Application of a dihydrazide compound in ion detection and detection method

Abstract

This invention belongs to the field of metal ion detection technology, specifically relating to the application and detection method of diacylhydrazine compounds in ion detection. This invention uses diacylhydrazine compounds as the identifier for Zn. 2+ and / or Al 3+ The fluorescent probe has high selectivity and sensitivity, strong binding ability, and good anti-interference ability.

Description

Technical Field

[0001] This invention belongs to the field of metal ion detection technology, specifically relating to the application and detection method of a dihydrazide compound in ion detection. Background Technology

[0002] The accurate identification and detection of metal ions is one of the key challenges in modern analytical chemistry, biomedicine, and environmental science. Zinc ions (Zn) 2+ ) and aluminum ions (Al 3+ As two metal ions that are of great significance in both biological systems and environmental media, the demand for their detection is particularly urgent, but they also face unique technical dilemmas determined by their own physicochemical properties.

[0003] Zinc is an essential trace element for living organisms, participating in hundreds of key physiological processes, including gene expression regulation, nerve signal transduction, and immune function maintenance. Disruption of zinc homeostasis in the body is closely related to various neurodegenerative diseases, such as Alzheimer's disease. Furthermore, as a common industrial pollutant, excessive zinc in the environment can be toxic to aquatic ecosystems. Aluminum is the most abundant metallic element in the Earth's crust, and its products are widely used in industry and daily life. However, aluminum is not an essential element for life; its ionic form (Al) 3+ It has clear neurotoxicity and is associated with the occurrence and development of diseases such as Alzheimer's disease.

[0004] Currently, Zn 2+ And Al 3+ Detection methods include atomic absorption spectroscopy and inductively coupled plasma mass spectrometry, but these techniques typically require complex sample pretreatment, expensive instruments, and are difficult to implement in-situ real-time monitoring. In contrast, the design and synthesis of fluorescence-based probes are becoming increasingly important due to their simple synthesis, tunable performance, and ability to rapidly, selectively, and sensitively detect analytes at target locations, making them a promising alternative strategy. Therefore, this patent aims to provide a novel fluorescent probe structure for the detection of Zn... 2+ And Al 3+ With its high selectivity and high sensitivity, and potentially superior photostability and biocompatibility, this technology aims to provide a more reliable analytical tool for research on zinc and aluminum ions. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides an application and detection method for dihydrazide compounds in ion detection. According to this invention, dihydrazide compounds can be used to detect Zn. 2+ and / or Al 3+ Conduct testing.

[0006] The technical solution provided by this invention is as follows: An application of a dihydrazide compound in ion detection, as a means of identifying Zn. 2+ and / or Al 3+ The fluorescent probe, the structural formula of the dihydrazide compound is as follows: .

[0007] The inventors discovered that the above-mentioned dihydrazide compounds can be used as Zn 2+ and / or Al 3+ The fluorescent probe has high selectivity and sensitivity, strong binding ability, and good anti-interference ability.

[0008] Specifically: the minimum detectable concentration of the dihydrazide compound is greater than or equal to 1 × 10⁻⁶. -6 mol·L -1 .

[0009] Based on the above technical solution, detection of dihydrazide compounds can be performed at relatively low detection concentrations.

[0010] Specifically: Zn 2+ The minimum detection concentration is greater than or equal to 0.2 × 10⁻⁶. -6 mol·L.

[0011] Based on the above technical solution, low Zn content can be achieved. 2+ Content detection. Generally speaking, it meets the requirements for Zn content detection in environmental water quality monitoring or biological samples. 2+ The required content for detection.

[0012] Specifically: Al 3+ The minimum detection concentration is greater than or equal to 0.4 × 10⁻⁶. -6 mol·L.

[0013] Based on the above technical solutions, low Al can be achieved. 3+ Content detection. Generally speaking, it meets the requirements for Al content detection in environmental water quality monitoring or biological samples. 3+ The required content for detection.

[0014] Specifically: the solvent used for testing is a mixture of ethanol and water.

[0015] The solvents mentioned above have the advantages of good solubility, environmental friendliness and low cost, and are generally suitable for use in environmental water quality monitoring or biological samples.

[0016] Preferred: The volume mixing ratio of ethanol and water is (7-9):(3-1).

[0017] The aforementioned ratio can improve the solubility and dispersion stability of probe molecules, thereby enhancing the intensity and stability of the fluorescence signal; it also helps to prevent probe aggregation or fluorescence quenching in a pure water environment, ensuring that the detection system maintains reliable analytical performance over a longer period of time.

[0018] Specifically, 300 nm-400 nm ultraviolet light is used as the excitation light.

[0019] Specifically, it resists interference from Na ions, K ions, Ag ions, Mg ions, Ca ions, Co ions, Ni ions, Cu ions, Ba ions, Hg ions, Pb ions, or Fe ions.

[0020] Based on the above technical solutions The probe can effectively resist Fe 3+ The influence of key interfering ions is considered, thus making it applicable to Zn in complex environmental water samples or biological samples. 2+ Or Al 3+ The detection.

[0021] The present invention also provides a detection method, comprising the following steps: in a solvent, using a dihydrazide compound as a fluorescent probe to detect Zn 2+ and / or Al 3+ The structure of the dihydrazide compound was determined by testing and is as follows: .

[0022] Specifically, in the solvent, the concentration of the dihydrazide compound is greater than or equal to 1 × 10⁻⁶. -6 mol·L -1 .

[0023] Specifically, the solvent is a mixture of ethanol and water.

[0024] Preferably, the volume mixing ratio of ethanol and water is (7-9):(3-1).

[0025] Specifically, ultraviolet light of 300 nm-400 nm is used as the excitation light.

[0026] This invention uses dihydrazide compounds as fluorescent probes for the detection of Zn. 2+ And Al 3+ It exhibits high selectivity and sensitivity, and strong resistance to ion interference. The application method is simple and can be used for environmental water quality monitoring or for detecting Zn in biological samples. 2+ And Al 3+ The detection. Attached Figure Description

[0027] Figure 1 The 1H NMR spectrum is used to characterize the structure of a diacylhydrazine-based fluorescent probe.

[0028] Figure 2 This is a graph showing the changes in the ultraviolet absorption spectrum of the dihydrazide-based fluorescent probe of this invention interacting with different metal ions.

[0029] Figure 3 This is a graph showing the fluorescence emission spectrum changes of the dihydrazide-based fluorescent probe of the present invention interacting with different metal ions.

[0030] Figure 4 The present invention relates to a dihydrazide-based fluorescent probe and Zn. 2+ The fluorescence emission spectrum change curve of the effect.

[0031] Figure 5 The present invention provides a dihydrazide-based fluorescent probe for Al 3+ The fluorescence emission spectrum change curve of the effect.

[0032] Figure 6 For other metal ions, the dihydrazide fluorescent probe of this invention is used for Al 3+ Interference histogram for identification and detection. Detailed Implementation

[0033] The principles and features of the present invention are described below. The embodiments given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0034] Unless otherwise specified, the test methods used in the embodiments are conventional methods; unless otherwise specified, the materials and reagents used are commercially available.

[0035] The fluorescent probe detection reagent can be prepared as follows: Add the dihydrazide compound to a mixed solvent of ethanol and water at a volume ratio of 8:2 to prepare a solution with a concentration of 1×10⁻⁶. -5 mol·L -1 A solution of ethanol and water is obtained.

[0036] Dihydrazide compounds can be obtained using existing technologies, or they can be prepared by the following methods: S1. Weigh 2 mmol of 4-diethylamino-2-hydroxybenzaldehyde and 1 mmol of terephthalohydrazide, add 15 mL of anhydrous ethanol and stir to dissolve to obtain solution A; S2. The A solution obtained in step S1 is stirred and refluxed at 75°C for 3 h, then cooled to room temperature and concentrated under reduced pressure to obtain the crude product. S3. The crude product obtained in step S2 is recrystallized with anhydrous ethanol, filtered and dried to obtain a yellow powder, which is a dihydrazide compound.

[0037] The structural formulas of the above-mentioned dihydrazide-based fluorescent probes are as follows: .

[0038] The reaction formulas in the above preparation method are as follows: The structures of the above-mentioned dihydrazide fluorescent probes were characterized by 1H NMR spectroscopy (e.g., Figure 1 ): Figure 1 The chemical shifts in the 1H NMR spectrum are as follows: 11.93 ppm for amide hydrogen (-CO-NH), 11.41 ppm for imino nitrogen hydrogen (-C=NH), 8.45 ppm for imino hydrocarbon hydrogen (-N=CH), 8.04 ppm and 7.22-6.28 ppm for benzene ring hydrogen (-Ar-H), 3.33 ppm for methylene hydrogen (-CH2), and 1.11 ppm for methyl hydrogen (-CH3). 1 H NMR (400 MHz, DMSO) δ11.93 (s, 1H), 11.41 (s,1H), 8.45 (s, 1H), 8.04 (s, 2H), 7.22 (d, J = 8.8 Hz, 1H), 6.28 (dd, J = 8.8,2.2 Hz, 1H), 6.14 (d, J = 2.2 Hz, 1H), 3.33 (s, 4H), 1.11 (t, J = 7.0 Hz, 6H). Experimental Example 1: Ultraviolet Recognition Experiments of Different Metal Ions The diazid fluorescent probe prepared in Example 1 was formulated into 1×10⁻⁶ units. -5 mol·L -1 Ethanol and water solutions of diazid-based fluorescent probes were prepared. Different metal ion salts (NaCl, KCl, AgNO3, MgCl2, CaCl2, CoCl2, NiCl2, CuCl2, ZnCl2, BaCl2, HgCl2, PbCl2, AlCl3, FeCl3) were prepared using ethanol and water in a volume ratio of 8:2 to prepare 1×10⁻⁶ solutions. -3 mol·L -1 In parallel experiments, 0.02 mL solutions of various metal ions were added to separate 2 mL probe solutions. The binding of the diacidhydrazide fluorescent probes to different metal ions was detected using UV-Vis spectroscopy. Specific results are shown below. Figure 2 As shown. Among them. Figure 2 Multiple lines in the diagram represent the addition of the same amount of different metal ions.

[0039] Depend on Figure 2It can be seen that dihydrazide-based fluorescent probes only show an absorption peak at 383 nm. When different metal ions are added: 1) with the addition of Zn... 2 With the addition of ⁺, the absorption peak at 383 nm gradually redshifted to 426 nm, a redshift of 43 nm; 2) with Al 3 + With the addition of [specific ion], the absorption peak at 383 nm gradually red-shifted to 424 nm, a shift of 41 nm; 3) with the addition of other metal ions, the absorption peak at 383 nm did not shift significantly. Therefore, the dihydrazide-based fluorescent probe prepared in Example 1 is effective for Zn [specific ion]. 2 ⁺ and Al 3+ It has a high recognition function.

[0040] Experimental Example 2: Fluorescence recognition experiments of different metal ions The diazid fluorescent probe prepared in Example 1 was formulated into 1×10⁻⁶ units. -5 mol·L -1 Ethanol and water solutions of diazid-based fluorescent probes were prepared. Different metal ion salts (NaCl, KCl, AgNO3, MgCl2, CaCl2, CoCl2, NiCl2, CuCl2, ZnCl2, BaCl2, HgCl2, PbCl2, AlCl3, FeCl3) were prepared using ethanol and water in a volume ratio of 8:2 to prepare 1×10⁻⁶ solutions. -3 mol·L -1 In parallel experiments, 0.02 mL solutions of various metal ions were added to separate 2 mL probe solutions. The binding of the diazid fluorescent probes to different metal ions was detected using fluorescence spectroscopy. Specific results are shown below. Figure 3 As shown. Among them. Figure 3 Multiple lines in the diagram represent the addition of the same amount of different metal ions.

[0041] Depend on Figure 3 It is known that the maximum fluorescence emission peak of the dihydrazide-based fluorescent probe is at 596 nm, with a fluorescence intensity of 40 a.u., exhibiting only a very weak orange-red fluorescence. When different metal ions are added: 1) with the addition of Zn... 2 The addition of ⁺ shifted the maximum fluorescence emission peak to 557 nm, and the fluorescence intensity significantly increased to 740 au, turning into a strong yellow fluorescence; 2) with Al 3+ The addition of [a specific substance] caused a blue shift in the maximum fluorescence emission peak to 540 nm, and the fluorescence intensity significantly increased to 781 au, becoming a strong yellow-green fluorescence. 3) With the addition of other metal ions, neither the fluorescence intensity nor the maximum fluorescence emission peak showed significant changes. Therefore, the diazid-based fluorescent probe prepared in Example 1 is effective against Zn [a specific substance]. 2⁺ and Al 3+ It has a high recognition function.

[0042] Experimental Example 3: For Zn 2 Fluorescence recognition experiment of ⁺ The diazid fluorescent probe prepared in Example 1 was formulated into 1×10⁻⁶ units. -5 mol·L -1 A solution of diazid-based fluorescent probes in ethanol and water. ZnCl2 was prepared by dissolving ZnCl2 in ethanol and water at a volume ratio of 8:2 to obtain a 1×10⁻⁶ solution. -3 mol·L -1 A solution of ethanol and water, with 0.02 mL of Zn 2 The ⁺ ion solution was divided into 12 equal portions and gradually added dropwise to 2 mL of probe solution. The reaction between the diazid fluorescent probe and Zn was detected by fluorescence spectroscopy. 2 The combination of ⁺. Specific results are as follows: Figure 4 As shown. Among them. Figure 4 The multiple lines in the image represent the Zn content in the detection solution. 2 ⁺ represents different concentrations, ranging from 0.08 to 1 times the concentration of the probe ions.

[0043] Depend on Figure 4 It is known that the maximum fluorescence emission peak of the dihydrazide-based fluorescent probe is at 596 nm, with a fluorescence intensity of 40 a.u., exhibiting only a very weak orange-red fluorescence. With the addition of Zn... 2 With increasing the amount of ⁺, at the same concentration as the probe, the fluorescence intensity significantly increased to 1257 au, and the maximum fluorescence emission peak blue-shifted to 561 nm. Therefore, the diazid fluorescent probe prepared in Example 1 is effective for Zn. 2 ⁺ It has a high recognition function.

[0044] Experimental Example 4: For Al 3+ Fluorescence recognition experiment The diazid fluorescent probe prepared in Example 1 was formulated into 1×10⁻⁶ units. -5 mol·L -1 An ethanol and water solution of a dihydrazide-based fluorescent probe. AlCl3 was prepared by dissolving AlCl3 in ethanol and water at a volume ratio of 8:2 to prepare a 1×10⁻⁶ solution. -3 mol·L -1 A solution of ethanol and water, with 0.02 mL of Al 3+ The ion solution was divided into 10 equal portions and gradually added dropwise to 2 mL of probe solution. The reaction between the diacidhydrazide fluorescent probe and Al was detected by fluorescence spectroscopy. 3+ The combination. Specific results are as follows: Figure 5 As shown. Among them. Figure 5 The multiple lines in the image represent Al in the detection solution. 3+The concentrations were 0.1 to 1 times the concentration of the probe ions.

[0045] Depend on Figure 5 It is known that the maximum fluorescence emission peak of the dihydrazide-based fluorescent probe is at 596 nm, with a fluorescence intensity of 40 a.u., exhibiting only a very weak orange-red fluorescence. With the addition of Al... 3+ With increasing concentration, when the concentration is the same as the probe concentration, the fluorescence intensity significantly increases to 888 au, and the maximum fluorescence emission peak blue-shifts to 550 nm. Therefore, the diazid-based fluorescent probe prepared in Example 1 is effective against Al. 3+ It has a high recognition capability.

[0046] Experimental Example 5: Other metal ions on Al 3+ Identification interference experiment The diazid fluorescent probe prepared in Example 1 was formulated into 1×10⁻⁶ units. -5 mol·L -1 Ethanol and water solutions of diazid-based fluorescent probes were prepared. Different metal ion salts (NaCl, KCl, AgNO3, MgCl2, CaCl2, CoCl2, NiCl2, CuCl2, ZnCl2, BaCl2, HgCl2, PbCl2, AlCl3, FeCl3) were prepared using ethanol and water in a volume ratio of 8:2 to prepare 1×10⁻⁶ solutions. -3 mol·L -1 An ethanol and water solution was prepared, and 0.02 mL of the metal ion solution was added to 2 mL of the probe solution. Other metal ions were detected using fluorescence spectroscopy to support the recognition of Al by the diacidhydrazide-based fluorescent probe. 3+ The interference effect. Specific results are as follows: Figure 6 As shown. Figure 6 The medium gray bars represent the maximum emission peak intensity of fluorescence when equal amounts of different metal ions are added to the diacylhydrazine fluorescent probe, while the black bars represent the maximum emission peak intensity when equal amounts of Al are added to the diacylhydrazine fluorescent probe. 3+ Then, equal amounts of other metal ions were added to measure the maximum emission peak intensity of fluorescence.

[0047] Depend on Figure 6 It can be seen that adding equal amounts of Al to dihydrazide-based fluorescent probes... 3+ Subsequently, its fluorescence intensity significantly increased. After adding equal amounts of other metal ions, its fluorescence intensity only fluctuated slightly, without significant decrease or increase. Therefore, iron ions and other metal ions can effectively detect Al in the dihydrazide-based fluorescent probe prepared in Example 1. 3+ It has very little interference and strong anti-interference ability.

[0048] As can be seen from Experiments 1-5, the diazid fluorescent probes prepared in Example 1 are effective against Zn. 2 ⁺ and Al 3+ It has a highly efficient identification function and can be widely used for Zn identification. 2 ⁺ and Al 3+ The detection.

[0049] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An application of a dihydrazide compound in ion detection, characterized in that: As an identification of Zn 2+ and / or Al 3+ The fluorescent probe, the structural formula of the dihydrazide compound is as follows: 。 2. The application of the dihydrazide compound according to claim 1 in ion detection, characterized in that: The minimum detectable concentration of the dihydrazide compound is greater than or equal to 1 × 10⁻⁶. -6 mol·L -1 .

3. The application of the dihydrazide compound according to claim 1 in ion detection, characterized in that: Zn 2+ The minimum detection concentration is greater than or equal to 0.2 × 10⁻⁶. -6 mol·L -1 .

4. The application of the dihydrazide compound according to claim 1 in ion detection, characterized in that: Al 3+ The minimum detection concentration is greater than or equal to 0.4 × 10⁻⁶. -6 mol·L -1 .

5. A detection method, characterized in that, Includes the following steps: In a solvent, dihydrazide compounds were used as fluorescent probes for Zn. 2+ and / or Al 3+ The structure of the dihydrazide compound was determined by testing and is as follows: 。 6. The detection method according to claim 5, characterized in that: In the solvent, the concentration of the dihydrazide compound is greater than or equal to 1 × 10⁻⁶. -6 mol·L -1 .

7. The detection method according to claim 5, characterized in that: The solvent is a mixture of ethanol and water.

8. The detection method according to claim 7, characterized in that: The volume ratio of ethanol to water is (7-9):(3-1).

9. The detection method according to claim 5, characterized in that: Ultraviolet light of 300 nm-400 nm was used as the excitation light.

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