CN114935562A - Fluorescent probe based on gold nanocluster supramolecular assembly and application of fluorescent probe in perfluorooctanesulfonic acid detection - Google Patents

Abstract

A fluorescent probe based on gold nanocluster supramolecular assembly and application thereof in perfluorooctanesulfonic acid detection belong to the technical field of fluorescent detection. The invention uses HAuCl ₄ ·3H ₂ The method comprises the steps of preparing a gold nanocluster by using O as an Au source, cytidine-5' phosphate as a stabilizer and citric acid as a reducing agent, taking an assembly formed by the gold nanocluster and CLD215 as a fluorescent probe, dissociating the assembly by virtue of competition effect of perfluorooctanesulfonic acid to generate fluorescence quenching response, and establishing an AuNCs/CLD215 fluorescence emission spectrum fluorescence intensity-PFOS concentration linear curve, so that high-sensitivity quantitative detection of pollutant perfluorooctanesulfonic acid (PFOS) is realized, and the method has high sensitivity and a wide detection range. In addition, the fluorescent probe successfully detects PFOS in mineral water and soil water in real time and obtains high recovery rate.

Description

Fluorescent probe based on gold nanocluster supramolecular assembly and application of fluorescent probe in perfluorooctanesulfonic acid detection

Technical Field

The invention belongs to the technical field of fluorescence detection, and particularly relates to a fluorescent probe based on a gold nanocluster supramolecular assembly and application thereof in perfluorooctanesulfonic acid detection.

Background

Perfluorinated compounds are synthetic fluorinated organic compounds that have been widely used in surfactants, dye protection products, adhesives, fire fighting foams, pesticides and food packaging due to their unique hydrophobic and lipophobic properties. Because the perfluoro compound has very strong C-F bond (485 kJ. mol) ^-1 ) And thus has very high thermal and chemical stability. In addition, they are classified as persistent organic pollutants due to their toxicity and bioaccumulation properties.

In recent years, numerous reports have evaluated the toxicity of perfluorochemicals and their health risks to animals and humans. They can cause adverse damage to the kidney, liver and immune system by binding to proteins. The perfluorinated compounds have a high environmental persistence due to the thermal and chemical stability of the high energy fluorocarbon bond. At the same time, it can carry out transport, bioaccumulation and bioamplification along the food chain. Meanwhile, perfluorooctanesulfonic acid (PFOS) with a long chain (the carbon number of fluorine-containing bonds is more than or equal to 8) and a sulfonic group is easier to accumulate and amplify in organisms. Thus, among the large number of perfluorinated compounds, perfluorooctanesulfonic acid (PFOS) is the most representative persistent organic contaminant. Its presence is now found in the sera of many animals, both by workers and by the public, who are exposed to the job, in oceans and rivers around the world. Indicating that these perfluorinated compounds are distributed globally, it is of great interest to monitor PFOS in environmental systems.

Currently, common methods for quantitative detection of PFOS include: high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), gas chromatography-mass spectrometry (GC/MS), Surface Enhanced Raman Scattering (SERS), resonance light scattering, electrochemical analysis, and the like. Although these methods have certain advantages, the methods still have the disadvantages of complex synthesis process, complex sample preparation, expensive instrument requirements, time-consuming procedures and the like, and thus the application of the methods in high-throughput monitoring of environmental samples is hindered. Fluorescent sensors are receiving more and more attention due to their high sensitivity, convenient operation and non-destructive testing. However, fluorescent probes for PFOS detection are still very rare, e.g. up-converting nanoparticles, quantum dots and organic conjugated materials. However, many materials have limited applications due to poor water solubility, high cost, and poor selectivity. Therefore, it remains a challenge to develop a simple, rapid, cost effective assay for PFOS.

On the other hand, the metal nanoclusters have a unique core-shell structure and discrete energy levels, so that AuNCs have full-spectrum photoluminescence from blue to near infrared. In addition, excellent photostability, long carrier lifetime and stokes shift, low toxicity and good biocompatibility, excellent performance in analysis, sensing and bio-imaging. However, the luminescence of gold nanoclusters is generally weak, which severely limits their applicability in luminescence detection. In view of this, several strategies of doping metal ions (Ag and Cu), host-guest assembly and embedding into polymer matrix, aggregation-induced emission enhancement, etc. have been adopted to improve the light emitting performance. Aggregation-induced emission enhancement (AIEE), which mainly refers to the fact that molecules are stacked to reduce intermolecular interaction and greatly limit molecular rotation in an aggregation state, so that a non-radiative inactivation process of a single molecule is strongly inhibited, and finally, the fluorescence intensity of an AIEE (aggregation-induced emission enhancement) compound in a solid state or an aggregation state is far greater than that of the AIEE compound in a dilute solution. Therefore, in this experiment, the calix [4] arene functionalized by an amino group causes the metal nanoclusters to aggregate by supramolecular assembly, thereby greatly enhancing the luminescence intensity of the metal nanoclusters.

Disclosure of Invention

The invention aims to provide a fluorescent probe based on a gold nanocluster supramolecular assembly and application thereof in perfluorooctanesulfonic acid detection.

The invention enhances the fluorescence of the gold nanoclusters by supermolecular assembly and is applied to the detection of PFOS in an aqueous medium. The gold nanoclusters are synthesized by a hydrothermal method, cytidine-5 'phosphate (5' CMP) is used as a ligand, the excitation wavelength is 370-380 nm, and the strongest emission wavelength is 570-590 nm. The gold nanocluster has poor luminescence property and low stability. Therefore, supramolecular assembly is carried out by the supramolecular assembly of the supramolecular assembly and amino functionalized calix [4] arene (CLD215), and the fluorescence emission intensity of the gold nanocluster is greatly improved. The fluorescence enhancement is attributed to the supramolecular assembly of CLD215 and gold nanoclusters, which effectively improves the radiative transition rate and simultaneously inhibits the non-radiative rate, thereby enhancing the luminous intensity of the metal nanoclusters. The assembly formed by the gold nanoclusters and the CLD215 is used as a fluorescent probe, perfluorooctane sulfonate dissociates the assembly through competition, fluorescence quenching response is generated, and a fluorescence intensity-PFOS concentration linear curve of AuNCs/CLD215 fluorescence emission spectrum is established, so that high-sensitivity quantitative detection of a pollutant perfluorooctane sulfonate (PFOS) is realized. As a result, it was found that: the linear range for detecting PFOS is 0-100 mu M, the detection limit is 5.1 mu M, and the PFOS detection kit has high sensitivity and a wide detection range. In addition, the fluorescent probe successfully detects PFOS in mineral water and soil water in real time and obtains high recovery rate.

The invention relates to a fluorescent probe based on gold nanocluster supramolecular assembly, which is HAuCl ₄ ·3H ₂ O as Au source, cytidine-5 'phosphate (5' CMP) as stabilizer, citric acid as reducing agent; firstly, HAuCl is added ₄ ·3H ₂ Sequentially adding O, cytidine-5' phosphoric acid and citric acid-sodium citrate buffer solution with the pH value of 4.5 into the ultrapure water solution to form a mixed solution; in a mixed solution of HAuCl ₄ ·3H ₂ The final concentration of O is 8-15 mu M, the final concentration of cytidine 5' -monophosphate is 25-35 mu M, and the final concentration of sodium citrate is 200-300 mu M; carrying out hydrothermal reaction on the obtained mixed solution at 95-105 ℃ for 15-30 min to obtain a nucleotide-protected gold nanocluster solution, carrying out centrifugal freeze-drying to obtain solid powder, and preparing into AuNCs solution by using MES-NaOH buffer solution; then adding the amino functionalized cup [4] into the AuNCs solution]Aromatic hydrocarbon (CLD215) is subjected to supramolecular assembly, so that a fluorescent probe solution based on the gold nanocluster supramolecular assembly is obtained through non-covalent bonds, namely electrostatic interaction; concentration of AuNCs in AuNCs solution and cup [4]]The ratio range of the final concentration of the aromatic hydrocarbon is 0.1 mg/mL: 16-24 μ M.

Drawings

FIG. 1: (a) fluorescence excitation spectrum (left curve) and fluorescence emission spectrum (right curve) of AuNCs in aqueous solution, (b) Transmission Electron microscopy (HR-TEM) image and grain size distribution plot (inset) of AuNCs; corresponding to example 1;

FIG. 2 is a schematic diagram: (a) fluorescence emission spectra of AuNCs at different CLD215 concentrations, (b) a plot of the fluorescence intensity of the highest emission peak in the fluorescence emission spectra of AuNCs as a function of CLD215 concentration; corresponding to example 2;

FIG. 3: (a) transmission electron microscopy (HR-TEM) image and grain size distribution map (inset) of AuNCs/CLD215 (b) uv absorption spectra of AuNCs at different CLD215 concentrations; corresponding to example 3;

FIG. 4 is a schematic view of: (a) fluorescence emission spectra of AuNCs at different PFOS concentrations, (b) a point diagram of the change of fluorescence intensity of the AuNCs fluorescence emission spectra at 510nm along with the PFOS concentration; corresponding to example 4;

FIG. 5: fluorescence emission spectra of AuNCs/CLD215 at different PFOS concentrations; corresponding to example 4;

FIG. 6: (a) point diagram of change of fluorescence intensity at 510nm of AuNCs/CLD215 fluorescence emission spectrum with concentration of PFOS (0-180 mu M), (b) linear curve of fluorescence intensity at 510nm of AuNCs/CLD215 fluorescence emission spectrum-PFOS concentration (0-100 mu M); corresponding to example 4;

FIG. 7 is a schematic view of: (a) transmission electron microscopy (HR-TEM) and grain size distribution plot (inset) of AuNCs/CLD215+ PFOS; (b) ultraviolet absorption spectra of AuNCs/CLD215 at different PFOS concentrations; corresponding to example 5;

FIG. 8: selectivity for PFOS fluorescence response by AuNCs/CLD215 (a) and anti-interference analysis (b) histograms; the fluorescence quenching intensity ratio refers to the fluorescence intensity (I) at 510nm before PFOS is added ₀ ) Quenching difference (I) with fluorescence intensity (I) at 510nm after PFOS addition ₀ -I) and fluorescence intensity at 510nm before PFOS addition (I) ₀ ) Is a ratio of (I) ₀ -I)/I ₀ (ii) a Corresponding to example 6;

by way of reference ^[1] The fluorescent emission position of AuNCs (FIG. 1a), and it was preliminarily determined that AuNCs had been synthesized. Next, the prepared AuNCs were morphologically characterized (FIG. 1 b). The average size of the grains was found to be-1.45 nm after statistical analysis of the particle size. The fluorescent spectrum and the electron microscope characterization prove that the nucleotide-protected gold nanoclusters are successfully synthesized.

As shown in fig. 2a and b, with the gradual addition of calix [4] arene (CLD215) at different concentrations (0, 4, 8, 12, 16, 20, 24 μ M) to the AuNCs solution, the fluorescence intensity of AuNCs was significantly enhanced with a slight increase in lifetime (table 1), fluorescence was enhanced (-8 times), and accompanied by a certain degree of blue shift (-60 nm).

Then, the process is characterized in a certain way, as shown in fig. 3a, AuNCs/CLD215 is characterized in a shape, the particle size statistics of about 200 particles is carried out, the final statistical result is 10.07nm, and the particle size of the assembly is increased relative to AuNCs, so that the CLD215 and AuNCs are shown to generate supermolecule assembly through electrostatic interaction, and fluorescence emission is enhanced after aggregation is induced.

As shown in fig. 4a and b, as PFOS was added to the AuNCs solution in different concentrations (0, 20, 40, 80, 120, 200, 400 μ M) step by step, there was no significant quenching of fluorescence intensity, indicating that PFOS did not quench the fluorescence of gold nanoclusters themselves. However, as PFOS with different concentrations (0-180 μ M) is gradually added into AuNCs/CLD215 solution, the fluorescence intensity is obviously quenched (FIG. 5), which shows that PFOS can quench the fluorescence of the gold nanocluster and calixarene assembly. From FIG. 6b, it can be seen that AuNCs showed a very good linear response to PFOS in a wide range from 0 to 100. mu.M, with the fluorescence intensity of the fluorescent probe at 510nm decreasing with increasing PFOS concentration and finally reaching a plateau at 180. mu.M (FIG. 6 a). The linear relationship between the fluorescence intensity I at 510nm and the concentration of PFOS is shown in FIG. 6b, and the linear response to PFOS is 0-100 μ M (R) ² 0.995). And AuNCs/CLD215 was diluted with 20. mu.M MES-NaOH buffer (pH 6.5) and PFOS detection limit was calculated to be 5.1. mu.M.

In addition, other interferents such as PFOA, CTAB, caprylic acid, sodium 1-octanesulfonate, Na were also analyzed ₂ SO ₄ 、KCl、MgCl ₂ And NaCl on AuNCs/CLD215, and the results show that no interferents except PFOS can cause obvious change of fluorescence intensity of AuNCs/CLD215, and figure 8(a) shows that only PFOS can obviously quench the fluorescence of AuNCs/CLD 215. FIG. 8(b) shows that the addition of other interferents to PFOS containing solutions did not affect the fluorescent response of AuNCs/CLD215 to PFOS. Therefore, it is considered that these interfering substances and the like detect PF using a fluorescent AuNCs/CLD215 probeOS has no influence, which shows that the method is an effective means for detecting PFOS in practical application.

Detailed Description

Cytidine 5' -monophosphate (CMP) used in the present invention was purchased from TCI (shanghai) development limited. Chloroauric acid trihydrate (HAuCl) ₄ ·3H ₂ O), sodium citrate, citric acid were purchased from Beijing chemical factories. Tetraethylammonium heptadecafluorooctanesulfonate (PFOS), sodium 1-octanesulfonate, and maleic ethanesulfonic acid Monohydrate (MES) were purchased from Shanghai Aladdin reagent. Sodium Perfluorooctanoate (PFOA), n-octanoic acid, cetyl trimethylammonium bromide (CTAB) were purchased from Shanghai Michelin Biochemical technology Ltd. Basic chemicals such as sodium hydroxide (NaOH) were purchased from Tianjin Wai-Kao. All chemicals were analytically pure and were not repurified. Ultrapure water was used throughout the experiment.

Example 1:

according to the literature reports ^[1] Sequentially adding HAuCl ₄ ·3H ₂ O, cytidine 5' -monophosphate (CMP), citric acid-sodium citrate solution (pH 4.5) were added to 7mL of ultrapure water, HAuCl ₄ ·3H ₂ The final concentration of O is 10 muM, the final concentration of cytidine 5' -monophosphate is 30 muM, and the final concentration of sodium citrate is 250 muM; then, the obtained mixture solution is put into a 20mL high-pressure reaction kettle, hydrothermal reaction is carried out for 20min at 100 ℃, and nucleotide-protected gold nanocluster solution (AuNCs) is obtained after cooling.

The results show that: based on the AuNCs obtained in example 1, the excitation wavelength is 370-380 nm, the emission wavelength is 570-590 nm (figure 1a), and the gold nanoclusters are successfully synthesized through the initial determination of the emission positions of fluorescence spectra. Secondly, the morphology of the prepared AuNCs is characterized (figure 1b), and the figure shows that the dispersibility of the nano-particles is high and the particle size is uniform. The average grain size was found to be 1.45nm by statistical analysis of the grain size of about 200 AuNCs, and the interplanar spacing of the grains of AuNCs (inset in FIG. 1b) was 0.24 nm.

Example 2:

centrifuging the AuNCs obtained in example 1 by an acetone precipitation method, freeze-drying the AuNCs into solid powder after centrifugation, and preparing 1mg/mL AuNCs mother solution by using MES-NaOH solution; then diluted ten-fold with MES-NaOH buffer solution to obtain 0.1mg/mL AuNCs solution. Taking 7 parts of 500 mu L and 0.1mg/mL AuNCs solution, respectively dropwise adding different amounts of CLD215 into the solution to enable the final concentration of CLD215 to be 0, 4, 8, 12, 16, 20 and 24 mu M respectively (the result of figure 2b shows that the fluorescence intensity of the gold nanoclusters is increased to be strongest when the final concentration of calix [4] arene is 20 mu M (thereby, when the concentration of AuNCs in the AuNCs solution is 0.1mg/mL, the more appropriate final concentration of the calix [4] arene is 16-24 mu M), so as to obtain a fluorescence-enhanced assembly AuNCs/CLD215(0.1mg/mL and 20 mu M), namely a fluorescence probe based on the gold nanocluster supramolecular assembly,

when CLD215 reached 20 μ M, the fluorescence enhancement almost reached a plateau (fig. 2, with a slight enhancement in lifetime (table 1), fluorescence enhancement-8 fold, and with some degree of blue shift (-50 nm).

Table 1: fluorescence lifetime measurement data of AuNCs and AuNCs/CLD215

Example 3:

a series of characterizations were performed on the fluorescence-enhanced assembly AuNCs/CLD215(0.1mg/mL, 20. mu.M) obtained in example 2, thereby demonstrating the binding pattern between AuNCs and CLD215 and the mechanism of fluorescence enhancement. As shown in FIG. 3a, AuNCs/CLD215 was morphologically characterized and the particle size statistic was 10.07nm, thus, the increase in particle size from AuNCs to AuNCs/CLD215(20 μ M) is indicative of increased fluorescence due to increased aggregation-induced emission.

In addition, the change of ultraviolet absorbance with the gradual addition of calix [4] arene (CLD215) at different concentrations (0, 4, 8, 12, 16, 20, 24 μ M) to the AuNCs solution was also monitored (3b), which was found to be somewhat enhanced, and also indicated that gold nanoclusters and calixarene undergo supramolecular assembly to form luminescent aggregates.

The results show that: indicating that AuNCs and CLD215 are subjected to electrostatic interaction, supermolecule assembly is carried out, the particle size is increased, and a luminescent aggregate is formed.

Example 4:

the fluorescence-enhanced assembly AuNCs/CLD215(0.1mg/mL, 20. mu.M) obtained in example 2 was used as a fluorescent probe for PFOS detection. The experimental feasibility was first tested and, as shown in figures 4a, b, there was no significant quenching of fluorescence intensity with the stepwise addition of PFOS at different concentrations (0, 20, 40, 80, 120, 200, 400 μ M) in AuNCs solution (figures 4a, b). AuNCs/CLD215(0.1mg/mL, 20. mu.M) obtained in example 2 was diluted twice with MES-NaOH buffer (in this case, the concentration of AuNCs in AuNCs/CLD215 was 50. mu.g/mL, and the concentration of CLD215 was 10. mu.M. according to the results of examples 2 and 4, when the concentration of AuNCs in AuNCs solution was 50. mu.g/mL, the final concentration of calix [4] arene was suitably 8 to 12. mu.M), 500. mu.L of AuNCs/CLD215 (50. mu.g/mL, 10. mu.M) was taken, PFOS was added thereto at different concentrations (0 to 180. mu.M, all concentrations of the present invention were final concentrations), and quenching phenomenon of fluorescence intensity was clearly observed (FIG. 5). The PFOS has no quenching effect on the gold nanoclusters and has a quenching effect on the assembly, so that AuNCs/CLD215(50 mu g/mL, 10 mu M) is used for detecting the PFOS.

The invention mainly aims to detect PFOS, and from figure 6b, it can be seen that the AuNCs/CLD215 fluorescent probes show good linear response to PFOS in a wide concentration range from 0 to 100 mu M. As the concentration of PFOS increases, the fluorescence intensity of the fluorescent probe at 510nm decreases, and finally reaches the plateau (6a) at 180. mu.M. The linear relationship between the fluorescence intensity at 510nm and the concentration of PFOS is shown in FIG. 6b, and the linear response range for PFOS is 0-100 μ M (Y-3.01X +447.256, R) ² 0.995, where Y is the fluorescence intensity at 510nm and X is the PFOS concentration). And after 20 mu M MES-NaOH buffer solution (pH 6.5) is adopted to dilute AuNCs/CLD215, the detection limit of the AuNCs/CLD215 to PFOS is calculated ^[2] At 5.1. mu.M. The results show that: AuNCs/CLD215 has wider detection range and better detection limit for detecting PFOS, and can be used as a fluorescent probe for detecting PFOS.

Example 5:

the procedure for detecting PFOS by AuNCs/CLD215 in example 4 was characterized. AuNCs/CLD215-PFOS was first topographically characterized (FIG. 7 a). It can be seen from the figure that the dispersibility of the nanoparticles is high and the particle size is uniform. The average size of the grains was found to be 6.45nm by statistical analysis of the grain size of about 200 grains. Comparison with AuNCs/CLD215 particle size (10.07nm) reveals that the process from assembly to PFOS addition is a depolymerization process. In addition, the ultraviolet absorption spectrogram analysis (figure 7b) also finds that the trend of the ultraviolet absorption is just opposite to the trend of the ultraviolet absorption of the assembly, and the ultraviolet absorption of the AuNCs/CLD215 gradually decreases along with the increase of the concentration of PFOS after the PFOS is dripped, which also proves that the ultraviolet absorption is a depolymerization process and is consistent with the result of an electron microscope. From Table 2, it can be found that AuNCs/CLD215 has almost no change in fluorescence lifetime compared with AuNCs/CLD215-PFOS, indicating that the fluorescence quenching mechanism of AuNCs/CLD215-PFOS is static quenching.

Table 2: fluorescence lifetime measurement data of AuNCs/CLD215, AuNCs/CLD215+ PFOS

Example 6:

to study the selectivity of AuNCs/CLD215 for PFOS. Mixing a certain amount (200 μ M) of PFOS, PFOA, CTAB, n-octanoic acid, octane sodium sulfonate, Na ₂ SO ₄ 、KCl、MgCl ₂ NaCl was added to AuNCs/CLD215 diluted in MES-NaOH buffer (pH 6.5) and mixed rapidly. All fluorescence measurements were performed at room temperature. The results show that PFOS quenches AuNCs/CLD215 fluorescence to the greatest extent, others have little or less assembly fluorescence quenched. Shows that the AuNCs/CLD215 fluorescent probe can effectively detect PFOS (figure 8a)

The method for testing interference is that PFOS (200 mu M) is respectively added into AuNCs/CLD215 solution diluted by MES-NaOH buffer solution (pH 6.5) for incubation for five minutes, and then a series of interferents (200 mu M) (CTAB, caprylic acid, octane sodium sulfonate, Na and Na) are respectively added ₂ SO ₄ 、KCl、MgCl ₂ NaCl), and then subjected to fluorescence spectroscopy. The results show that addition of other interferents to the PFOS-containing solution did not affect AuNFluorescence response of Cs/CLD215 to PFOS (FIG. 8 b).

Example 7:

the detection of mineral water sample mainly comprises adding 100 μ L mineral water into AuNCs/CLD215 solution with the same concentration, and adding PFOS (66 μ M, 83 μ M, 100 μ M) with three different final concentrations into the above solution (marked as # 1- # 3). After incubation for 2min, fluorescence spectroscopy was performed. The results show that the recovery rate is between 97.5% and 104.1%, and the Relative Standard Deviations (RSDs) are lower than 5%, which indicates that AuNCs/CLD215 can be applied to the real object detection (Table 3).

Table 3: measurement data of PFOS in mineral water

A soil water sample detection method comprises the following steps of firstly, according to documents ^[3] With minor changes, the soil was treated, dispersed (0.1g, available from Yanhu lake university of Jilin) in 100mL MES-NaOH buffer (20mM, pH 6.5), and extracted ultrasonically (10 min); the sample was then heated to boiling, cooled to room temperature, and centrifuged (8000rpm, 10 min); finally, the measurement was carried out under the same conditions by filtration through a 0.22 μm filterable membrane. The results show that the recovery rate is between 95.6% and 104.8%, and the Relative Standard Deviations (RSDs) are lower than 5%, which indicates that AuNCs/CLD215 can be applied to physical detection (Table 4).

Table 4: measurement data of PFOS in soil water sample

It should also be noted that the particular embodiments of the present invention are provided for illustrative purposes only and do not limit the scope of the present invention in any way, and that modifications and variations may be made by persons skilled in the art in light of the above teachings, but all such modifications and variations are intended to fall within the scope of the invention as defined by the appended claims.

Reference to the literature

[1] Zucui, Wangyu, Wuyuqing, Lihong Wei, etc.; development of gold nanoclusters protected by cytidine 5' -monophosphate by aggregation-induced emission enhancement as a direct luminescent substrate for ratiometric and inhibitor evaluation of alkaline phosphatase [ J ], colloid and surface a: physicochemical and engineering aspects, 640(2022), 128423;

[2] zheng Hui, Gungwen super, Gaojie, Lei Yijiang, Guo Dong; differential calixarene receptor generation distinguishes the glycosaminoglycan mode [ J ], in the context of organic chemistry, 2018,5, 2685-2691;

[3] zhangqiao Juan, Liaolinyu, Yao Yizhi, etc.; a water-soluble fluorescent probe based on peracetylenediimide, which is used for perfluorooctane sulfonate [ J ] in a 100% aqueous medium, and is characterized in that: B. chemical, 350(2022) 130851.

Claims (3)

1. A fluorescent probe based on gold nanocluster supramolecular assemblies is characterized in that: is HAuCl ₄ ·3H ₂ Taking O as an Au source, cytidine-5' phosphate as a stabilizer and citric acid as a reducing agent; firstly, HAuCl is added ₄ ·3H ₂ Sequentially adding O, cytidine-5' phosphoric acid and citric acid-sodium citrate buffer solution with the pH value of 4.5 into the ultrapure water solution to form a mixed solution; in a mixed solution of HAuCl ₄ ·3H ₂ The final concentration of O is 8-15 mu M, the final concentration of cytidine 5' -monophosphate is 25-35 mu M, and the final concentration of sodium citrate is 200-300 mu M; then carrying out hydrothermal reaction on the obtained mixed solution at the temperature of 95-105 ℃ for 15-30 min to obtain a gold nanocluster solution protected by nucleotide, carrying out centrifugal freeze-drying to obtain solid powder, and preparing the solid powder into an AuNCs solution by using MES-NaOH buffer solution; then adding the amino functionalized cup [4] into the AuNCs solution]Aromatic hydrocarbon is subjected to supramolecular assembly, so that a fluorescent probe solution based on the gold nanocluster supramolecular assembly is obtained through non-covalent bonds, namely electrostatic interaction; concentration of AuNCs in AuNCs solution with cup [4]]The ratio range of the final concentration of the aromatic hydrocarbon is 0.1 mg/mL: 16 to 24 μ M.

2. The use of the gold nanocluster supramolecular assembly-based fluorescent probe according to claim 1 in perfluorooctanesulfonic acid detection.

3. The application of the gold nanocluster supramolecular assembly-based fluorescent probe in perfluorooctanesulfonic acid detection, according to claim 3, is characterized in that: when the concentration of AuNCs in the AuNCs solution is 0.05mg/mL and the final concentration of calix [4] arene is 10 mu M, the linear response range of the fluorescent probe to the concentration of the perfluorooctanesulfonic acid is 0-100 mu M, and the detection limit is 5.1 mu M.

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