A dual-mode colorimetric-fluorometric method for detecting cyanide ions and applications thereof
By combining the TPE-M probe with colorimetric-fluorescence method, the problems of cumbersome, easily interfered with, and costly existing cyanide ion detection methods are solved, realizing rapid, simple, and low-cost dual-mode detection, which is suitable for a variety of detection scenarios and has a detection limit as low as 2.5 μmol/L.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINESE PEOPLES LIBERATION ARMY ARMY CHEM DEFENSE COLLEGE
- Filing Date
- 2026-03-05
- Publication Date
- 2026-06-09
AI Technical Summary
Existing methods for detecting cyanide ions are cumbersome to operate, susceptible to interference, costly, and require expensive equipment. Moreover, most of them are single-detection modes, which cannot meet the needs for rapid, simple, and low-cost on-site detection.
1-(4-(1,2,2-triphenylvinyl)phenyl)-1H-pyrrole-2,5-dione (TPE-M) was used as a dual-mode colorimetric-fluorescent probe, combined with organic solvents such as acetone, dimethyl sulfoxide, N,N-dimethylformamide, and acetonitrile, to achieve rapid, simple, and low-cost cyanide ion detection through colorimetric and fluorescence methods.
It achieves rapid, simple, and low-cost cyanide ion detection. The dual-mode detection method complements each other's advantages, with high sensitivity, strong anti-interference ability, and applicability to various detection scenarios. The detection limit is as low as 2.5 μmol/L.
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Figure CN122167332A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of analytical chemistry and sensor technology, and particularly relates to a dual-mode colorimetric-fluorescence method for detecting cyanide ions and its application. Background Technology
[0002] cyanide ions Due to its excellent complexing ability, it is widely used in electroplating, metallurgy, gold extraction, and chemical synthesis. Cyanide... Hydrogen cyanide ions are extremely toxic, capable of binding to ferric ions in cytochrome oxidases and disrupting the cellular respiratory chain. Even trace amounts can lead to tissue hypoxia and even rapid death, posing a serious threat to public health and safety. For example, in an accident at a chemical plant in Shanghai in 1983, a worker surnamed Li inhaled escaping hydrogen cyanide gas while cutting pipes, resulting in acute poisoning. He experienced symptoms such as dizziness and weakness and only gradually recovered after a long period of hospitalization. Given its high risk, developing rapid, sensitive, and reliable methods for detecting cyanide ions is crucial for environmental monitoring, food safety, and industrial production safety.
[0003] Currently, conventional methods for detecting cyanide ions still have limitations. For example, the silver nitrate titration method is cumbersome, requires highly skilled operators, and is susceptible to interference from various ions; the isonicotinic acid-pyrazolone spectrophotometric method has poor reproducibility and unsatisfactory reagent stability; while ion chromatography has high sensitivity, the equipment is expensive and the pretreatment is complex, making it difficult to use for rapid on-site screening; and electrochemical methods and flow injection analysis techniques suffer from problems such as easy electrode contamination, high maintenance costs, or poor automation. These traditional methods can no longer meet the urgent need for rapid, simple, and low-cost on-site detection.
[0004] In recent years, colorimetric and fluorescence methods based on molecular probes have attracted much attention due to their advantages such as high sensitivity, simple operation, and potential for visual detection. For example, the cyanide ion electrode method is used in environmental monitoring to determine cyanide, featuring simplicity, sensitivity, speed, and a wide measurement range. Furthermore, colorimetric and fluorescence methods have also demonstrated high sensitivity and accuracy in the detection of melamine. Colorimetric methods allow direct observation of color changes with the naked eye, eliminating the need for complex instruments and making them ideal for rapid on-site screening. Fluorescence methods generally offer higher sensitivity and provide richer signal dimensions. Ratiometric fluorescent probes, which quantify cyanide by measuring the ratio of fluorescence intensities at two different wavelengths, have been widely used in cyanide detection. For instance, studies have shown that these probes exhibit good specificity for cyanide detection in water, food, and biological tissues, as well as in bioimaging, and can effectively eliminate interference from environmental and instrument fluctuations, thereby improving detection accuracy.
[0005] Despite numerous reports on cyanide ion fluorescent or colorimetric probes, most existing probes only offer a single detection mode (colorimetric or fluorescence), limiting their application flexibility. In complex and variable real-world sample detection environments, a single mode may lead to reduced reliability due to sample matrix interference, light source limitations, or differences in human judgment.
[0006] In summary, existing technologies for detecting cyanide ions are problematic. Silver nitrate titration is cumbersome and susceptible to ion interference; isonicotinic acid-pyrazolone spectrophotometry suffers from poor reproducibility and reagent instability; ion chromatography involves expensive instruments and complex pretreatment, hindering rapid on-site screening; and electrochemical and flow injection methods face issues such as electrode contamination, high maintenance costs, and limited automation. None of these methods meet the demands for rapid, simple, and low-cost on-site detection. Furthermore, most molecular probe methods, which have gained attention in recent years, only offer single detection modes such as colorimetry or fluorescence. Therefore, developing a rapid, simple, low-cost method applicable to various detection scenarios is a pressing issue in this field. Summary of the Invention
[0007] The purpose of this invention is to overcome the shortcomings of the prior art and provide a dual-mode colorimetric-fluorescence method for detecting cyanide ions and its application, which is applicable to a variety of detection scenarios and can achieve rapid, simple and low-cost technical effects.
[0008] To achieve the above objectives, this application adopts the following technical solution: This invention provides a dual-mode colorimetric-fluorescent probe for detecting cyanide ions. The probe is a compound 1-(4-(1,2,2-triphenylvinyl)phenyl)-1H-pyrrole-2,5-dione, abbreviated as TPE-M. In the prior art, this compound is used as a core unit of aggregation-induced emission (AIE) to prepare novel aggregation-induced emission molecules. This application unexpectedly discovered that this compound can specifically recognize cyanide ions, can be used for qualitative and quantitative analysis, and can be detected in two ways, thus enhancing the broad spectrum of detection.
[0009] This invention also provides a dual-mode colorimetric-fluorescent reagent for detecting cyanide ions, comprising the probe and an organic solvent, wherein the organic solvent is any one or more of acetone, dimethyl sulfoxide, N,N-dimethylformamide, and acetonitrile. The concentration of the probe is 0.1 × 10⁻⁶. —3 mol / L to 10×10 —3 The selected organic solvent has minimal interference and ensures a clear and stable fluorescence signal during fluorescence detection.
[0010] This invention also provides a dual-mode colorimetric-fluorescence method for detecting cyanide ions. The analyte is placed in the detection reagent of this invention to obtain a reaction solution. If the analyte contains cyanide ions, a reddish-brown color will appear in the reaction solution. The detection time is 1-2 minutes. This detection method requires no specialized instruments or personnel, is simple to operate, and significantly reduces costs.
[0011] The present invention also provides a method for detection using a commonly used ultraviolet-visible spectrometer. The analyte is placed in the detection reagent of the present invention to obtain a reaction solution. If the analyte contains cyanide ions, a characteristic absorption peak appears in the ultraviolet-visible absorption spectrum at 480nm-510nm.
[0012] The detection reagent of the present invention can also be used to detect fluorescence signals. The analyte is placed in the detection reagent of the present invention to obtain a reaction solution. The reaction solution is detected by a fluorescence spectrophotometer with an excitation wavelength of 320nm-350nm. If the analyte contains cyanide ions, a fluorescence emission peak will appear at 510nm-530nm or 580nm-600nm.
[0013] Using the detection reagent of the present invention: the analyte is placed in the detection reagent of claim 2 to obtain a reaction solution. When the reaction solution is irradiated with a portable ultraviolet lamp at a wavelength of 365nm, if the analyte contains cyanide ions, the reaction solution will turn yellowish-brown. The detection time is 1-2 minutes.
[0014] In summary, by adopting the above technical solutions, this application has the following beneficial effects: 1. A new use for a known compound has been discovered: the application of TPE-M as a probe in the detection of cyanide ions has been revealed for the first time, and a complete dual-mode detection method has been developed, opening up a new and valuable application field for this known compound.
[0015] 2. Dual-mode detection, complementary advantages: Colorimetric method is intuitive and rapid, suitable for on-site screening; Fluorescence method has high sensitivity, strong anti-interference, and reliable results. The two modes can be flexibly selected or mutually verified as needed.
[0016] 3. Extremely high selectivity and anti-interference ability: TPE-M... The response is highly specific, and it is not interfered with by a large number of common anions and thiol compounds, ensuring the accuracy of detection in real complex samples.
[0017] 4. High sensitivity and rapid response: The detection limit of this method is as low as 2.5 μmol / L when using ultraviolet-visible spectroscopy and as low as 1.2 μmol / L when using fluorescence spectroscopy. The response time is as short as 2 minutes, which meets the requirements of rapid detection. Attached Figure Description
[0018] Figure 1TPE-M and UV-Vis absorption spectrum after reaction (using acetonitrile as solvent); Figure 2 TPE-M and Fluorescence emission spectra after reaction in different solvents (using acetonitrile as solvent); Figure 3 TPE-M testing The UV-Vis absorption spectra of cyanide ions and other potential interfering substances were detected in real time (using acetone as solvent). Figure 4 Color comparison photographs of TPE-M reacting with various interfering substances (using acetone as solvent) under sunlight. From left to right, the analytes are: blank, tetrabutylammonium cyanide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium nitrate, tetrabutylammonium thiocyanate, tetrabutylammonium phosphate, tetrabutylammonium acetate, 2-aminoethanethiol, methyl mercaptoacetate, 1-mercapto-1-propanol, and L-cysteine. Figure 5 Color comparison photographs of TPE-M reacting with various interfering substances (using acetone as solvent) under 365nm UV light. From left to right, the analytes are blank, tetrabutylammonium cyanide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium nitrate, tetrabutylammonium thiocyanate, tetrabutylammonium phosphate, tetrabutylammonium acetate, 2-aminoethanethiol, methyl mercaptoacetate, 1-mercapto-1-propanol, and L-cysteine. Figure 6 TPE-M testing The graph shows the change in visible light absorption intensity at 496 nm over time (using acetone as solvent). Figure 7 TPE-M fluorescence detection The fluorescence intensity at 580 nm changes over time (using acetone as solvent). Figure 8 TPE-M testing At that time, the visible light absorption intensity at 496 nm increased with... Concentration change graph (using acetonitrile as solvent); Figure 9 TPE-M testing At that time, the fluorescence intensity at 590 nm increased with... Concentration change graph (using acetonitrile as solvent); Figure 10 UV-Vis absorption spectra of TPE-M and CN- before and after the reaction in different solvents. Detailed Implementation
[0019] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the accompanying drawings. The following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
[0020] Example 1: This invention provides a dual-mode colorimetric-fluorescent probe for detecting cyanide ions. The probe is 1-(4-(1,2,2-triphenylvinyl)phenyl)-1H-pyrrole-2,5-dione. Dissolving this compound in an organic solvent yields a detection reagent capable of detecting the presence of cyanide ions. The organic solvent used is dimethyl sulfoxide, and the probe concentration is 0.1 × 10⁻⁶. —3 mol / L to 10×10 —3 mol / L, actual detection example: Take a chemical waste liquid organic solvent sample and add it to the detection solution. Within 2 minutes, whether the reaction solution shows / does not show a reddish-brown color can be used to determine cyanide ions.
[0021] Example 2: Prepare 2×10 —3 A mol / L TPE-M acetonitrile solution was used as the working solution. Prepare 10 × 10⁻⁶ mol / L solution. —3 mol / L tetrabutylammonium cyanide (as (Source) Acetonitrile solution. Equal volumes of the two solutions were mixed, and after reacting at room temperature for 2 minutes, a UV-Vis absorption spectrum scan was performed. The results are as follows: Figure 1 As shown, the reaction solution exhibits a maximum absorption peak at 496 nm, and the solution displays a distinct reddish-brown color under sunlight. The organic solvent acetone can be replaced with acetone, dimethyl sulfoxide, N,N-dimethylformamide, etc., and similar color changes and spectral characteristics can be observed after each replacement.
[0022] Example 3: This invention provides a dual-mode colorimetric-fluorescent probe for detecting cyanide ions. The probe is 1-(4-(1,2,2-triphenylvinyl)phenyl)-1H-pyrrole-2,5-dione. Dissolving this compound in an organic solvent yields a detection reagent capable of detecting the presence of cyanide ions. The organic solvent used is N,N-dimethylformamide, and the probe concentration is 0.1 × 10⁻⁶. —3 mol / L to 10×10 —3 mol / L, actual test example: Take the organic waste liquid from the acrylonitrile production process and add it to the reaction solution. Within 2 minutes, the reaction solution will show / not show a yellowish-brown color under a 365nm ultraviolet lamp to determine the cyanide ions.
[0023] Example 4: Prepare 2×10 —3 A mol / L TPE-M acetonitrile solution was used as the working solution. Prepare 10 × 10⁻⁶ mol / L solution. —3 mol / L tetrabutylammonium cyanide (as (Source) Acetonitrile solution. Equal volumes of the two solutions were mixed, and after reacting at room temperature for 2 minutes, the fluorescence emission spectrum was scanned at an excitation wavelength of 320 nm in the range of 400-600 nm. The results are as follows: Figure 2 As shown, the reaction solution exhibits a maximum emission peak at 580 nm and displays a distinct yellowish-brown color under a 365 nm UV lamp. Acetonitrile, the organic solvent, can be replaced with acetone, dimethyl sulfoxide, N,N-dimethylformamide, etc., and similar color changes and spectral characteristics are observed after each replacement.
[0024] The specificity of the probe of the present invention is illustrated by the following experiments. In the detection working solutions of Examples 1 and 2, the analyte was replaced with 10 × 10⁻⁶ ppm. —3 Multiple potential interfering substances (including tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium nitrate, tetrabutylammonium thiocyanate, tetrabutylammonium phosphate, tetrabutylammonium acetate, 2-aminoethanethiol, methyl mercaptoacetate, 1-mercapto-1-propanol, L-cysteine, etc.) were detected at mol / L concentrations. After a 2-minute reaction, their UV-Vis absorption spectra were measured, and the results are as follows: Figure 3 As shown, only by adding The sample exhibited significant absorption enhancement (496 nm), while other interfering substances did not cause significant signal changes, and a distinct reddish-brown change could be observed under sunlight. Figure 4 In addition, only those who join The sample showed obvious yellowish-brown fluorescence under a 365nm UV lamp. Figure 5 This demonstrates that the probe and detection reagent provided by this invention have extremely high selectivity for cyanide ions.
[0025] The following experiments illustrate the stability of the detection time of the detection method of the present invention: Prepare 1×10 -3 mol / L TPE-M acetone solution and 10×10 —3 A mol / L tetrabutylammonium cyanide acetone solution was prepared. Equal volumes of the two solutions were mixed, and the absorbance of the reaction solution at 496 nm was measured at different reaction times. The absorbance values were then plotted against time. Figure 6 As shown, add to the detection solution The reaction was rapid, and the absorbance at 496 nm stabilized within 2 minutes. Fluorescence emission spectra were scanned from 400 to 600 nm at an excitation wavelength of 336 nm. The results are as follows... Figure 7 As shown, the fluorescence emission intensity at 580 nm increases rapidly within 1 minute and stabilizes within 2 minutes.
[0026] The following describes the quantitative operation method using the method of the present invention: preparation Concentrations of 0, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, and 2 × 10⁻⁶ were used. —3 A stock solution of acetonitrile (mol / L) was mixed with an equal volume of TPE-M acetonitrile working solution (2 × 10⁻⁶ mol / L). —3 The reaction was carried out at a concentration of mol / L. After 2 minutes, the absorbance of each solution was measured at 496 nm. The absorbance values were then compared with those of the other solutions. Plot the concentrations to obtain a standard curve. For example... Figure 8 As shown, in the detection solution Within the concentration range of 0 to 0.7 mM, absorbance showed a good linear relationship with concentration, with a linear regression equation of y = 0.3707x + 0.0377 and a correlation coefficient R² = 0.9883. This indicates that the absorbance can be used... Accurate quantification was achieved. The detection limit was calculated to be 2.5 μM using the 3σ criterion.
[0027] The above preparation Concentrations of 0, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, and 2 × 10⁻⁶ were used. —3 A stock solution of acetonitrile (mol / L) was mixed with an equal volume of TPE-M acetonitrile working solution (2 × 10⁻⁶ mol / L). —3 The reaction was carried out at a concentration of mol / L. After 2 minutes, the fluorescence emission of each solution was measured at 580 nm under ultraviolet light excitation at a wavelength of 320 nm. The fluorescence intensity values were compared with those of the solutions. Plot the concentrations to obtain a standard curve. For example... Figure 9 As shown, in the detection solution Within the concentration range of 0 to 0.7 mM, fluorescence intensity showed a good linear relationship with concentration, with a linear regression equation of y = 139481x + 4520.7 and a correlation coefficient R² = 0.9790. This indicates that the fluorescence intensity can be used for... Accurate quantification was achieved. The detection limit was calculated to be 1.2 μM using the 3σ criterion.
[0028] If the test solution contains If the concentration exceeds 0.7 mM, the solution to be tested needs to be diluted before quantitative analysis.
[0029] The chosen solvent is not readily available and requires multiple experiments to determine. For example, if the organic solvent is ethanol, the reaction solution will not show a distinct reddish-brown color under sunlight. Figure 10 As shown, when measured with a UV-Vis spectrophotometer, there is no obvious absorption peak at 496 nm, which cannot achieve the detection purpose of colorimetric-fluorescence dual-mode detection.
[0030] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-described technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.
Claims
1. A dual-mode colorimetric-fluorescent probe for detecting cyanide ions, characterized in that, The probe is 1-(4-(1,2,2-triphenylvinyl)phenyl)-1H-pyrrole-2,5-dione.
2. A dual-mode colorimetric-fluorescent reagent for detecting cyanide ions, characterized in that, The device includes the probe as described in claim 1 and an organic solvent, wherein the organic solvent is any one or more of acetone, dimethyl sulfoxide, N,N-dimethylformamide, and acetonitrile, and the concentration of the probe is 0.1 × 10⁻⁶. —3 mol / L to 10×10 —3 mol / L.
3. A dual-mode colorimetric-fluorescence method for detecting cyanide ions, characterized in that, The analyte is placed in the detection reagent described in claim 2 to obtain a reaction solution. If the analyte contains cyanide ions, a reddish-brown color will appear in the reaction solution. The detection time is 1-2 minutes.
4. A dual-mode colorimetric-fluorescence method for detecting cyanide ions, characterized in that, The analyte is placed in the detection reagent described in claim 2 to obtain a reaction solution. The solution is then detected by a UV-Vis spectrometer. If the analyte contains cyanide ions, a characteristic absorption peak will appear in the UV-Vis absorption spectrum at 480nm-510nm.
5. A dual-mode colorimetric-fluorescence method for detecting cyanide ions, characterized in that, The analyte is placed in the detection reagent described in claim 2 to obtain a reaction solution. When the reaction solution is irradiated with a portable ultraviolet lamp at a wavelength of 365 nm, if the analyte contains cyanide ions, the reaction solution will turn yellowish-brown. The detection time is 1-2 minutes.
6. A dual-mode colorimetric-fluorescence method for detecting cyanide ions, characterized in that, The analyte is placed in the detection reagent described in claim 2 to obtain a reaction solution. The reaction solution is detected by a fluorescence spectrophotometer with an excitation wavelength of 320nm-350nm. If the analyte contains cyanide ions, a fluorescence emission peak appears at 510nm-530nm or 580nm-600nm.
7. The application of the probe / detection reagent / detection method according to any one of claims 1-6, characterized in that, This probe / detection reagent / detection method is applied to the detection of cyanide ions in fields such as chemical process monitoring, pharmaceutical industry, oil and gas industry, and environmental monitoring.