2 0.996. The results show that the red fluorescent silver nanocluster has ultrahigh sensitivity to copper ions, and can quantitatively detect the copper ions.
Compared with other reports in the literature, the red fluorescent silver nanocluster disclosed by the invention has a remarkable advantage in sensitivity for detecting copper ions, as shown in table 1.
In table 1, the corresponding references are: [1] -Biosensors,2020, 10; [2] -Photochemical & Photobiological Sciences,2011,10(1): 109-115; [3] -Journal of Photochemistry and Photobiology A: Chemistry,2022,427: 113841; [4] chemical Communications,2011,47(9): 2661-2663; [5] Nano-Micro Letters,2019,14(9): 952-.
The sensitivity of the present invention is 285 times that of the literature [ Biosensors,2020,10], 36 times that of [ Photochemical & Photobiological Sciences,2011,10(1): 109-.
Example 8
The red fluorescent silver nanocluster solution prepared in example 6 was mixed with 1mL 1mL of phosphate buffer (NaH) 2 PO 4 -Na 2 HPO 4 PBS buffer, pH 6, 20mmol/L) was added to the fluorescence cuvette and stirred until well mixed. Firstly, adding copper ions into the solution to measure the fluorescence intensity of the solution, and taking the solution as a blank control; secondly, respectively adding common potential interference substances (the concentration of coexisting ions is 100 times that of copper ions) and the like, measuring and recording the fluorescence intensity value; copper ions were added thereto, and the fluorescence intensity was measured and recorded. Measuring the fluorescence spectra of the samples with 400nm as the excitation wavelength, respectively, and drawing a histogram of the fluorescence intensities of the samples at 630nm corresponding to different interferents, as shown in FIG. 6; experiments prove that other interferents only slightly interfere with the detection of copper ions.
Example 9 application of the red fluorescent silver nanoclusters of the present invention to detection of copper ions in wine the red fluorescent silver nanocluster solution prepared in example 6 was mixed with 1mL of phosphate buffer (NaH) 2 PO 4 -Na 2 HPO 4 PBS buffer, pH 6, 20mmol/L) was added to the fluorescence cuvette, stirred until well mixed, different volumes of wine were added, and the fluorescence spectra were measured separately with 400nm as excitation wavelength. The measured fluorescence intensity was substituted into a linear equation to calculate the copper ion concentration, and the copper ion concentration in wine was measured to be 2.8 nmol/L.
Table 2 shows the results of detecting copper ions in wine using the red fluorescent silver nanoclusters of the present invention.
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 (9)
1. A preparation method of red fluorescent silver nanoclusters is characterized by comprising the following steps: the red fluorescent silver nanocluster solution is prepared by a one-pot method by using 5-mercapto- (1H) -tetrazolyl sodium acetate as a protective agent, sodium borohydride as a reducing agent and a silver nitrate solution as a matrix.
2. The method according to claim 1, comprising the steps of:
step one, uniformly mixing a 5-mercapto- (1H) -tetrazolyl sodium acetate solution and a silver nitrate solution, adding a sodium borohydride solution, and uniformly stirring;
and step two, reacting at room temperature for 6-36 hours, and taking out after reaction to obtain the red fluorescent silver nanocluster aqueous solution.
3. The method of claim 2, wherein: in the first step, 5-30 parts by volume of 5-mercapto- (1H) -tetrazolyl sodium acetate solution with the concentration of 5mmol/L and 5 parts by volume of silver nitrate solution with the concentration of 5mmol/L are mixed uniformly, and 0.1-0.5 part by volume of 0.5mol/L sodium borohydride solution is added and stirred uniformly.
4. The method of claim 2, wherein: the molar ratio of the silver nitrate to the sodium borohydride is 1: 5; the molar ratio of the silver nitrate to the 5-mercapto- (1H) -tetrazolyl sodium acetate is 1: 3.
5. The method of claim 2, 3 or 4, wherein: in the second step, the reaction is carried out for 24 hours at the room temperature under the control of the temperature.
6. The red fluorescent silver nanoclusters prepared by the method of any one of claims 1 to 5.
7. Use of the red fluorescent silver nanoclusters of claim 6 for detecting copper ions.
8. A method for detecting copper ions is characterized in that: adding 100 mu L of the aqueous solution of the red fluorescent silver nanocluster in claim 6 and 1mL of PBS buffer solution with the pH value of 6.0 and the concentration of 20mmol/L into a fluorescent cuvette, adding copper ion solutions with different concentrations, measuring the fluorescence spectrum of the copper ion solutions with the excitation wavelength of 400nm, and obtaining the linear relation between the fluorescence intensity and the concentration of copper ions; and according to the linear relation, quantitatively detecting the concentration of the copper ions in the sample to be detected through the change of the fluorescence intensity.
9. A method for measuring copper ions in wine is characterized in that: the red fluorescent silver nanoclusters of claim 6, which are prepared by adding 100 μ L of the aqueous solution of red fluorescent silver nanoclusters of claim 6 and 1mL of PBS buffer solution having a pH of 6.0 and a concentration of 20mmol/L to a fluorescence cuvette, adding different volumes of wine, measuring fluorescence spectra thereof with 400nm as an excitation wavelength, and substituting the measured fluorescence intensity into a linear equation to calculate the copper ion concentration.
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| CN115780818A (en) * | 2022-10-24 | 2023-03-14 | 山西大学 | Aggregation-induced gold-silver alloy nanocluster and preparation method and application thereof |
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