CN112916863B - Water-soluble luminescent silver nanocluster and preparation method and application thereof - Google Patents
Water-soluble luminescent silver nanocluster and preparation method and application thereof Download PDFInfo
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Abstract
The invention adopts 3, 4-dihydroxy-L-phenylalanine as a reducing agent and a ligand protective agent to prepare the water-soluble luminescent silver nanocluster with good luminescent property, the preparation process is simple and environment-friendly, the addition of chemical reagents such as common reducing agents sodium borohydride, ascorbic acid, a surfactant and the like is avoided, the fluorescence emission peak is about 460nm, when the fluorescence is observed by using a black background under ultraviolet light, strong blue fluorescence is presented, and the fluorescence quantum yield can reach 3.50%. The preparation method avoids the use of strong base NaOH, has controllable reaction, uniform particle size distribution, average particle size of 1.58nm, good photobleaching resistance, room-temperature storage stability of more than 6 months, can be used for directly detecting PPi, and shows high sensitivity and selectivity.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a water-soluble luminescent silver nanocluster and a preparation method and application thereof.
Background
Pyrophosphate (PPi) is one of the most important biological anions and plays an important role in biological processes such as DNA and RNA polymerization, Adenosine Triphosphate (ATP) hydrolysis, and regulation of enzyme activity, such as energy transduction, energy storage, cellular metabolism, gene regulation, and signal transduction. PPi is widely applied to food additives in the food industry, not only can compound metal ions to protect vitamin C from being damaged, but also can keep moisture of sausage and canned meat. PPi is also one of calcification inhibitors of organs such as muscles and blood vessels of the human body, and inhibits the conversion of amorphous salt into crystalline calcium phosphate, thereby inhibiting the growth of hydroxyapatite crystals, and thus it is often used as an anti-tartar ingredient of whitening toothpaste. However, recent studies have shown that excessive ingestion of PPi in humans increases the risk of cardiovascular disease, arthritis, chondrogenic calcification and calcium pyrophosphate deposition (CPDD) in humans. In addition, PPi is one of the major phosphorus contaminants, and excessive phosphate concentrations in natural waters can result in eutrophication of waters, thereby reducing the concentration of dissolved oxygen, and ultimately, suffocation death of certain fish and other aquatic animals. Therefore, for the environment and human beings, it is of great significance to establish a rapid and sensitive method for detecting PPi.
Currently, many methods have been used to detect PPi, including chemiluminescence, enzymatic techniques, capillary electrophoresis, electrochemical sensing, and spectrophotometry, but these methods have the disadvantages of being time consuming, complex in sample pretreatment, expensive in apparatus, and cumbersome to operate. 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. Common fluorescent materials are semiconductor quantum dots, organic fluorescent probes, and metal nanoclusters. Most quantum dot syntheses generally use highly toxic cadmium, and the synthesis process involves some toxic reagents. The preparation of organic fluorescent probes is complicated, and most probes are insoluble in water, so that the application of the organic fluorescent probes in biological systems is limited. The preparation process of the metal nanocluster is simple, organic and toxic solvents are hardly involved, and the metal nanocluster has the advantages of strong photoluminescence, good photobleaching property, water solubility and the like as those of quantum dot materials. The existing established method for detecting PPi by using metal nanoclusters is generally based on the phenomenon that PPi and metal ions are in strong coordination interaction, the metal ions (such as copper ions) induce fluorescence quenching of the nanomaterial, and the PPi is more capable of complexing the metal centers, so that the addition of PPi to the nanoclusters containing the metal ions can cause the fluorophore to be released into the solution again and the fluorescence is recovered. Since the fluorescence detection process relies on the fluorescence-shutdown process of copper ions, interference with the detection of thiol-containing species in PPi in complex matrices (e.g., serum) may be significant. Therefore, the development of reliable and sensitive fluorescence methods for the direct detection of PPi remains a great challenge.
Silver nanoclusters (AgNCs), one type of metal nanoclusters, have demonstrated tremendous applications in chemical/biological sensing and biological imaging. Compared with gold nanoclusters, AgNCs not only have lower cost, but also have the advantages of strong photoluminescence, good light stability, good water solubility and the like. At present, the literature reports that silver nanoclusters are prepared by using polymers, DNA, peptides, proteins and the like as templates are reported. Such as: min Yang et al (Journal of Alloys and Compounds,2019,781,1021-1027) synthesizes silver nanoparticles by using PVP as a ligand template and sodium borohydride and ascorbic acid as reducing agents and adopting a seed crystal method. Xiaodong Lin et al (Microchimica Acta,2019,186:648) purified AgNO3And mixing the solution and the DNA solution, incubating for 30 minutes, adding sodium borohydride serving as a reducing agent, and placing in a dark environment at 4 ℃ overnight to obtain the fluorescent AgNCs. Chuanxi Wang et al (Sensors and activators B, 2017,238: 1136-1143) sonicate for 15 minutes with glutathione GSH as a ligand and hydrazine hydrate as a reducing agent, precipitate silver nanoclusters by adding isopropanol, and centrifugally disperse in an aqueous solution to obtain fluorescent AgNCs. Guizou Yue et al (Sensors and activators B, 2019,287: 408-415) react BSA with AgNO3And mixing under an alkaline condition, and stirring for 2 hours at room temperature by using sodium borohydride as a reducing agent to obtain the fluorescent AgNCs. Xixiandong et al (journal of inorganic chemistry 2014,30(10),2341-2346) in the reaction of AgNO3And 3, 4-dihydroxy-L-phenylalanine under alkaline conditions (pH value is adjusted to 8.0 by NaOH), and the fluorescent silver nanocluster is obtained after 1h of sunlight irradiation. At present, the methods all need to add common reducing agents such as sodium borohydride, ascorbic acid, hydrazine hydrate and the like, are not beneficial to the stability of nanoclusters, and some methods also need to use NaOH with strong irritation and corrosiveness to control the pH of a system, so that the exploration of an environment-friendly, green and simple chemical synthesis method is very important for the development of AgNCs.
Disclosure of Invention
In view of the problems in the prior art, the present invention is directed to provide a water-soluble luminescent silver nanocluster and a method for preparing the same, which is intended to overcome the disadvantage of complicated preparation process in the existing preparation process of silver nanoclusters. PPi direct fluorescence detection is performed by using the silver nanoclusters, and the result is reliable and the operation is sensitive.
The invention provides a water-soluble luminescent silver nanocluster in a first aspect, which comprises the following raw materials: 3, 4-dihydroxy-L-phenylalanine, silver nitrate and water.
In some preferred embodiments of the silver nanoclusters of the present invention, the preparation raw material is 1 to 6 molar parts of 3, 4-dihydroxy-L-phenylalanine per 1 molar part of silver nitrate.
In some preferred embodiments of the silver nanoclusters of the present invention, the preparation raw material may be in an amount of 1, 2, 3,4, 5, and 6 molar parts, and any number therebetween, per 1 molar part of silver nitrate, corresponding to 3, 4-dihydroxy-L-phenylalanine; preferably, every 1mol part of silver nitrate corresponds to 2-4 mol parts of 3, 4-dihydroxy-L-phenylalanine; more preferably 3 molar parts of 3, 4-dihydroxy-L-phenylalanine per 1 molar part of silver nitrate.
The second aspect of the present invention provides a method for preparing the above water-soluble luminescent silver nanocluster, including: mixing the 3, 4-dihydroxy-L-phenylalanine aqueous solution with the silver nitrate aqueous solution, and reacting under the condition of heating reflux; the reaction conditions include: the heating temperature is 50-90 ℃; the reflux time is 6-42 h.
In some preferred embodiments of the preparation method of the present invention, the heating temperature may be 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃,78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃ and 90 ℃ and any value therebetween; preferably, the heating temperature is 70 ℃ to 80 ℃, more preferably 80 ℃.
In some preferred embodiments of the preparation method of the present invention, the reflux time may be 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, 15h, 15.5h, 16h, 16.5h, 17h, 17.5h, 18h, 18.5h, 19h, 19.5h, 20h, 20.5h, 21h, 21.5h, 22h, 22.5h, 23h, 23.5h, 24h, 24.5h, 25h, 25.5h, 26h, 26.5h, 27h, 27.5h, 28h, 28.5h, 29h, 29.5h, 30h, 30.5h, 31.5h, 32h, 34h, 34.5h, 34h, and any number therebetween; preferably, the reflux time is 18h to 36h, more preferably 24 h.
In some preferred embodiments of the preparation method of the present invention, the method further comprises centrifugal purification after cooling the reaction product.
In some preferred embodiments of the preparation process according to the invention, 1 part by volume of an aqueous solution of 3, 4-dihydroxy-L-phenylalanine at a concentration of 1mmol/L to 6mmol/L is mixed with 1 part by volume of a silver nitrate solution at a concentration of 1 mmol/L.
In some preferred embodiments of the preparation process according to the invention, 1 part by volume of an aqueous 3, 4-dihydroxy-L-phenylalanine solution having a concentration of 2mmol/L to 4mmol/L is mixed with 1 part by volume of a silver nitrate solution having a concentration of 1 mmol/L.
In some preferred embodiments of the preparation process according to the invention, 1 part by volume of an aqueous 3, 4-dihydroxy-L-phenylalanine solution having a concentration of 3mmol/L is mixed with 1 part by volume of a silver nitrate solution having a concentration of 1 mmol/L.
The third aspect of the present invention provides an application of the above silver nanocluster or the above method for preparing a silver nanocluster to PPi detection.
The technical scheme provided by the embodiment of the invention has the beneficial effects that at least:
(1) the invention adopts 3, 4-dihydroxy-L-phenylalanine as a reducing agent and a ligand protective agent to prepare the water-soluble luminescent silver nanocluster with good luminescent property, the preparation process is simple and environment-friendly, the addition of chemical reagents such as common reducing agents sodium borohydride, ascorbic acid, a surfactant and the like is avoided, the fluorescence emission peak is about 460nm, when the fluorescence is observed by using a black background under ultraviolet light, strong blue fluorescence is presented, and the fluorescence quantum yield can reach 3.50%.
(2) The water-soluble luminescent silver nanocluster prepared by the invention avoids the use of strong base NaOH, the reaction is controllable, the particle size distribution is uniform, the particle size distribution is between 0.60nm and 2.09nm, the average particle size is 1.58nm, the photobleaching resistance is good, and the storage stability at room temperature can reach more than 6 months.
(3) The water-soluble luminescent silver nanocluster prepared by the invention does not depend on the fluorescence closing process of copper ions, can be used for directly detecting PPi, and shows high sensitivity and selectivity, and the detection limit is 1.36 nM.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a transmission electron microscope image of water-soluble luminescent silver nanoclusters provided in example 8 of the present invention;
fig. 2 is a fluorescence excitation and emission spectrum of a water-soluble luminescent silver nanocluster provided in example 8 of the present invention;
fig. 3 is a graph of the photostability of water-soluble luminescent silver nanoclusters provided in example 8 of the present invention;
fig. 4 is a graph of the storage stability of water-soluble luminescent silver nanoclusters provided in example 8 of the present invention;
fig. 5 is an X-ray photoelectron spectrum of the water-soluble luminescent silver nanocluster provided in example 8 of the present invention;
fig. 6 is a working curve of the response of water-soluble luminescent silver nanoclusters provided by embodiment 8 of the present invention to PPi;
fig. 7 is a linear relationship between fluorescence intensity ratio F0/F and PPi concentration of the water-soluble luminescent silver nanocluster provided in example 8 of the present invention, where experimental data of the linear relationship is shown in table 2;
fig. 8 is a fluorescence histogram of the water-soluble luminescent silver nanoclusters provided in embodiment 8 of the present invention after being reacted with various anions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available from commercial sources.
In the following embodiments, each performance index testing apparatus is as follows:
1. the morphology of the water-soluble luminescent silver nanoclusters is characterized: transmission Electron Microscope (TEM), JEOL Ltd, JEM-2100, Japan.
2. Fluorescence excitation and emission spectrum determination of the water-soluble luminescent silver nanoclusters: full-function steady-state transient fluorescence spectrometer, Edinburgh, UK, FLS-920.
3. Determination of photobleaching resistance of water-soluble luminescent silver nanoclusters: full-function steady-state transient fluorescence spectrometer, Edinburgh, UK, FLS-920.
4. The chemical valence state of the water-soluble luminescent silver nanocluster is characterized in that: x-ray photoelectron spectrometer, Leybold Heraeus, China, SKL-12.
In the following examples, the water-soluble luminescent silver nanoclusters were prepared according to the following method, unless otherwise specified: mixing the 3, 4-dihydroxy-L-phenylalanine aqueous solution with the silver nitrate aqueous solution, reacting under the condition of heating reflux, cooling, and centrifuging and purifying the product.
The fluorescence emission peak of the prepared water-soluble luminescent silver nanocluster is about 460nm, and the water-soluble luminescent silver nanocluster is observed with a black background under ultraviolet light.
The quantum yield of silver nanoclusters was calculated according to formula (I) using quinine sulfate as a control and quinine sulfate QY in 0.1mol/L sulfuric acid of 0.54 as a reference standard:
Φx＝Φs×(As/Ax)×(Ix/Is)×(nx/ns)2formula (I)
In formula (I), "Φ" is the quantum yield; "A" is absorbance; "I" is the integrated area of fluorescence intensity; "n" is the refractive index of the solvent; the subscripts "x" and "s" represent the test sample (AgNCs) and the control sample (quinine sulfate), respectively.
[ example 1 ]
Uniformly mixing 1 part by volume of 1 mmol/L3, 4-dihydroxy-L-phenylalanine aqueous solution and 1 part by volume of 1mmol/L silver nitrate solution, heating the mixed solution to 50 ℃ for refluxing for 42h, cooling, taking out a product, and performing centrifugal purification to obtain the water-soluble luminescent silver nanocluster.
The fluorescence emission peak of the water-soluble luminescent silver nanocluster is about 460nm, and when the water-soluble luminescent silver nanocluster is observed under ultraviolet light and on a black background, relatively strong blue fluorescence is presented, and the quantum yield is 1.10% calculated according to the formula (I).
[ example 2 ]
Uniformly mixing 1 part by volume of 2 mmol/L3, 4-dihydroxy-L-phenylalanine aqueous solution and 1 part by volume of 1mmol/L silver nitrate solution, heating the mixed solution to 60 ℃, refluxing for 36h, cooling, taking out a product, and performing centrifugal purification to obtain the water-soluble luminescent silver nanocluster.
The fluorescence emission peak of the water-soluble luminescent silver nanocluster is about 460nm, and when the water-soluble luminescent silver nanocluster is observed under ultraviolet light and on a black background, relatively strong blue fluorescence is presented, and the quantum yield is 1.50% calculated according to the formula (I).
[ example 3 ]
Uniformly mixing 1 part by volume of 3 mmol/L3, 4-dihydroxy-L-phenylalanine aqueous solution and 1 part by volume of 1mmol/L silver nitrate solution, heating the temperature of the mixture to 70 ℃ for refluxing for 30h, cooling, taking out the product, and performing centrifugal purification to obtain the water-soluble luminescent silver nanocluster.
The fluorescence emission peak of the water-soluble luminescent silver nanocluster is about 460nm, and when the water-soluble luminescent silver nanocluster is observed under ultraviolet light and on a black background, relatively strong blue fluorescence is presented, and the quantum yield is calculated according to the formula (I) and is 2.80%.
[ example 4 ]
Uniformly mixing 1 part by volume of 4 mmol/L3, 4-dihydroxy-L-phenylalanine aqueous solution and 1 part by volume of 1mmol/L silver nitrate solution, heating the mixed solution to 80 ℃ for refluxing for 18h, cooling, taking out a product, and performing centrifugal purification to obtain the water-soluble luminescent silver nanocluster.
The fluorescence emission peak of the water-soluble luminescent silver nanocluster is about 460nm, and when the water-soluble luminescent silver nanocluster is observed under ultraviolet light and on a black background, relatively strong blue fluorescence is presented, and the quantum yield is calculated according to the formula (I) and is 3.00%.
[ example 5 ]
Uniformly mixing 1 part by volume of 5 mmol/L3, 4-dihydroxy-L-phenylalanine aqueous solution and 1 part by volume of 1mmol/L silver nitrate solution, heating the temperature of the mixture to 90 ℃, refluxing for 12 hours, cooling, taking out the product, and performing centrifugal purification to obtain the water-soluble luminescent silver nanocluster.
The fluorescence emission peak of the water-soluble luminescent silver nanocluster is about 460nm, and when the water-soluble luminescent silver nanocluster is observed under ultraviolet light and on a black background, relatively strong blue fluorescence is presented, and the quantum yield is calculated according to the formula (I) and is 0.80%.
[ example 6 ]
Uniformly mixing 1 part by volume of 6 mmol/L3, 4-dihydroxy-L-phenylalanine aqueous solution and 1 part by volume of 1mmol/L silver nitrate solution, heating the mixed solution to 80 ℃ for refluxing for 6h, cooling, taking out a product, and performing centrifugal purification to obtain the water-soluble luminescent silver nanocluster.
The fluorescence emission peak of the water-soluble luminescent silver nanocluster is about 460nm, and when the water-soluble luminescent silver nanocluster is observed under ultraviolet light and on a black background, relatively strong blue fluorescence is presented, and the quantum yield is calculated according to the formula (I) and is 2.40%.
[ example 7 ]
Uniformly mixing 1 part by volume of 2 mmol/L3, 4-dihydroxy-L-phenylalanine aqueous solution and 1 part by volume of 1mmol/L silver nitrate solution, heating the mixed solution to 80 ℃ for refluxing for 24h, cooling, taking out a product, and performing centrifugal purification to obtain the water-soluble luminescent silver nanocluster.
The fluorescence emission peak of the water-soluble luminescent silver nanocluster is about 460nm, and when the water-soluble luminescent silver nanocluster is observed under ultraviolet light and on a black background, relatively strong blue fluorescence is presented, and the quantum yield is calculated according to the formula (I) and is 3.20%.
[ example 8 ]
Uniformly mixing 1 part by volume of 3 mmol/L3, 4-dihydroxy-L-phenylalanine aqueous solution and 1 part by volume of 1mmol/L silver nitrate solution, heating the mixed solution to 80 ℃ for refluxing for 24h, cooling, taking out a product, and performing centrifugal purification to obtain the water-soluble luminescent silver nanocluster.
The fluorescence emission peak of the water-soluble luminescent silver nanocluster is about 460nm, and when the water-soluble luminescent silver nanocluster is observed under ultraviolet light and on a black background, relatively strong blue fluorescence is presented, and the quantum yield is calculated according to the formula (I) and is 3.50%.
(1) And (3) morphology characterization: the morphology of the synthesized water-soluble luminescent silver nanoclusters (AgNCs) is characterized by a transmission electron microscope, and as shown in FIG. 2, the water-soluble luminescent silver nanoclusters synthesized by the method of the present invention are spherical, uniformly dispersed, and have an average particle size of 1.36 nm.
(2) Fluorescence excitation and emission spectra: the fluorescence excitation and emission spectrum of 100. mu.L of the luminescent silver nanocluster solution having a concentration of 0.5mmol/L was measured by adding it to a fluorescence cuvette containing 1000. mu.L of HAC-NaAC buffer solution (pH 5) having a concentration of 25mmol/L, and the fluorescence emission peak of the luminescent silver nanocluster was 460nm as shown in FIG. 1.
(3) Photobleaching resistance test: and (3) placing the luminescent silver nanocluster under ultraviolet light for continuous irradiation for 60min, setting a fluorescence program as a dynamic scanning program, and detecting the fluorescence intensity of the water-soluble luminescent silver nanocluster every 0.5 s.
As shown in fig. 3, the water-soluble luminescent silver nanocluster solution can maintain good luminescent performance within 60min, which indicates that the photobleaching resistance is good. The aqueous solution of the fluorescent silver nanoclusters was left at room temperature, and the fluorescence intensity at 460nm was measured every 7 days for the first month, and then every 15 days. As shown in FIG. 4, the fluorescence intensity value remains unchanged after 6 months, and the fluorescence stability of the fluorescence intensity value is superior to that reported in the existing literature (Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy,2018,201,112-118) and remains for one month, which indicates that the fluorescent silver nanocluster has good light stability to the outside air, solution systems and the like.
(4) And (3) electronic energy spectrum characterization: the chemical valence of the synthesized luminescent silver nanoclusters was characterized by X-ray photoelectron spectroscopy (XPS), and fig. 5 is an XPS spectrum of Ag3d, indicating Ag3d5/2And Ag3d3/2The maximum peak values of the binding energy of (a) are 368.05eV and 374.38eV, respectively. Ag3d5/2Has a binding energy of 368.05eV between Ag+(367.5eV) and bulk Ag0(368.2eV), indicating that silver is Ag+And Ag0Exist in the form of (1). However, most of the silver should be in Ag0Due to Ag3d5/2Has a binding energy very close to that of Ag0The value of (c).
Comparative example 1
Comparative example 1 silver nanoclusters were synthesized using a photo-reduction method under alkaline conditions:
1 volume part of 2.0 mmol/L3, 4-dihydroxy-L-phenylalanine aqueous solution and 1 volume part of 1.0mmol/L silver nitrate solution are mixed uniformly, the pH value is adjusted to 8.0 by using NaOH, and the mixture is irradiated for 1 hour in the sunlight. The color of the solution is gradually changed from colorless to light red, and the excessive unreacted substances are purified by dialysis to obtain the silver nanoclusters. Under the ultraviolet light, when the fluorescent material is observed on a black background, the fluorescent material presents strong blue fluorescence, and the quantum yield is 2.30%.
Comparative example 1 was compared with example 8 and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the preparation process of example 8 does not require the addition of the strong basic compound NaOH and does not require exposure to ultraviolet light, which simplifies the operation method and avoids the damage to operators due to the strong irritation and corrosivity of NaOH and the radiation of ultraviolet light. Specifically, the method comprises the following steps:
(1) AgNO is used in the process of preparing silver nanocluster3And 3, 4-dihydroxy-L-benzeneThe alanine aqueous solution is acidic, and after the strong alkaline compound NaOH is added, a large amount of heat is emitted due to acid-base reaction violently, so that the temperature of the system is quickly raised, the reaction speed is accelerated, the nucleation speed of the silver nanocluster precursor is influenced, and the particle size of the silver nanocluster is uncontrollable.
(2) The mechanism of the mechanism is that high-energy ultraviolet light is utilized to irradiate a reaction solution to generate free radicals with high reduction capability, and then reduction reaction is carried out, but the light radiation has strong dependence on the external environment, and because the ultraviolet light intensity in all seasons and all time periods of a day is different, the experimental repeatability is poor, and the method is not suitable for wide application.
(3) In addition, sodium hydroxide (NaOH) is strongly irritating and corrosive, dust or smoke can irritate the eyes and respiratory tract, corrode nasal septum, burns can be caused by direct contact of skin and eyes with sodium hydroxide, and burns of digestive tract, mucosal erosion, bleeding and shock can be caused by misuse. Excessive uv light exposure can cause side effects or permanent damage to some people's body, and can easily induce skin cancer. NaOH has strong corrosivity, and ultraviolet light has strong radiativity, so the NaOH easily causes harm to operators.
(4) According to the method, silver nitrate and 3, 4-dihydroxy-L-phenylalanine aqueous solution are mixed at room temperature, heating and refluxing are carried out for 24 hours, after 24 hours of reaction, oxidation-reduction reaction occurs between the silver nitrate and the 3, 4-dihydroxy-L-phenylalanine, a silver nanocluster precursor is gradually nucleated and aged to generate a silver nanocluster with stable luminescence property, and the particle size is controllable through 24 hours of slow reaction, so that the silver nanocluster with uniform particle size and excellent luminescence property is generated.
[ application example 1 ] use of Water-soluble luminescent silver nanoclusters in detection of PPi
Injecting 100 mu L of water-soluble luminescent silver nanocluster with the concentration of 5mmol/L and 1000 mu L of HAC-NaAC buffer solution (25mmol/L, pH 5) into a fluorescence cuvette, stirring until the mixture is uniformly mixed and no bubble is generated, adding the mixture into the fluorescence cuvette in sequence from small to large according to the concentration of PPi solution, and measuring the fluorescence spectra of the mixture respectively by taking 342nm as an excitation wavelength. As shown in fig. 6, withThe PPi concentration is increased from 0.08 mu mol/L to 0.94 mu mol/L, and the fluorescence intensity of the silver nanocluster is gradually quenched; as shown in FIG. 7, the ratio F of fluorescence intensity before and after addition of PPi0The concentration of/F and PPi is linear (the experimental data is shown in Table 2), and the ratio of fluorescence intensity is F0Is represented by/F, wherein F0And F respectively represent the fluorescence intensity of the silver nanoclusters in the absence and presence of PPi, and the detection limit of PPi is 1.36nM (calculated according to the formula LOD of 3 σ/k, σ is standard deviation of fluorescence intensity values of the silver nanoclusters for 11 times, and k is the slope of the fitted straight line in fig. 7). The regression equation of the silver nanoclusters obtained by linear fitting is: y is 0.7518+2.6228X, and the linear coefficient is R2 is 0.995. Based on the method, the water-soluble luminescent silver nanocluster can be applied to detection of PPi.
TABLE 2
| Serial number | [PPi]/(μmol/L) | F0/ |
| 1 | 0.08 | 1.05 |
| 2 | 0.11 | 1.10 |
| 3 | 0.15 | 1.12 |
| 4 | 0.18 | 1.23 |
| 5 | 0.23 | 1.32 |
| 6 | 0.27 | 1.41 |
| 7 | 0.30 | 1.50 |
| 8 | 0.35 | 1.59 |
| 9 | 0.39 | 1.74 |
| 10 | 0.45 | 1.91 |
| 11 | 0.50 | 2.04 |
| 12 | 0.57 | 2.25 |
| 13 | 0.63 | 2.42 |
| 14 | 0.72 | 2.60 |
| 15 | 0.76 | 2.77 |
| 16 | 0.83 | 3.00 |
| 17 | 0.94 | 3.18 |
[ application example 2 ] use of Water-soluble luminescent silver nanoclusters in detection of PPi
100. mu.L of water-soluble luminescent silver nanoclusters at a concentration of 5mmol/L and 1000. mu.L of HAC-NaAC buffer solution (25mmol/L, pH 5) were injected into a fluorescence cuvette. PPi is added to the reaction solution to measure the normalized fluorescence intensity of the PPi to be 0.322 as a blank control; then 15 common anion potential interference substances are respectively added as coexisting ions of PPi (the concentration of the coexisting ions is 100 times that of the PPi), and the fluorescence intensity values are measured and recorded; PPi was added thereto, and the fluorescence intensity was measured and recorded. The fluorescence spectra were measured at 342nm as the excitation wavelength, and histograms of the fluorescence intensities at 460nm for different ions were plotted, as shown in FIG. 8. Experiments prove that other anions do not interfere the detection of PPi by the system.
The anions are each NO3 -、NO2 -、CO3 2-、HCO3 -、SO4 2-、HSO4 -、HSO3 2-、S2O3 2-、Cl-、Br-、I-、ClO4 -、SCN-、HPO4 2-、H2PO4 -。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. The preparation method of the water-soluble luminescent silver nanocluster is characterized in that the raw materials for preparing the silver nanocluster comprise: 3, 4-dihydroxy-L-phenylalanine, silver nitrate and water;
the preparation method comprises the following steps: mixing the 3, 4-dihydroxy-L-phenylalanine aqueous solution with the silver nitrate aqueous solution, and reacting under the condition of heating reflux; the reaction conditions include: the heating temperature is 50-90 ℃; the reflux time is 6-42 h; 1 volume part of 3, 4-dihydroxy-L-phenylalanine aqueous solution with the concentration of 1 mmol/L-6 mmol/L is mixed with 1 volume part of silver nitrate solution with the concentration of 1 mmol/L.
2. The preparation method according to claim 1, wherein the raw material for preparation is 2 to 4 parts by mole of 3, 4-dihydroxy-L-phenylalanine per 1 part by mole of silver nitrate.
3. The method according to claim 1, wherein the starting material is prepared in a molar ratio of 3, 4-dihydroxy-L-phenylalanine per 1 molar ratio of silver nitrate.
4. The method of claim 1, wherein the reaction conditions include: the heating temperature is 70-80 ℃; the reflux time is 18-36 h.
5. The method of claim 1, further comprising cooling the reaction product and purifying by centrifugation.
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