CN107254307B - Silver nanocluster fluorescent vesicle and preparation method thereof and Fe detection method3+Application of - Google Patents

Silver nanocluster fluorescent vesicle and preparation method thereof and Fe detection method3+Application of Download PDF

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CN107254307B
CN107254307B CN201710440531.6A CN201710440531A CN107254307B CN 107254307 B CN107254307 B CN 107254307B CN 201710440531 A CN201710440531 A CN 201710440531A CN 107254307 B CN107254307 B CN 107254307B
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silver nanocluster
silver
vesicle
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fluorescent
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CN107254307A (en
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辛霞
沈静林
孙頔
苑世领
王芝
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Shandong University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • 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
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • 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
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching

Abstract

The invention relates to a silver nanocluster fluorescent vesicle and a preparation method thereof, and Fe detection3+The fluorescent vesicle is prepared from Ag6Dissolving into polar organic solvent to form fluorescent vesicle. The fluorescent vesicle is added with Fe3+Quenching after fluorescence, and continuously adding reducing agent DL-dithiothreitol to recover fluorescence, so that the dual detection effect is achieved, and Fe can be detected by multiple use3+. The preparation method of the silver nanocluster fluorescent vesicle is simple and low in cost; the detection means is simple and quick, and is easy to observe; can be repeatedly used.

Description

Silver nanocluster fluorescent vesicle and preparation method thereof and Fe detection method3+Application of
Technical Field
The invention relates to a silver nanocluster fluorescent vesicle and a preparation method thereof, and Fe detection3+Belonging to the field of new materials.
Background
The iron element is a necessary trace element in a human body, and the total content of the iron element is about 4-5 g. Hemoglobin in red blood cells is a carrier for transporting oxygen, and iron is a component of hemoglobin, and is combined with oxygen and transported to each part of a body for respiratory oxidation of people to provide energy and obtain nutrition; iron can also promote development, increase resistance to diseases, regulate tissue respiration, prevent fatigue, form heme, prevent and treat anemia due to iron deficiency, and restore good blood color of skin. However, excessive iron storage in the body also has potentially deleterious effects, resulting in iron poisoning, which is associated with a variety of diseases, such as heart and liver diseases, diabetes and certain tumors. In addition, if too much iron element is present in water, it may affect the color, smell, taste, etc. of water, and may even affect special industries such as textile, paper and food industries. Therefore, it is necessary to develop a convenient, fast, simple and easy-to-observe method for detecting iron, and the method has a great application prospect.
Fluorescent substances are often chosen as fluorescent probes for the detection of toxic substances. The principle is that interaction occurs between the detected substance and the fluorescent substance to influence the luminescence of the fluorescent substance, thereby achieving the purpose of detection. The metal nanocluster has a unique luminescence phenomenon due to the ligand-metal charge transfer, the metal-metal action and the pi-pi accumulation action between the ligand and the ligand, so the metal nanocluster can be used as a fluorescent probe to detect toxic substances.
Silver nanoclusters are popular among people in the industry due to their special properties and wide sources of raw materials, and there are many reports on the silver nanoclusters, such as: chinese patent document CN104227016A (application number: 201410494598.4) discloses a method for rapidly preparing silver nanoclusters with strong fluorescence emission, which is characterized in that 14.75 parts by volume of redistilled water is put into a container, 2.0 parts by volume of AgNO are sequentially added into a constant-temperature water bath kettle under the stirring condition3Solution, 0.25 part NaBH4And stirring the solution and 3.0 parts of amino black 10B for 3-90 min at the temperature of 30-80 ℃ to obtain the silver nanocluster with strong fluorescence emission. For another example: chinese patent document CN103878386A (application No. 201410120530.X) discloses a method for preparing fluorescent silver nanoclusters, which relates to a method for preparing fluorescent silver nanoclusters, and the preparation method comprises the following steps: firstly, respectively dispersing a certain amount of silver salt and sodium oleate into solvent water; mixing and stirring the two solutions for a period of time, placing the solution on a constant-temperature magnetic stirrer for heating treatment for a period of time after the solution is uniform; thirdly, the method comprises the following steps: and filtering the solution after the reaction to remove solid matters to obtain the fluorescent silver nanoclusters.
However, at present, reports on silver nanoclusters are only limited to research on exploration of a synthesis method and solid-state properties, and few reports on aggregation behaviors of silver nanoclusters in a solution and application research of aggregates are available.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a silver nanocluster fluorescent vesicle and a preparation method thereof, and Fe detection3+The use of (1).
Description of terms:
Ag6: is a six-core silver nanocluster, and due to pi-pi action between ligands, charge transfer action of ligands to metal and metal-metal action, Ag6Has certain luminescent property.
The technical scheme of the invention is as follows:
silverThe nano-cluster fluorescent vesicle is made of Ag6Dissolving into polar organic solvent to form fluorescent vesicle.
According to the present invention, preferably, the polar organic solvent is dimethyl sulfoxide, ethylene glycol, methanol or acetonitrile.
According to the present invention, preferably, the Ag is6The molar concentration of the organic solvent is 10-70 mu mol.L-1。
According to the present invention, preferably, the Ag is6The preparation method comprises the following steps:
mixing silver nitrate (AgNO)3) Aqueous solution and 2-mercaptonicotinic acid (H)2mna) aqueous solution, and carrying out ultrasonic treatment to obtain a precipitate; adding ammonia water dropwise into the precipitate to obtain a solution, slowly volatilizing the solvent to dry to obtain Ag6。
According to the invention, the preparation method of the silver nanocluster fluorescent vesicle comprises the following steps:
(1)Ag6synthesis of molecules
Mixing silver nitrate (AgNO)3) Aqueous solution and 2-mercaptonicotinic acid (H)2mna) aqueous solution, and carrying out ultrasonic treatment to obtain a precipitate; adding ammonia water dropwise into the precipitate to obtain solution, volatilizing the solvent to dry to obtain Ag6；
(2) Preparation of silver nanocluster fluorescent vesicle
Mixing Ag with water6Dissolving the silver nanocluster in a polar organic solvent, and dissolving the silver nanocluster in an ultrasonic manner to obtain the silver nanocluster fluorescent vesicle.
According to the production method of the present invention, preferably, AgNO in step (1)3The concentration of the aqueous solution is 0.1 to 1 mol.L-1, H2The concentration of the mna aqueous solution is 0.1-1 mol.L-1；AgNO3And H2The molar ratio of mna is 1: (0.8 to 1.2), and more preferably 1: 1;
preferably, the ultrasonic frequency of ultrasonic treatment is 30-50 kHz, the ultrasonic power is 140-160W, and the ultrasonic time is 10-30 minutes.
According to the preparation method disclosed by the invention, preferably, the mass concentration of the ammonia water in the step (1) is 20-30%; the amount of ammonia added was such that the precipitate was completely dissolved. The resulting solution was a yellow clear solution.
According to the present invention, it is preferable that the polar organic solvent described in the step (2) is dimethyl sulfoxide, ethylene glycol, methanol or acetonitrile;
preferably, Ag6The molar concentration of the organic solvent is 10-70 mu mol.L-1；
Preferably, the ultrasonic frequency of ultrasonic dissolution is 30-50 kHz, the ultrasonic power is 140-160W, and the ultrasonic time is 5-10 s. The ultrasonic-assisted ultrasonic dissolving device is kept stand for 20-30 hours at 18-25 ℃ after complete ultrasonic dissolving.
According to the invention, the silver nanocluster fluorescent vesicle is made of Fe3+Application in detection.
The principle of the invention is as follows:
Ag6in a solvent of appropriate polarity, exhibits amphiphilicity, with mna in the periphery thereof2-The carboxylic acid counter ion is a solvophilic agent, a middle silver core and mna2-In which the other part than the carboxylate radical is solvophobic, mna2-There is a pi-pi interaction between them, therefore, Ag6Amphiphilicity between molecules and pi-pi action allows Ag to act6Can aggregate to form vesicles. Meanwhile, the electron transfer effect between the ligand and the metal and the pi-pi effect between the ligand and the ligand lead the vesicle to show the fluorescent characteristic. When a specific metal ion is added, the metal ion and Ag6There is a competitive energy absorption relationship between them, so that Ag6Cannot absorb enough energy and cannot emit fluorescence, thereby playing a role in detecting specific metal ions.
In the present invention, Ag6The solvent to be dissolved is inventively selected by a large number of experiments. If dissolved in water, Ag6No vesicle can be formed, and no fluorescence effect exists; for less polar solvents (e.g., n-heptane), Ag6It is not dissolved and no more vesicles are formed.
The invention has the outstanding characteristics and beneficial effects that:
1. ag in the invention6Is a multi-metal cluster compound, belongs to a novel inorganic material, and has novel structure and propertiesIs unique; can induce Ag under specific conditions by using a supramolecular self-assembly method6Self-aggregates to form vesicles. Ag6The formed supramolecular vesicles retain the fluorescent properties in the solid state.
2. The invention can prepare the fluorescent vesicle in various solvents, and the fluorescence color changes with the variety of the solvents.
3. The fluorescent vesicle of the present invention is paired with Fe3+The detection has high selectivity and sensitivity. And the detection is convenient, the change of the fluorescence intensity can be observed by using a portable ultraviolet lamp, the operation is simple, and the realization is easy.
4. The fluorescent vesicle prepared by the invention is added with Fe3+Quenching after fluorescence, and continuously adding reducing agent DL-dithiothreitol to recover fluorescence, so that the dual detection effect is achieved, and Fe can be detected by multiple use3+。
The material characteristics described in the present invention were tested in the following way:
1. transmission Electron Microscopy (TEM). The morphology of the fluorescent vesicles can be observed by TEM.
2. High resolution transmission electron microscopy (HR-TEM). The fine structure of the fluorescent vesicles can be observed by HR-TEM.
3. Fluorescence spectroscopy. The fluorescence intensity of the sample was measured by fluorescence spectrophotometer.
4. Ultraviolet-visible spectroscopy. The absorption curve of the sample can be determined by ultraviolet-visible spectroscopy.
Drawings
FIG. 1 shows Ag as a synthesized substance in example 1 of the present invention6The molecular structure of (1).
FIG. 2 is TEM images of different magnifications of silver nanocluster fluorescent vesicles prepared in example 1 of the present invention.
Fig. 3 is a TEM image of silver nanocluster fluorescent vesicles prepared in examples 2, 3 and 4 of the present invention. Wherein: (a) example 2, (b) is example 3, and (c) is example 4. The inset is an image at greater magnification, with a scale of 20 nm.
FIG. 4 is an optical photograph of silver nanocluster fluorescent vesicle samples prepared in examples 1-4 of the present invention. Wherein: (a) example 2 is shown, (b) is example 1, (c) is example 3, and (d) is example 4.
FIG. 5 is a fluorescence spectrum of the silver nanocluster fluorescent vesicles prepared in examples 1 to 4 of the present invention.
FIG. 6 shows the same concentration (2mmol L) added in Experimental example 1 of the present invention-1) After different kinds of metal ions are added to the silver nanocluster fluorescent vesicle prepared in example 1 of the present invention, an optical photograph of the sample is taken under the irradiation of an ultraviolet lamp with a wavelength of 365 nm.
FIG. 7 shows the same concentration (2mmol L) added in Experimental example 1 of the present invention-1) Fluorescence spectra of silver nanocluster fluorescent vesicles prepared by different kinds of metal ions in example 1 of the invention.
FIG. 8 shows that after metal ions are added (I) and before metal ions are added (I) into the silver nanocluster fluorescent vesicles prepared in example 1 of the present invention0) Histogram of fluorescence intensity ratio at wavelength 485nm (left). Fe is continuously added into the system of adding other kinds of metal ions into the silver nanocluster fluorescent vesicles prepared in the embodiment 1 of the invention3+Then, at 485nm (I/I)0) Histogram of ratios (right).
FIG. 9 shows the addition of Fe at different concentrations in Experimental example 2 of the present invention3+Fluorescence spectra of the fluorescent vesicles prepared in example 1 of the present invention.
FIG. 10 shows the addition of Fe at different concentrations in Experimental example 2 of the present invention3+After (I) adding Fe3+Front (I)0) Curve of the ratio of the fluorescence intensity at a wavelength of 485 nm.
FIG. 11 shows that 2mmol L of silver nanocluster fluorescent vesicle prepared in example 1 is added into silver nanocluster fluorescent vesicle prepared in experiment example 3 of the present invention-1Fe3 +And then adding an optical photograph of the sample change of DL-dithiothreitol. Wherein: (a) silver nanocluster fluorescent vesicles prepared in example 1, and (b) silver nanocluster fluorescent vesicles are added with L of 2mmol-1Fe3+And (c) is the addition of Fe3+Then 4mmol L of L was added-1DL-dithiothreitol (1). (a) In (b) and (c), the left side shows a photograph under a fluorescent lamp, and the right side shows a photograph under an ultraviolet lamp having a wavelength of 365 nm.
FIG. 12 shows that 2mmol L of silver nanocluster fluorescent vesicle prepared in example 1 is added into silver nanocluster fluorescent vesicle prepared in experiment example 3 of the present invention-1Fe3 +Then adding different amounts of DL-dithiothreitol, and obtaining the fluorescence spectrogram of the sample.
FIG. 13 shows that 2mmol L of silver nanocluster fluorescent vesicle prepared in example 1 is added into experimental example 3-1Fe3+Then adding different amounts of DL-dithiothreitol (I) and DL-dithiothreitol (I)0) Front ratio change curve of fluorescence intensity at 485 nm.
FIG. 14 shows silver nanocluster fluorescent vesicles prepared in example 1 of Experimental example 3 of the present invention and 2mmol L of the fluorescent vesicles are sequentially added thereto-1Fe3+And UV absorption spectrum after DL-dithiothreitol.
Detailed Description
The invention is further illustrated, but not limited, by the following examples and the accompanying drawings.
The raw materials used in the examples are conventional raw materials, commercially available products, wherein: AgNO3Purchased from Kemiou Chemicals, Inc., Tianjin, H2mna was purchased from sigma aldrich, various metal salts were nitrates purchased from kyou chemical reagent limited, tianjin, and solvents were purchased from national drug group chemical reagent limited and used directly without treatment before use.
Example 1
A preparation method of a silver nanocluster fluorescent vesicle comprises the following steps:
(1)Ag6synthesis of molecules
Accurately weighing 1mmol (167mg) of AgNO3And 1mmol (155mg) of H2The mna solid was dissolved in 6mL of water in a round bottom flask and sonicated for 20 min at room temperature (160W,40kHz) to give a precipitate. To the precipitate was added dropwise ammonia (25 wt%, 8 drops) to give a yellow clear solution. Slowly volatilizing the solvent to dry to obtain Ag6。
(2) Preparation of silver nanocluster fluorescent vesicle
Weighing 1.674mg of Ag6Dissolving in 20mL of ethylene glycol, performing ultrasonic treatment for 10s to dissolve the ethylene glycol, and standing in a thermostat at 20 ℃ for 24h to obtain the product.
Ag obtained in this example6The molecular structure of (A) is shown in FIG. 1. From FIG. 1, Ag is shown6Is a six-core silver nanocluster.
In this example, TEM images of different magnifications of silver nanocluster fluorescent vesicles are shown in fig. 2. As can be seen from fig. 2, the silver nanocluster fluorescent vesicles are in a vesicle state.
Example 2
A preparation method of a silver nanocluster fluorescent vesicle comprises the following steps:
(1)Ag6synthesis of molecules
Accurately weigh 2mmol (334mg) of AgNO3And 2mmol (310mg) of H2The mna solid was dissolved in 6mL of water in a round bottom flask and sonicated for 20 min at room temperature (160W,40kHz) to give a precipitate. To the precipitate was added dropwise ammonia (25 wt%, 16 drops) to give a yellow clear solution. Slowly volatilizing the solvent to dry to obtain Ag6。
(2) Preparation of silver nanocluster fluorescent vesicle
Weighing 1.674mg of Ag6Dissolving in 20mL of dimethyl sulfoxide, performing ultrasonic treatment for 10s to dissolve the dimethyl sulfoxide, and standing in a thermostat at 20 ℃ for 24h to obtain the product.
A TEM image of the silver nanocluster fluorescent vesicles obtained in this example is shown in fig. 3 (a).
Example 3
A preparation method of a silver nanocluster fluorescent vesicle comprises the following steps:
(1)Ag6synthesis of molecules
Accurately weighing 1mmol (167mg) of AgNO3And 1mmol (155mg) of H2The mna solid was dissolved in 6mL of water in a round bottom flask and sonicated for 20 min at room temperature (160W,40kHz) to give a precipitate. To the precipitate was added dropwise ammonia (25 wt%, 8 drops) to give a yellow clear solution. Slowly volatilizing the solvent to dry to obtain Ag6。
(2) Preparation of silver nanocluster fluorescent vesicle
0.6696mg of Ag are weighed6Dissolving in 20mL of methanol, performing ultrasonic treatment for 10s to dissolve, and standing in a thermostat at 20 ℃ for 24h to obtain the product.
A TEM image of the silver nanocluster fluorescent vesicles obtained in this example is shown in fig. 3 (b).
Example 4
A preparation method of a silver nanocluster fluorescent vesicle comprises the following steps:
(1)Ag6synthesis of molecules
Accurately weighing 1mmol (167mg) of AgNO3And 1mmol (155mg) of H2The mna solid was dissolved in 6mL of water in a round bottom flask and sonicated for 20 min at room temperature (160W,40kHz) to give a precipitate. To the precipitate was added dropwise ammonia (25 wt%, 8 drops) to give a yellow clear solution. Slowly volatilizing the solvent to dry to obtain Ag6。
(2) Preparation of silver nanocluster fluorescent vesicle
0.6696mg of Ag are weighed6Dissolving in 40mL acetonitrile, performing ultrasonic treatment for 10s to dissolve the acetonitrile, and standing in a thermostat at 20 ℃ for 24h to obtain the product.
A TEM image of the silver nanocluster fluorescent vesicles obtained in this example is shown in fig. 3 (c).
Experimental example 1
Transferring 20. mu.L of 200 mmol. multidot.L-1Metal ion (Ba) of2+,Zn2+,Pb2+,Ni2+,Mg2+,Na+,Cu2+,Co2+,Cd2+,Fe3+) The ethylene glycol solution was added into 2mL of the silver nanocluster fluorescent vesicles prepared in example 1, mixed uniformly by vortexing for 10 seconds, and the mixture was left standing for 2 hours, and the sample was observed under an ultraviolet lamp having a wavelength of 365nm, and an optical photograph is shown in fig. 6 (anions of metal ions are all nitrate).
The silver nanocluster fluorescent vesicles and the samples added with different types of metal ions are transferred to a quartz cuvette respectively, and the emission spectrograms of the samples are measured by a fluorescence spectrophotometer, as shown in fig. 7. After (I) and before (I) metal ions are added into silver nano-cluster fluorescent vesicles0) Fluorescence at a wavelength of 485nmThe histogram of the intensity ratio is shown in fig. 8 (left).
Ag6The molecules still maintain the original luminescence property after being aggregated to form vesicles due to pi-pi action between ligands due to the transfer of the ligands to metal charges. As can be seen from FIGS. 7 and 8, only Fe was found after addition of the metal ions3+Can completely quench the fluorescence, and the addition of other metal ions has smaller fluorescence intensity. The silver nanocluster fluorescent vesicle prepared by the invention is used for detecting Fe3+Has high selectivity in aspect. The phenomenon can be observed by using a portable ultraviolet lamp and a fluorescence spectrum, and the detection result is easy to observe and determine.
Experimental example 2
Removing different amounts of Fe3+In 2mL of the silver nanocluster fluorescent vesicle prepared in example 1, the concentration of the ethylene glycol solution is from 1 to 1333 μmol L-1Vortex for 10s to mix well and let stand for 2 hours. Adding Fe with different concentrations3+The sample was transferred to a quartz cuvette, and the emission spectrum of the sample was measured using a fluorescence spectrophotometer, and the result is shown in FIG. 9. Fe is added into silver nanocluster fluorescent vesicles3+After (I) and addition of Fe3+Front (I)0) The change curve of the fluorescence intensity ratio at a wavelength of 485nm is shown in FIG. 10.
Calculated, the detection line is 24.8 mu mol L-1，Fe3+And Ag6Has an action constant of 2.59X 104M-1. The silver nanocluster fluorescent vesicle prepared by the invention is used for detecting Fe3+The aspect has high sensitivity.
Experimental example 3
2mmol L of silver nanocluster fluorescent vesicle prepared in example 1 is added-1Fe3+Then 4mmol L of L are added-1The photographs of the sample changes with a fluorescent lamp and a 365nm ultraviolet lamp are shown in FIG. 11. Wherein: (a) silver nanocluster fluorescent vesicles prepared in example 1, and (b) silver nanocluster fluorescent vesicles are added at a concentration of 2 mmols L-1Fe3+And (c) is the addition of Fe3+Then 4mmol L of L was added-1DL-dithiothreitol (1). (a) Middle left of (b) and (c)The side is a photograph under a fluorescent lamp, and the right side is a photograph under an ultraviolet lamp having a wavelength of 365 nm.
2mmol L of silver nanocluster fluorescent vesicle prepared in example 1 is added-1Fe3+Then, different amounts of a solution of DL-dithiothreitol in ethylene glycol (concentration from 0 to 4.66mmol L) were removed-1) Add to it, vortex for 10s to mix well, and let stand for 2 hours. The fluorescence spectra of the samples after addition of different amounts of DL-dithiothreitol are shown in FIG. 12. After addition of DL-dithiothreitol (I) and addition of DL-dithiothreitol (I)0) FIG. 13 shows the ratio of the fluorescence intensity at 485 nm. Silver nanocluster fluorescent vesicle prepared in example 1 and to which 2mmol L was sequentially added-1Fe3+And DL-dithiothreitol, as shown in FIG. 14.
As can be seen from FIGS. 12, 13 and 14, the silver nanocluster fluorescent vesicles with completely quenched fluorescence gradually recover from the addition of DL-dithiothreitol, because DL-dithiothreitol has strong reducibility and can cause Fe3+Reduction to Fe2+The absorption intensity of ions at 320nm is obviously reduced, the competitive absorption is greatly weakened, and Ag6More energy can be absorbed to restore the fluorescence. The silver nanocluster fluorescent vesicle can realize Fe pairing3+And DL-dithiothreitol, and in addition, the silver nanocluster fluorescent vesicle can be repeatedly utilized to realize Fe3+Multiple detections of (2).
Although the embodiments of the present invention have been described with reference to the accompanying drawings, the scope of the present invention is not limited thereto, and various modifications and variations which do not require inventive efforts and which are made by those skilled in the art are within the scope of the present invention.

Claims (10)

1. A silver nanocluster fluorescent vesicle is characterized in that the fluorescent vesicle is made of Ag6Dissolving into polar organic solvent to form fluorescent vesicle.
2. The silver nanocluster fluorescent vesicle of claim 1, wherein said polar organic solvent is dimethyl sulfoxide, ethylene glycol, methanol or acetonitrile.
3. The silver nanocluster fluorescent vesicle according to claim 1, wherein the Ag is6The molar concentration of the organic solvent is 10-70 mu mol.L-1。
4. The silver nanocluster fluorescent vesicle according to claim 1, wherein the Ag is6The preparation method comprises the following steps:
mixing a silver nitrate aqueous solution and a 2-mercaptonicotinic acid aqueous solution, and carrying out ultrasonic treatment to obtain a precipitate; adding ammonia water dropwise into the precipitate to obtain a solution, slowly volatilizing the solvent to dry to obtain Ag6。
5. The preparation method of the silver nanocluster fluorescent vesicle of claim 1, comprising the steps of:
（1）Ag6synthesis of molecules
Mixing a silver nitrate aqueous solution and a 2-mercaptonicotinic acid aqueous solution, and carrying out ultrasonic treatment to obtain a precipitate; adding ammonia water dropwise into the precipitate to obtain solution, volatilizing the solvent to dry to obtain Ag6；
(2) Preparation of silver nanocluster fluorescent vesicle
Mixing Ag with water6Dissolving the silver nanocluster in a polar organic solvent, and dissolving the silver nanocluster in an ultrasonic manner to obtain the silver nanocluster fluorescent vesicle.
6. The method according to claim 5, wherein the concentration of the silver nitrate aqueous solution in the step (1) is 0.1 to 1 mol-L-1The concentration of the 2-mercaptonicotinic acid aqueous solution is 0.1-1 mol.L-1(ii) a The molar ratio of silver nitrate to 2-mercaptonicotinic acid is 1: (0.8 to 1.2).
7. The preparation method according to claim 5, wherein the ultrasonic frequency of the ultrasonic treatment is 30-50 kHz, the ultrasonic power is 140-160W, and the ultrasonic time is 10-30 minutes.
8. The preparation method according to claim 5, wherein the mass concentration of the ammonia water in the step (1) is 20-30%.
9. The method according to claim 5, wherein the polar organic solvent in the step (2) is dimethyl sulfoxide, ethylene glycol, methanol or acetonitrile;
Ag6the molar concentration of the organic solvent is 10-70 mu mol.L-1；
The ultrasonic frequency of ultrasonic dissolution is 30-50 kHz, the ultrasonic power is 140-160W, and the ultrasonic time is 5-10 s.
10. The silver nanocluster fluorescent vesicle of claim 1 in Fe3+Application in detection.
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