A copper ion probe, its preparation method and application

Abstract

This invention discloses a copper ion probe, its preparation method, and its application. The copper ion probe of this invention has a structure where M is selected from at least one of Li, Na, and K; X... ‑ It is a halide ion, selected from F ‑ Cl ‑ ,Br ‑ and I ‑ Any one of the following. This copper ion probe is prepared by a substitution reaction of lithium 3,3-dimethyl-5-sulfonate / sodium / potassium halogen-bridged heptamethylcarbazone and diethanolamine. The copper ion probe of this invention not only has a deep sensory color, which is beneficial for visual detection, but also exhibits a specific ultraviolet-visible absorption spectral response to copper ions, enabling specific detection of copper ions. Furthermore, the copper ion probe provided by this invention has a maximum absorption peak at 688 nm, which is in the near-infrared region, and its long maximum absorption wavelength effectively resists background absorption interference during spectroscopic detection.

Description

Technical Field

[0001] This invention relates to the field of environmental monitoring technology, and in particular to a copper ion probe, its preparation method, and its application. Background Technology

[0002] Copper ions are a common heavy metal ion pollutant in modern industry and a key research target in environmental monitoring. Achieving rapid detection of copper ions is a major task in analytical chemistry. Techniques for detecting copper ions mainly include atomic absorption spectrometry, ultraviolet-visible absorption spectrometry, fluorescence analysis, electrochemical analysis, and inductively coupled plasma mass spectrometry. Among these, ultraviolet-visible absorption spectrometry and fluorescence analysis offer advantages such as rapid detection, ease of operation, and high sensitivity, and have become important methods for heavy metal ion detection. Spectroscopic detection of copper ions requires the use of chromogenic agents with specific absorption characteristics, such as detection kits or nanoparticles, gel chromogenic agents, and organic dyes. Currently, dye probes capable of detecting copper ions often have their maximum absorption peaks located in shorter wavelength regions, exhibiting weak resistance to background absorption interference. Furthermore, the low molar extinction coefficient of the dye chromophores results in inconspicuous color changes, hindering rapid and visual detection applications. Therefore, developing probes with long-wavelength absorption, high molar extinction coefficients, and specific ultraviolet-visible absorption spectral responses to copper ions is of great significance for achieving sensitive detection of copper ions. Summary of the Invention

[0003] To address the aforementioned technical problems, this invention provides a copper ion probe, its preparation method, and its application.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] On the one hand, the present invention provides a copper ion probe, the structure of which is shown in Formula I:

[0006]

[0007] In Formula I, M is selected from at least one of Li, Na, and K; X - It is a halide ion, selected from F - Cl - ,Br - and I - Any one of them.

[0008] In a preferred embodiment, M is K;

[0009] Preferably, X - For Cl - .

[0010] In another aspect, the present invention provides a method for preparing the above-mentioned copper ion probe, comprising the following steps:

[0011] The copper ion probe is obtained by a substitution reaction of lithium 3,3-dimethyl-5-sulfonate / sodium / potassium halogen-bridged ring heptamethrin and diethanolamine in a reaction solvent.

[0012] In a preferred embodiment, the dosage relationship between lithium 3,3-dimethyl-5-sulfonate / sodium / potassium halogenated heptamethrin and diethanolamine is as follows: 0.1 ml to 6 ml of diethanolamine per gram of lithium 3,3-dimethyl-5-sulfonate / sodium / potassium halogenated heptamethrin.

[0013] Preferably, the amount of the reaction solvent is 5 ml to 200 ml per gram of lithium 3,3-dimethyl-5-sulfonate / sodium / potassium halogenated heptamethrin.

[0014] In a preferred embodiment, the reaction solvent is selected from at least one of methanol, ethanol, acetonitrile, and N,N-dimethylformamide (DMF).

[0015] As a preferred embodiment, the substitution reaction is carried out at 5°C to 80°C for 2 to 48 hours.

[0016] Preferably, the substitution reaction is carried out in an inert gas; the inert gas is preferably any one of nitrogen, helium, and argon.

[0017] In some specific embodiments, the preparation method further includes post-treatment; the post-treatment includes rotary evaporation, dissolution and precipitation, filtration and drying; the dissolution and precipitation involves dissolving the crude product obtained by rotary evaporation in a good solvent, and then adding a poor solvent to precipitate it; the good solvent is selected from any one of methanol, ethanol, and N,N-dimethylformamide (DMF); the poor solvent is selected from any one of isopropanol, n-butanol, acetone, diethyl ether, and tetrahydrofuran.

[0018] In a preferred embodiment, the structure of the lithium 3,3-dimethyl-5-sulfonate / sodium / potassium halogen-bridged ring heptamethrin is shown in Formula II:

[0019]

[0020] In some specific embodiments, the preparation method of the lithium 3,3-dimethyl-5-sulfonate / sodium / potassium halogen-bridged ring heptamethrin includes the following steps:

[0021] Under a nitrogen atmosphere, lithium 2,3,3-trimethyl-N-ethyl-5-sulfonate / sodium / potassium indoline, 2-halo-1-formyl-3-hydroxymethylcyclohexene, and anhydrous sodium acetate were reacted in acetic anhydride. After the reaction was completed, dichloromethane was added to precipitate the precipitate, which was then filtered and dried under vacuum to obtain the lithium 3,3-dimethyl-5-sulfonate / sodium / potassium halogen-bridged heptamethrin.

[0022] The structure of the 2,3,3-trimethyl-N-ethyl-5-sulfonate lithium / sodium / potassium indoline is shown in Formula III:

[0023]

[0024] The structure of the 2-halo-1-formyl-3-hydroxymethylcyclohexene is shown in Formula IV:

[0025]

[0026] In some specific embodiments, the preparation method of the 2-halo-1-formyl-3-hydroxymethyl cyclohexene includes the following steps: under ice bath conditions, cyclohexanone is added dropwise to a mixed solution of phosphorus trihalomethane, N,N-dimethylformamide (DMF) and dichloromethane; the mixture is heated under reflux at 40-80°C for 2-6 hours; after the reaction is completed, the mixture is poured into crushed ice to precipitate the precipitate, and the precipitate is obtained by filtration.

[0027] In another aspect, the present invention provides the application of the above-mentioned copper ion probe in the detection of copper ions.

[0028] In some specific implementations, the application includes the following steps:

[0029] (1) Prepare a standard solution of the copper ion probe, mix the sample to be tested with the standard solution, and determine whether the sample to be tested contains copper ions by the color change of the solution; the judgment standard is: if the color of the standard solution changes from blue to light or to colorless after mixing with the sample to be tested, it indicates that the sample to be tested contains copper ions.

[0030] Alternatively, (2) prepare the copper ion probe into a standard solution and test its ultraviolet-visible absorption spectrum or ultraviolet spectrophotometric value at 688 nm; mix the sample to be tested with the standard solution and test the ultraviolet-visible absorption spectrum or ultraviolet spectrophotometric value at 688 nm of the mixed solution; compare the absorption intensity of the standard solution and the mixed solution at 688 nm, and determine whether the sample to be tested contains copper ions by the change in absorption intensity and solution color. The judgment criteria are: if the absorption intensity of the mixed solution at 688 nm is lower than that of the standard solution, and the color of the standard solution changes from blue to light or to colorless after mixing with the sample to be tested, it indicates that the sample to be tested contains copper ions.

[0031] In a preferred embodiment, the solvent of the standard solution is acetonitrile;

[0032] Preferably, the concentration of the copper ion probe in the standard solution is 10. -4 ~10 -6 mol L -1 .

[0033] Compared with existing technologies, the technical solution provided by this invention has the following advantages:

[0034] This invention provides a copper ion probe, its preparation method, and its application in the detection of copper ions. The copper ion probe provided by this invention uses a bridged ring heptamethrin with a high extinction coefficient as the chromophore, resulting in a deep sensory color that facilitates visual detection. The specific molecular structure of this copper ion probe exhibits a specific UV-Vis absorption spectrum response to copper ions. In acetonitrile solution, the maximum absorption peak of this copper ion probe is located at 688 nm, in the near-infrared region. The relatively long maximum absorption wavelength effectively resists background absorption interference during spectroscopic detection. Attached Figure Description

[0035] Figure 1 The normalized UV-Vis absorption spectra of the copper ion probe prepared in Example 1 of this invention in different solvents are shown.

[0036] Figure 2 The normalized fluorescence emission spectra of the copper ion probe prepared in Example 1 of this invention in different solvents are shown.

[0037] Figure 3 The image shows the UV-Vis absorption spectra of the copper ion probe prepared in Example 1 of this invention before and after adding the copper ions to be tested to an acetonitrile solution.

[0038] Figure 4 The fluorescence emission spectra of the copper ion probe prepared in Example 1 of this invention before and after adding the copper ions to be tested to an acetonitrile solution are shown.

[0039] Figure 5 The image shows the UV-Vis absorption spectrum of the copper ion probe prepared in Example 1 of this invention after adding the copper ions to be tested to an acetonitrile solution and then adding EDTA.

[0040] Figure 6 The image shows the UV-Vis absorption spectra of the copper ion probe prepared in Example 1 of this invention after adding different metal ions to an acetonitrile solution.

[0041] Figure 7 The synthesis routes of the copper ion probes in Examples 1-5 of this invention are shown. Detailed Implementation

[0042] The following embodiments are merely some, not all, of the embodiments of the present invention. Therefore, the detailed descriptions of the embodiments provided below are not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0043] In this invention, unless otherwise specified, all equipment and raw materials are commercially available or commonly used in the industry. The methods described in the following embodiments are conventional methods in the art, unless otherwise specified.

[0044] Manufacturing example: Preparation of potassium chlorobridged heptamethrin 3,3-dimethyl-5-sulfonate

[0045] (1) Under ice bath conditions, 10 mL of N,N-dimethylformamide (DMF), 20 mL of dichloromethane, and 9.5 mL of phosphorus oxychloride were mixed evenly and stirred for 30 minutes; 10 g of cyclohexanone was added dropwise, and the mixture was heated to reflux at 45 °C for 4 hours; the mixture was poured into crushed ice and refrigerated overnight to precipitate the precipitate, which was then filtered and dried to obtain 2-chloro-1-formyl-3-hydroxymethyl cyclohexene condensing agent.

[0046] (2) The intermediate 2,3,3-trimethyl-N-ethyl-5-sulfonate potassium indoline was prepared by referring to the method in Chinese Patent CN200810055344.7.

[0047] (3) Dissolve 3.27 g of potassium indoline 2,3,3-trimethyl-N-ethyl-5-sulfonate intermediate, 1 g of 2-chloro-1-formyl-3-hydroxymethyl cyclohexene condensing agent, and 200 mg of anhydrous sodium acetate in 40 mL of acetic anhydride. Stir and react for 4 hours under nitrogen protection at room temperature. Add dichloromethane to precipitate the precipitate, filter and dry under vacuum to obtain potassium 3,3-dimethyl-5-sulfonate chlorobridged heptamethrin.

[0048] The structure of the product obtained in this manufacturing example was determined by infrared, ultraviolet, and nuclear magnetic resonance spectroscopy.

[0049]

[0050] Example 1

[0051] like Figure 1As shown, the preparation method of the copper ion probe in this embodiment is as follows: 1g of potassium 3,3-dimethyl-5-sulfonate-based chlorobridged heptamethrin and 0.6mL of diethanolamine were dissolved in 20mL of ethanol and reacted at 20℃ for 12h under nitrogen protection; after the reaction was completed and cooled, rotary evaporation was performed to obtain the crude product; the crude product was dissolved in a small amount of ethanol and then isopropanol was added until a blue solid precipitated, which was then filtered and dried to obtain the copper ion probe.

[0052] Figure 1 The normalized UV-Vis absorption spectra of the copper ion probe prepared in this embodiment in different solvents are shown. The maximum absorption peaks of the copper ion probe in water, ethanol, isopropanol, n-butanol, acetonitrile, N,N-dimethylformamide and dimethyl sulfoxide are located at 672 nm, 683 nm, 690 nm, 687 nm, 688 nm, 693 nm and 698 nm, respectively.

[0053] Figure 2 The normalized fluorescence emission spectra of the copper ion probe prepared in this embodiment in different solvents are shown. The maximum emission peaks of the copper ion probe in water, ethanol, isopropanol, n-butanol, acetonitrile, N,N-dimethylformamide and dimethyl sulfoxide are located at 750 nm, 760 nm, 763 nm, 761 nm, 798 nm, 803 nm and 806 nm, respectively.

[0054] The copper ion probe was dissolved in acetonitrile solution to prepare a solution of 10... -5 mol L -1 Take 4 mL of the standard solution and place it in a cuvette. Measure its UV-Vis absorption spectrum and fluorescence emission spectrum, then... -3 mol L -1 Copper nitrate solution was added to the test standard solution in a volume of 200 μL. After mixing thoroughly, the UV-Vis absorption spectrum and fluorescence emission spectrum were measured again. Then, another 200 μL of 10... -2 mol L -1 The aqueous solution of ethylenediaminetetraacetic acid (EDTA) was mixed evenly, and its ultraviolet-visible absorption spectrum and fluorescence emission spectrum were tested again. Figure 3 The copper ion probe prepared for this embodiment was used in acetonitrile solution (10). -5 mol L -1 The UV-Vis absorption spectra of the standard solution before and after the addition of the copper ions to be tested are shown. The maximum absorption peak of the copper ion probe in acetonitrile is located at 688 nm. After the addition of the copper ions to be tested, the absorption intensity of the solution at 688 nm is significantly reduced. Figure 4The fluorescence emission spectra of the copper ion probe prepared in this embodiment before and after the addition of the copper ion to be tested to the acetonitrile solution are shown. The maximum emission peak of the copper ion probe in acetonitrile is located at 798 nm. After the addition of the copper ion to be tested, the fluorescence intensity of the solution at 798 nm is significantly reduced. Figure 5 The image shows the UV-Vis absorption spectrum of the copper ion probe prepared in this embodiment after adding the copper ions to an acetonitrile solution and then adding EDTA. After adding EDTA, the UV-Vis absorption intensity of the test sample did not recover.

[0055] The copper ion probe was dissolved in acetonitrile solution to prepare a solution of 10... -5 mol L -1 For the detection standard solution, take 4 mL of 20 groups of detection standard solutions and place them in cuvettes. One group serves as the blank control group. Then, add 200 μL of 10% standard solution to each of the other groups. - 3 mol L -1 After thoroughly mixing the metal nitrate solution, its UV-Vis absorption spectrum and fluorescence emission spectrum were tested again. Figure 6 The copper ion probe prepared in this embodiment was prepared by adding Ag to an acetonitrile solution. + Al 3+ Ca 2+ Cd 2+ Ce 3+ Co 3+ Cr 3+ Cu 2 + Fe 2+ Hg 2+ K + Mg 2+ Mn 2+ Na + Ni 2+ Pb 2+ Sn 2+ Sn 4+ and Zn 2+ The UV-Vis absorption spectrum of the nitrate solution; Cu was added to the detection standard solution. 2+ Subsequently, the absorption intensity at the maximum absorption peak of 688 nm decreased significantly, while the addition of other metal ions did not significantly change the absorption intensity, indicating that the copper ion probe of this invention is effective against Cu. 2+ It has a specific UV-Vis absorption spectral response.

[0056] The above tests showed that the copper ion probe prepared by this invention has a maximum absorption peak at 688 nm in acetonitrile solution, located in the near-infrared region. Its maximum absorption wavelength in acetonitrile solution is superior to that of the existing copper ion probe in squaricocyanate, which has a maximum absorption wavelength of 642 nm. Therefore, the copper ion probe of this invention has significant spectral performance advantages and good resistance to background absorption interference.

[0057] Example 2

[0058] like Figure 1 As shown, the preparation method of the copper ion probe in this embodiment is as follows: 1g of potassium 3,3-dimethyl-5-sulfonate chlorobridged heptamethrin and 0.1mL of diethanolamine were dissolved in 5mL of DMF and reacted at 80℃ for 2h under nitrogen protection; after the reaction was completed and cooled, rotary evaporation was performed to obtain the crude product; the crude product was dissolved in a small amount of methanol and then acetone was added until a blue solid precipitated, which was then filtered and dried to obtain the copper ion probe.

[0059] Example 3

[0060] like Figure 1 As shown, the preparation method of the copper ion probe in this embodiment is as follows: 0.5 g of potassium 3,3-dimethyl-5-sulfonate chlorobridged heptamethrin and 3 mL of diethanolamine were dissolved in 100 mL of acetonitrile. The reaction was carried out at 5 °C for 48 h under helium protection. After the reaction was completed and cooled, rotary evaporation was performed to obtain the crude product. The crude product was dissolved in a small amount of methanol and then diethyl ether was added until a blue solid precipitated. After filtration and drying, the copper ion probe was obtained.

[0061] Example 4

[0062] like Figure 1 As shown, the preparation method of the copper ion probe in this embodiment is as follows: 0.5 g of potassium 3,3-dimethyl-5-sulfonate chlorobridged heptamethrin and 1 mL of diethanolamine were dissolved in 40 mL of methanol and reacted at 25 °C for 6 h under helium protection; after the reaction was completed and cooled, rotary evaporation was performed to obtain the crude product; the crude product was dissolved in a small amount of DMF and then tetrahydrofuran was added until a blue solid precipitated, which was then filtered and dried to obtain the copper ion probe.

[0063] Example 5

[0064] like Figure 1 As shown, the preparation method of the copper ion probe in this embodiment is as follows: 0.5 g of potassium 3,3-dimethyl-5-sulfonate chlorobridged heptamethrin and 1 mL of diethanolamine were dissolved in 40 mL of ethanol and reacted at 25 °C for 4 h under argon protection; after the reaction was completed and cooled, rotary evaporation was performed to obtain the crude product; the crude product was dissolved in a small amount of methanol and then n-butanol was added until a blue solid precipitated, which was then filtered and dried to obtain the copper ion probe.

[0065] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An application of a copper ion probe in the detection of copper ions, characterized in that, The structure of the copper ion probe is shown in Formula I: Equation I; In Formula I, M is selected from at least one of Li, Na, and K; X - It is a halide ion, selected from F - Cl - ,Br - and I - Any one of them.

2. The application according to claim 1, characterized in that, M is K.

3. The application according to claim 1, characterized in that, X - For Cl - .

4. The application according to any one of claims 1-3, characterized in that, The preparation method of the copper ion probe includes the following steps: The copper ion probe is obtained by a substitution reaction of lithium 3,3-dimethyl-5-sulfonate / sodium / potassium halogen-bridged ring heptamethrin and diethanolamine in a reaction solvent.

5. The application according to claim 4, characterized in that, The dosage relationship between lithium 3,3-dimethyl-5-sulfonate / sodium / potassium halogenated heptamethrin and diethanolamine is as follows: 0.1 mL to 6 mL of diethanolamine per gram of lithium 3,3-dimethyl-5-sulfonate / sodium / potassium halogenated heptamethrin.

6. The application according to claim 4, characterized in that, The amount of the reaction solvent used is 5 ml to 200 ml per gram of lithium 3,3-dimethyl-5-sulfonate / sodium / potassium halogenated heptamethrin.

7. The application according to claim 4, characterized in that, The reaction solvent is selected from at least one of methanol, ethanol, acetonitrile, and N,N-dimethylformamide.

8. The application according to claim 4, characterized in that, The substitution reaction is carried out at 5℃ to 80℃ for 2 h to 48 h.

9. The application according to claim 4, characterized in that, The substitution reaction is carried out in an inert gas.

10. The application according to claim 9, characterized in that, The inert gas is any one of nitrogen, helium, and argon.

11. The application according to claim 4, characterized in that, The preparation method further includes post-processing; the post-processing includes rotary evaporation, dissolution and desorption, filtration and drying.

12. The application according to claim 11, characterized in that, The dissolution and precipitation process involves dissolving the crude product obtained by rotary evaporation in a good solvent, and then adding a poor solvent to precipitate it out. The good solvent is selected from any one of methanol, ethanol, and N,N-dimethylformamide. The poor solvent is selected from any one of isopropanol, n-butanol, acetone, diethyl ether, and tetrahydrofuran.

13. The application according to claim 4, characterized in that, The structure of the lithium 3,3-dimethyl-5-sulfonate / sodium / potassium halogen-bridged ring heptamethrin is shown in Formula II: Formula II.

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