A bimetallic nanocluster fluorescent probe compound and application thereof in preparation of a product for rapidly detecting acetylene

Abstract

The application belongs to the technical field of fluorescent probe detection, and discloses a bimetallic nanocluster fluorescent probe compound and application thereof in preparation of a product for rapidly detecting acetylene. The fluorescent probe compound is a gold-copper bimetallic nanocluster solution modified by adamantane thiol, which is used as a fluorescent probe for acetylene detection. The solution has a clear and controllable preparation process. Through specific proportioning and reaction conditions of cuprous chloride, adamantane thiol, tetrachloroauric acid, sodium borohydride and other reagents, a probe solution with stable fluorescence characteristics can be prepared. The bimetallic nanocluster fluorescent probe compound is applied in preparation of a product for rapidly detecting acetylene. Through specific combination of fluorescent molecules and acetylene gas to trigger the secondary effect of fluorescence quenching, detection is realized, and other substances cannot trigger quenching. At a wavelength of 700 nm, the linear relationship (R 2 >0.99) between the fluorescence intensity and the acetylene concentration realizes accurate quantification of the acetylene concentration, and the minimum detection limit is 0.026 muL / L.

Description

Technical Field

[0001] This invention belongs to the field of fluorescent probe detection technology, specifically relating to a bimetallic nanocluster fluorescent probe compound and its application in the preparation of products for rapid detection of acetylene. Background Technology

[0002] Acetylene (C2H2), a highly flammable, explosive, and toxic unsaturated hydrocarbon gas, requires precise and rapid detection in various fields, including industrial production, power systems, environmental monitoring, and safety protection. In industrial settings, acetylene is commonly used in metal welding and organic synthesis processes; leaks can lead to explosions, poisoning, and other safety accidents, posing a serious threat to human life and property. In the power industry, when faults occur inside oil-immersed electrical equipment such as power transformers and instrument transformers, the insulating oil decomposes to produce characteristic gases such as acetylene. Detecting acetylene concentration allows for timely assessment of the severity of equipment failure, preventing the fault from escalating and causing power grid paralysis. Furthermore, rapid qualitative and quantitative analysis of acetylene plays an irreplaceable role in scenarios such as tail gas emission monitoring in chemical industrial parks and ventilation safety monitoring in mines. Therefore, developing high-performance acetylene detection technology is of significant practical importance for ensuring production safety, maintaining equipment stability, and protecting the ecological environment.

[0003] Currently, there are many types of acetylene detection technologies developed in the industry, but their core performance has significant defects, making it difficult to meet the needs of efficient monitoring in complex scenarios. Specifically, electrochemical sensor detection technology is one of the most widely used acetylene detection methods. Its principle is to use the electrochemical reaction of acetylene on the surface of the sensor electrode to generate an electrical signal, and then convert the acetylene concentration through the signal intensity.

[0004] For example, CN202410774616.8 discloses a high-performance acetylene gas sensor and its preparation method. It relates to the field of gas-sensitive materials technology, and particularly to a gas-sensitive material, a gas sensor, its preparation method, and its applications. The gas-sensitive material is a bimetallic (Sm and Ag) modified semiconductor material SnO2, prepared using a sol-gel method with Sm2O3-modified SnO2; then, Ag-containing materials are added and calcined. The gas sensor includes a ceramic tube-based side-heated structure and the gas-sensitive material distributed on the ceramic tube. The gas-sensitive material, gas sensor, and their preparation method of this application have higher sensitivity, lower detection limit, lower operating temperature, and good selectivity, and can be used for the selective detection of acetylene gas. CN202310249660.2 discloses a low-detection-limit MEMS acetylene gas sensor and its preparation method. This low-detection-limit MEMS acetylene gas sensor and its fabrication method include: fabricating SiO2-Si3N4 bilayer composite films on the front and back sides of a Si substrate, respectively; depositing an insulating layer on the front composite film; using self-assembled monolayer SiO2 microspheres as templates, and combining radio frequency sputtering of SnO2 metal oxide, ultrasonically removing the SiO2 microspheres in acetone to prepare a SnO2 porous film; then depositing Au using electron beam evaporation technology, followed by heat treatment to form aggregated particles; obtaining a sensitive electrode and lead pad, a heating electrode and lead pad on the front side of the silicon wafer; and etching a groove on the back side to obtain a sensor with an insulating groove. The Au nanoparticle-modified SnO2 porous film exhibits high uniformity, fast sensor response speed, and low power consumption, meeting the requirements of ultra-low detection limit and volume constraints in acetylene detection. While this type of technology has the advantages of fast response speed and small device size, it has two major drawbacks: First, it has extremely poor anti-interference ability. Common reducing gases in industrial environments, such as hydrogen, carbon monoxide, and ethylene, can easily compete with acetylene for reaction on the electrode surface, leading to serious deviations in the detection results. Second, the sensor has a short lifespan. Electrode materials are prone to oxidation and poisoning failure during long-term use, and usually need to be replaced every 3-6 months. This not only increases maintenance costs but may also lead to the risk of missed detections due to untimely replacement.

[0005] Semiconductor sensor detection technology, due to its low cost and simple structure, has found applications in low-end detection scenarios. This type of detection works by calculating concentration based on the change in resistance caused by the contact between acetylene and a semiconductor sensitive material. However, this technology suffers from serious deficiencies in accuracy and stability: firstly, the sensitivity of semiconductor materials is easily affected by environmental factors such as temperature and humidity; in scenarios with high temperature and humidity or drastic temperature and humidity fluctuations, detection errors can reach over 30%; secondly, the sensor exhibits significant baseline drift, requiring frequent calibration to maintain basic detection accuracy. For remote areas and unattended monitoring points, the difficulty of frequent calibration operations greatly limits its application scope.

[0006] Gas chromatography (GC) is one of the most accurate traditional detection techniques. By separating the components in the analyte gas and performing qualitative and quantitative analysis, it can achieve accurate detection of acetylene. For example, CN201910145158.0 discloses a fluorescent probe for detecting intracellular hydrogen sulfide, its preparation method, and its application. However, this technique has limitations in achieving non-invasive in-situ monitoring, as electrochemical analysis and chromatography methods are difficult to implement.

[0007] In addition to the mainstream technologies mentioned above, some traditional detection methods (such as infrared spectroscopy and laser absorption spectroscopy) are also used for acetylene detection, but each has its own limitations: infrared spectroscopy is affected by the overlapping absorption of gas components, resulting in low detection sensitivity and difficulty in identifying low concentrations of acetylene; laser absorption spectroscopy has high equipment costs, requires stringent optical conditions in the detection environment, and is easily affected by factors such as dust and fog, making it unsuitable for harsh industrial environments.

[0008] In summary, existing acetylene detection technologies generally suffer from problems such as weak anti-interference capabilities, insufficient accuracy and stability, slow response speed, high maintenance costs, complex operation, or bulky equipment. They cannot simultaneously meet the core requirements of high sensitivity, high selectivity, rapid response, low cost, and ease of operation. These shortcomings are particularly pronounced in scenarios such as real-time monitoring of low-concentration acetylene, anti-interference detection in complex environments, and portable on-site detection, becoming key bottlenecks restricting the improvement of acetylene safety monitoring levels.

[0009] Therefore, developing a comprehensive and practical acetylene detection technology has become a pressing technical challenge for the industry. Summary of the Invention

[0010] To address the above-mentioned technical problems, the first objective of this invention is to provide a bimetallic nanocluster fluorescent probe compound. This compound utilizes an adamantanethiol-modified gold-copper bimetallic nanocluster (ADM-AuCu NCs) solution as a fluorescent probe for acetylene detection, which differs from traditional electrochemical and semiconductor detection sensors. Furthermore, the solution has a well-defined and controllable preparation process. By using specific ratios and reaction conditions of reagents such as cuprous chloride, adamantanethiol, tetrachloroauric acid, and sodium borohydride, a probe solution with stable fluorescence properties can be prepared for detecting the fluorescence quenching reaction of acetylene.

[0011] The second objective of this invention is to provide an application of a bimetallic nanocluster fluorescent probe compound in the preparation of products for rapid detection of acetylene. Detection is achieved through a secondary effect of fluorescence quenching triggered by the specific binding of fluorescent molecules to acetylene gas; other substances cannot induce quenching. A linear relationship (R0) between fluorescence intensity and acetylene concentration is observed at a wavelength of 700 nm. 2(>0.99) to achieve accurate quantification of acetylene concentration. An acetylene detection workflow was constructed, involving reaction with the analyte gas in a headspace vial, detection by a fluorescence spectrophotometer, and concentration conversion from a standard curve. This method not only has extremely high detection sensitivity, capable of identifying acetylene as low as 0.026 μL / L, but also possesses strong anti-interference capabilities (no response to common gases such as H2, CO, CO2, CH4, C2H6, and C2H4). Furthermore, it is fast, easy to operate, and low in cost. Compared with the standard gas chromatography method, the detection data showed no significant difference, verifying its reliability.

[0012] To achieve the above objectives, the present invention adopts the following technical solution: A bimetallic nanocluster fluorescent probe compound, wherein the fluorescent probe compound is a solution of gold-copper nanoclusters modified with adamantanethiol, labeled as ADM-AuCu NCs solution; The preparation method of the fluorescent probe compound is as follows: Adamantane thiol solution and cuprous chloride solution were selected and mixed at room temperature. Then, a solution of tetrachloroauric acid solution and sodium borohydride solution premixed in a certain volume ratio was slowly added dropwise. The mixture was stirred under a light-proof and nitrogen atmosphere to obtain ADM-AuCuNCs solution. The ADM-AuCu NCs solution exhibits a fluorescence emission peak in the wavelength range of 660~800 nm and undergoes a specific interaction with acetylene to induce fluorescence quenching.

[0013] Preferably, the adamantane thiol solution and the cuprous chloride solution are mixed at a molar concentration ratio of 1:4; The premixed molar ratio of the tetrachloroauric acid solution and the sodium borohydride solution is 10:1.

[0014] Preferably, the mixture is stirred at room temperature for 10-15 minutes. The slow dripping rate is 0.5~1 mL / min; Stir for 22-24 hours under a light-protected nitrogen atmosphere.

[0015] Preferably, the mixture is stirred for 24 hours under a light-protected nitrogen atmosphere.

[0016] Preferably, the amount of solute in the adamantane thiol solution is 0.8 mmol; The amount of solute in the cuprous chloride solution is 0.2 mmol; The amount of solute in the tetrachloroauric acid solution is 0.4 mmol; The amount of solute in the sodium borohydride solution is 2 mmol.

[0017] Preferably, the ADM-AuCu NCs solution exhibits the strongest fluorescence emission peak at a wavelength of 700 nm.

[0018] An application of a bimetallic nanocluster fluorescent probe compound in the preparation of products for rapid detection of acetylene.

[0019] Preferably, the concentration range of acetylene detected by the product is 0.026 μL / L to 26000 μL / L.

[0020] Preferably, the amount of acetylene used in the product detection is 0.8~1.2 mL.

[0021] The detection principle of this product is as follows: Using acetylene as a quencher and adamantane-thiol-modified bimetallic nanoclusters as a fluorescent probe, fluorescence quenching was achieved through the specific interaction between acetylene and ADM-AuCu NCs solution. Quantification was achieved by observing the linear relationship between the fluorescence intensity change (quenching rate) and the acetylene concentration.

[0022] Compared with the prior art, the present invention has at least the following technical effects: This invention provides a bimetallic nanocluster fluorescent probe compound that utilizes an adamantanethiol-modified gold-copper bimetallic nanocluster (ADM-AuCu NCs) solution as a fluorescent probe for acetylene detection, unlike traditional electrochemical and semiconductor detection sensors. Furthermore, the solution has a well-defined and controllable preparation process. By using specific ratios and reaction conditions of reagents such as cuprous chloride, adamantanethiol, tetrachloroauric acid, and sodium borohydride, a probe solution with stable fluorescence properties can be prepared for detecting the fluorescence quenching reaction of acetylene. The solution can be stored for a long time with stable fluorescence lifetime.

[0023] This bimetallic nanocluster fluorescent probe compound is used in the preparation of products for rapid detection of acetylene. Detection is achieved through a secondary effect of fluorescence quenching triggered by the specific binding of fluorescent molecules to acetylene gas; other substances cannot induce quenching. A linear relationship (R0) between fluorescence intensity and acetylene concentration is observed at a wavelength of 700 nm. 2 >0.99) to achieve precise quantification of acetylene concentration.

[0024] The reaction principle is as follows: 2Cu + +C₂H₂=Cu₂C₂↓+2H₂ + The acetylene detection procedure constructed in this invention involves the reaction of the analyte gas in a headspace vial, detection by a fluorescence spectrophotometer, and concentration conversion from a standard curve. This method not only boasts extremely high detection sensitivity, capable of identifying acetylene as low as 0.026 μL / L with excellent linearity, but also exhibits strong anti-interference capabilities (experiments have demonstrated that the fluorescent probe compound is unresponsive to common gases such as H2, CO, CO2, CH4, C2H6, and C2H4). Furthermore, it offers fast detection speed, simple operation, low cost, and requires no complex instruments. Compared with standard gas chromatography, the detection data shows no significant difference, thus verifying its reliability. Attached Figure Description

[0025] Figure 1 The standard curves of the reaction between the gold-copper nanocluster solution prepared in Example 1 and acetylene of different concentrations are shown. Figure 2 The fluorescence spectra of the reaction between the gold-copper nanocluster solution prepared in Example 1 and acetylene of different concentrations are shown. Figure 3 This is a schematic diagram illustrating the specific selectivity of the gold-copper nanocluster solution prepared in Example 1; Figure 4 A schematic diagram of the reaction response time of the gold-copper nanocluster solution prepared in Example 1 with acetylene. Figure 5 A schematic diagram of the ultraviolet absorption curve of the gold-copper nanocluster solution prepared in Example 1; Figure 6 XPS diagram of the gold-copper nanocluster solution prepared in Example 1; Figure 7 This is an XPS diagram of the gold-copper nanocluster solution prepared in Example 1 combined with acetylene. Detailed Implementation

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the present invention will be briefly introduced below in conjunction with the accompanying drawings and descriptions of the embodiments or the prior art. Obviously, the following description of the structure of the accompanying drawings is only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. It should be noted that the description of these embodiments is for the purpose of helping to understand the present invention, but does not constitute a limitation of the present invention.

[0027] One specific embodiment of the present invention is as follows: A bimetallic nanocluster fluorescent probe compound, wherein the fluorescent probe compound is a solution of gold-copper nanoclusters modified with adamantanethiol, labeled as ADM-AuCu NCs solution; The ADM-AuCu NCs solution exhibits a fluorescence emission peak in the wavelength range of 660~800 nm and undergoes a specific interaction with acetylene to induce fluorescence quenching.

[0028] The fluorescent probe is a solution of metal nanoclusters, which exhibits a fluorescence emission peak and undergoes fluorescence quenching upon contact with acetylene. In other words, quenching depends on the specific binding of the fluorescent molecule to the quencher; only substances capable of forming a ground-state complex with the fluorescent molecule can trigger quenching. Non-specific substances (such as irrelevant ions and impurities) cannot trigger it.

[0029] In addition, fluorescence intensity decreases with increasing quencher concentration (i.e. acetylene concentration), but fluorescence lifetime remains basically unchanged (because the excited-state free fluorescent molecules are not affected, their decay kinetics are still normal, only their number decreases).

[0030] Example 1: A bimetallic nanocluster fluorescent probe compound, wherein the fluorescent probe compound is a solution of gold-copper nanoclusters modified with adamantanethiol, labeled as ADM-AuCu NCs solution; The preparation method of the fluorescent probe compound is as follows: Adamantane thiol solution and cuprous chloride solution were selected, and after stirring and mixing at room temperature, a mixed solution of tetrachloroauric acid and sodium borohydride was slowly added dropwise. The mixture was stirred under a light-proof, nitrogen atmosphere to obtain an ADM-AuCu NCs solution.

[0031] To prepare a 0.2 mmol (20 mmol / L) cuprous chloride solution: Dissolve 0.0198 g of cuprous chloride (CuCl) in 5 mL of acetonitrile and 5 mL of methanol; To prepare a 0.8 mmol (concentration 14.6 mmol / L) adamantane mercaptan (ADM) solution: Dissolve 0.1346 g of adamantane mercaptan (ADM) in 55 mL of methanol; To prepare a 0.4 mmol (4 mmol / L) tetrachloroauric acid (HAuCl4) solution: Dissolve 0.0143 g of tetrachloroauric acid in 100 mL of methanol; To prepare a 2 mmol (2 mmol / L) sodium borohydride (NaBH4) solution: Dissolve 80 mg of sodium borohydride in 1 mL of water. Take 10 mL of adamantane thiol (ADM) solution and mix it with 5 mL of cuprous chloride solution. Stir at room temperature for 15 min. Then slowly add a mixed solution of tetrachloroauric acid and sodium borohydride. Protect from light and under nitrogen protection. Stir for 24 h to obtain an ADM-AuCu NCs solution with fluorescent properties.

[0032] Example 2: This embodiment is used to verify the high sensitivity and linear response of the ADM-AuCu NCs solution.

[0033] The concentration range of acetylene selected is 0.026 μL / L ~ 26000 μL / L, specifically 0.026 μL / L acetylene, 0.26 μL / L acetylene, 2.6 μL / L acetylene, 26 μL / L acetylene, 260 μL / L acetylene, 2600 μL / L acetylene, and 26000 μL / L acetylene.

[0034] The specific operation process is as follows: Add 1 mL of the ADM-AuCu NCs solution prepared in Example 1 to the headspace vial and cap it.

[0035] Add acetylene gas or blank gas (pure nitrogen or argon) of different concentrations to the headspace vial using a microsyringe, shake to mix, and ensure complete reaction.

[0036] Pour the completed reaction solution into a cuvette and detect its fluorescence value using a fluorescence spectrophotometer.

[0037] Specifically, a fluorescence spectrophotometer is used to detect fluorescence intensity, providing continuous wavelengths of excitation light to cover the estimated excitation peak range, with the scanning range set to 660~800 nm.

[0038] in conclusion: The method for quantifying acetylene concentration by the degree of fluorescence quenching is as follows: A fluorescence standard curve was plotted using the changes in fluorescence intensity at different acetylene concentrations. Stable fluorescence values ​​at each concentration were recorded at a wavelength of 700 nm. A linear regression function was plotted with the acetylene concentration as the x-axis and the corresponding fluorescence value as the y-axis.

[0039] like Figure 1 The figure shows the standard linear regression curves obtained by reacting the gold-copper nanocluster solution prepared in Example 1 with acetylene of different concentrations.

[0040] Combination Figure 1 The standard curve shows good linearity, and R0 is... 2 >0.99.

[0041] This function allows for the quantitative calculation of acetylene concentration in the sample by measuring the final fluorescence intensity.

[0042] like Figure 2The image shows the fluorescence spectra obtained by reacting the gold-copper nanocluster solution prepared in Example 1 with different concentrations of acetylene. Finally, fluorescence spectra of the ADM-AuCu NCs solution and the ADM-AuCu NCs solution with different concentrations of acetylene under fluorescence quenching were obtained, with wavelength as the x-axis and fluorescence intensity as the y-axis.

[0043] Combination Figure 2 It can be seen that the fluorescence emission peak is strongest at a wavelength of 700 nm.

[0044] Under the same wavelength conditions, the higher the acetylene concentration, the lower the fluorescence intensity.

[0045] Furthermore, the ADM-AuCu NCs solution still exhibits detection capability at an acetylene concentration of 0.026 μL / L, demonstrating the high sensitivity of the ADM-AuCu NCs solution.

[0046] Example 3: This example is used to verify the high selectivity and anti-interference properties of the ADM-AuCu NCs solution.

[0047] Hydrogen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propane, and propylene gases were selected as controls to investigate whether these gases would cause fluorescence quenching with ADM-AuCu NCs solution.

[0048] The operation process in this embodiment is as follows: Add 1 mL of the ADM-AuCu NCs solution prepared in Example 1 to the headspace vial and cap it.

[0049] Add hydrogen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propane, propylene, or acetylene gas to the headspace vial using a microsyringe, and mix by shaking.

[0050] Pour the completed reaction solution into a cuvette and detect the fluorescence value using a fluorescence spectrophotometer.

[0051] Specifically, the fluorescence value (reflecting fluorescence intensity) of the original ADM-AuCu NCs solution was first measured using a fluorescence spectrophotometer and labeled as F0. Then, different gases of the same concentration were introduced into the headspace flask clock according to the steps, and the stable fluorescence value F after the different gases reacted with the ADM-AuCu NCs solution was recorded. The fluorescence quenching rate Q was calculated according to the formula: Q = (F0 - F) / F0 × 100%.

[0052] like Figure 3 The diagram shown illustrates the specific selectivity of the gold-copper nanocluster solution prepared in Example 1.

[0053] Results combined Figure 3It can be seen that the quenching rates of gases such as hydrogen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propane, and propylene are all close to 1. Therefore, it can be concluded that the ADM-AuCu NCs solution has no significant response to gases such as hydrogen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propane, and propylene, but exhibits a specific interaction with acetylene gas, with obvious fluorescence quenching.

[0054] This also demonstrates that the ADM-AuCu NCs solution exhibits high selectivity for acetylene and shows no response to interfering factors such as hydrogen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propane, and propylene, demonstrating strong anti-interference capabilities.

[0055] Example 4: This embodiment compares with traditional detection methods to verify the reliability of the data.

[0056] Specifically, the method for detecting acetylene concentration in this embodiment is as follows: 5 mL of nitrogen gas was added to 40 mL of insulating oil as a balance gas, and the mixture was shaken at 50 °C for 30 min. The shaken gas was then collected and used as the gas to be tested.

[0057] Add 1 mL of the ADM-AuCu NCs solution prepared in Example 1 to the headspace vial and cap it.

[0058] Inject 1 mL of the gas to be tested using a microsyringe. The gas to be tested is divided into three groups: sample 1, sample 2 and sample 3. Shake and let stand for 3 min.

[0059] Pour the reacted solution into a cuvette and use a fluorescence spectrophotometer to detect the fluorescence values.

[0060] The final acetylene concentration value was measured based on the linear regression function obtained in Example 2.

[0061] The existing methods for detecting acetylene concentration are as follows: 1 mL of shaken gas was injected into a standard gas chromatograph (GC) for detection. The standard GC concentrations of Sample 1, Sample 2 and Sample 2 were all 0.11 μL / L. The final results are shown in Table 1.

[0062] Table 1 Comparison of detection concentrations between standard gas chromatography and this embodiment

[0063] The two methods are compared. A t-test is performed, which essentially determines the "reliability" of the difference by "quantifying the difference between the means of the two sets of data" and "the degree of fluctuation in the data itself".

[0064] As shown in Table 1, no significant difference was found. This demonstrates that the method described in this embodiment is feasible for quantitative detection of acetylene concentration.

[0065] Example 5: This embodiment is used to verify the response rate of ADM-AuCu NCs solution to acetylene quenching.

[0066] The operation process in this embodiment is as follows: Add 1 mL of the ADM-AuCu NCs solution prepared in Example 1 to a sealed cuvette and cap it. Add acetylene gas to the sealed cuvette using a microsyringe and immediately measure the fluorescence value until the fluorescence value stabilizes.

[0067] like Figure 4 The diagram shown illustrates the reaction time of the gold-copper nanocluster solution prepared in Example 1 with acetylene.

[0068] Results combined Figure 4 It is known that it has the advantages of short response time, stable fluorescence intensity within 2 minutes after reaction, and fast quenching speed.

[0069] Example 6: This embodiment is used to verify the changes in the ultraviolet absorption characteristics of ADM-AuCu NCs solution before and after the reaction with acetylene.

[0070] The operation process in this embodiment is as follows: ADM solution, cuprous chloride solution, tetrachloroauric acid solution, and ADM-AuCuNCs solution prepared in Example 1 were prepared separately. The absorption spectra of each single component solution and the ADM-AuCuNCs solution were measured using a UV-Vis spectrophotometer, and the absorption curves were recorded. Then, acetylene gas was added to a sealed cuvette containing 1 mL of ADM-AuCuNCs solution, the cuvette was capped, and after the reaction stabilized, the UV absorption spectra were measured again, and the absorption curves after the reaction were recorded.

[0071] like Figure 5 The image shows the UV absorption curves of the gold-copper nanocluster solution prepared in Example 1 before and after reaction with acetylene. Specifically, these are the UV absorption curves for ADM solution, cuprous chloride solution, tetrachloroauric acid solution, sodium borohydride solution, ADM-AuCu NCs solution, and the UV absorption curve after the addition of acetylene.

[0072] Results combined Figure 5 It can be seen that before the solution was synthesized, the UV absorption of both substances was very low. After the synthesis of the ADM-AuCu NCs solution, the UV absorption at 280 nm increased significantly. Upon reaction with acetylene, the UV absorption decreased significantly.

[0073] Example 7: This example is used to verify the valence states of each element in the synthesized ADM-AuCu NCs solution.

[0074] The operation process in this embodiment is as follows: Take a small amount of ADM-AuCu NCs solution and dry it at 45℃. XPS test procedure: Take an appropriate amount of powder, press it into a size of about 5 mm, attach it to the sample tray, and place the sample into the sample chamber of the Thermo Scientific K-Alpha XPS instrument. The pressure in the sample chamber should be less than 2.0 × 10⁻⁶. -7 When the sample is in mbar, the sample is sent into the analysis chamber with a spot size of 400 μm, an operating voltage of 12 kV, and a filament current of 6 mA. The full spectrum scan pass energy is 100 eV with a step size of 1 eV; the narrow spectrum scan pass energy is 50 eV with a step size of 0.1 eV. After setting the spectral information, the instrument automatically performs the test.

[0075] like Figure 6 The figure shown is an XPS plot of ADM-AuCu NCs.

[0076] The results are combined as follows: Figure 6 The X-ray photoelectron spectroscopy (XPS) curves of ADM-AuCu NCs indicate the presence of C, N, O, Cu, S, and Au. In the Cu 2p spectrum, two peaks appear at 947.43 and 932.45 eV, representing Cu 2p... 1 / 2 and 2p 3 / 2 .

[0077] This result is consistent with the Cu(0) state, and the low peak near 942.0 eV indicates the presence of a small amount of Cu in ADM-AuCu NCs. 2+ After tetrachloroauric acid participates in the reaction, the +3 valence Au is reduced to the 0 valence metallic state (corresponding to Au 4f). 7 / 2 Based on the energy (84.44 eV), the Au 4f peak shape, and the XPS characteristics of related elements, it can be concluded that the gold-copper cluster has been successfully synthesized.

[0078] Example 8: This example is used to verify the valence states of each element in the ADM-AuCu NCs solution after reaction with acetylene.

[0079] The operation process in this embodiment is as follows: Add 10 mL of ADM-AuCu NCs solution to a headspace vial, purge with 10 mL of C2H2, and allow to stand for 3 min to allow for complete reaction. Then dry the reacted solution at 45°C. XPS testing procedure: Take an appropriate amount of powder, press it to approximately 5 mm in size, attach it to the sample tray, and place the sample into the sample chamber of the Thermo Scientific K-Alpha XPS instrument. The pressure in the sample chamber should be less than 2.0 × 10⁻⁶. -7 When the sample is in mbar, the sample is sent into the analysis chamber with a spot size of 400 μm, an operating voltage of 12 kV, and a filament current of 6 mA. The full spectrum scan pass energy is 100 eV with a step size of 1 eV, and the narrow spectrum scan pass energy is 50 eV with a step size of 0.1 eV. After setting the spectral information, the instrument automatically performs the test.

[0080] like Figure 7 The image shown is an XPS plot of ADM-AuCu NCs+C2H2. The results are combined as follows: Figure 7 It can be seen that before the reaction, Cu 2p 3 / 2 Binding energy corresponds to low valence state Cu 0 / Cu + (≈932.08 eV), contains a small amount of Cu 2+ The characteristic peak shifts to a higher binding energy (≈934.25 eV) after the reaction and shows a significant Cu content. 2+ Satellite peaks indicate that Cu 0 / Cu + Oxidized by acetylene to Cu 2+ The introduction of acetylene after the reaction led to an increase in the intensity of the C1s C1s peak. These changes together verified that low-valence Cu was oxidized by acetylene, eventually forming acetylene copper precipitate, which is consistent with the fluorescence quenching mechanism mentioned above.

[0081] Finally, it should be noted that the above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A bimetallic nanocluster fluorescent probe compound, characterized in that, The fluorescent probe compound is a solution of gold-copper nanoclusters modified with adamantanethiol, labeled as ADM-AuCu NCs solution; The preparation method of the fluorescent probe compound is as follows: Adamantane thiol solution and cuprous chloride solution were selected and mixed at room temperature. Then, a solution of tetrachloroauric acid solution and sodium borohydride solution premixed in a certain volume ratio was slowly added dropwise. The mixture was stirred under a light-proof and nitrogen atmosphere to obtain ADM-AuCu NCs solution. The ADM-AuCu NCs solution exhibits a fluorescence emission peak in the wavelength range of 660~800 nm and undergoes a specific interaction with acetylene to induce fluorescence quenching.

2. The bimetallic nanocluster fluorescent probe compound according to claim 1, characterized in that, The adamantane thiol solution and cuprous chloride solution are mixed at a molar concentration ratio of 1:4; The premixed molar ratio of the tetrachloroauric acid solution and the sodium borohydride solution is 10:

1.

3. The bimetallic nanocluster fluorescent probe compound according to claim 1, characterized in that, Stir at room temperature for 10-15 minutes; The slow dripping rate is 0.5~1 mL / min; Stir for 22-24 hours under a light-protected nitrogen atmosphere.

4. The bimetallic nanocluster fluorescent probe compound according to claim 3, characterized in that, Stir for 24 hours under a light-protected nitrogen atmosphere.

5. The bimetallic nanocluster fluorescent probe compound according to claim 1, characterized in that, The amount of solute in the adamantane thiol solution is 0.8 mmol; The amount of solute in the cuprous chloride solution is 0.2 mmol; The amount of solute in the tetrachloroauric acid solution is 0.4 mmol; The amount of solute in the sodium borohydride solution is 2 mmol.

6. The bimetallic nanocluster fluorescent probe compound according to claim 1, characterized in that, The ADM-AuCu NCs solution exhibits the strongest fluorescence emission peak at a wavelength of 700 nm.

7. The use of a bimetallic nanocluster fluorescent probe compound as described in any one of claims 1 to 6 in the preparation of a product for rapid detection of acetylene.

8. The application of the bimetallic nanocluster fluorescent probe compound according to claim 7 in the preparation of products for rapid detection of acetylene, characterized in that, The product can detect acetylene concentrations ranging from 0.026 μL / L to 26000 μL / L.

9. The application of the bimetallic nanocluster fluorescent probe compound according to claim 7 in the preparation of products for rapid detection of acetylene, characterized in that, The amount of acetylene used in the product testing is 0.8~1.2 mL.

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