Aluminum ion detection reagent, preparation method and application thereof

Abstract

The application provides an aluminum ion detection reagent and a preparation method and application thereof, and aims to solve the problems of high cost, complex technology, time consumption and unallowable high-throughput analysis of aluminum ion detection in the prior art. 3+ The aluminum ion detection reagent contains the following structure: and the preparation method comprises the following steps: (1) adding 2-chlorobenzaldehyde and 2-chloroaniline into a first solvent, carrying out a heating reflux reaction, and then carrying out purification treatment to obtain an intermediate product; (2) adding alkali, 8-hydroxyquinoline and a second solvent into the intermediate product, carrying out a reaction at room temperature, and then carrying out purification treatment, and the aluminum ion detection reagent is obtained. ‑7 The aluminum ion detection reagent can qualitatively and quantitatively detect aluminum ions, and the detection limit reaches 2.24*10 MM.

Description

Technical Field

[0001] The present invention belongs to the field of metal ion detection, and in particular relates to an aluminum ion detection reagent and a preparation method and application thereof. Background Art

[0002] Aluminum (Al) is the most abundant metallic element in the Earth's crust. Over the past few decades, approximately 400 million tons of primary aluminum have been used annually in human social activities (such as aviation, construction, electricity, industrial production, household appliances, agriculture, medicine, chemicals, and electronic information). With the large-scale production and use of aluminum in human production and life, more and more aluminum has entered the ecosystem. Generally, intake of aluminum through diet can damage the nervous system and immune system, leading to brain degeneration, memory loss, and affected intelligence and personality, and even Alzheimer's disease. Excessive Al 3+ It not only inhibits the intestinal absorption of phosphorus, but also interferes with the normal calcium and phosphorus metabolism in the body, especially for patients with renal failure, which will seriously threaten the patient's bones, brain and nervous system. Therefore, it is necessary to develop a method to detect Al in biological and environmental analysis. 3+ Although there are some fluorescent probes for the detection of Al 3+ ions, but for Al 3+ The design of ions with low toxicity, high affinity and high selectivity toward other metal ions remains a challenging task.

[0003] Currently, traditional methods such as voltammetry, potentiometry, atomic absorption spectroscopy (AAS), inductively coupled plasma mass spectrometry (ICP-MS), and atomic emission spectroscopy (AES) have been used to detect metal ions. However, these methods are costly, technically complex, and time-consuming, preventing high-throughput analysis. Fluorescence sensing offers the advantages of rapidity, simplicity, and low cost for detecting metal ions. Therefore, developing a highly sensitive and selective fluorescence detection method for aluminum ions that can operate under weakly acidic conditions is of great practical significance.

[0004] Patent 202110560215.9 discloses a fluorescent sensor based on a quinoline derivative, its synthesis, and its application in detecting aluminum ions. However, the aluminum ion detection reagent in this solution is used to detect aluminum ions in solution and cannot be used to detect aluminum ions in biological cells. Moreover, the synthesis method disclosed in this solution has a low product yield. Summary of the Invention

[0005] The purpose of the present invention is to provide an aluminum ion detection reagent and its preparation method and application, so as to solve the problem of aluminum ion detection in the prior art. 3+Ion detection is costly, technically complex and time-consuming, and does not allow high-throughput analysis. To achieve the above objectives, the present invention adopts the following technical solution: designing an aluminum ion detection reagent, the aluminum ion detection reagent comprising the following structure:

[0006] Furthermore, the aluminum ion detection reagent contains one of the following structures:

[0007] 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 .

[0008] Further, its synthetic route is as follows:

[0009] .

[0010] The present invention provides a method for preparing the aluminum ion detection reagent, comprising the following steps:

[0011] (1) adding the raw material aldehyde and the raw material 2-chloroaniline derivative to a first solvent, heating under reflux for reaction, and then purifying to obtain an intermediate product;

[0012] (2) adding a base, a quinoline derivative and a second solvent to the intermediate product, purifying and treating after reaction at room temperature, to obtain.

[0013] Further, the 2-chloroaniline derivative raw material is at least one of 2-bromo-6-chloroaniline, 2-chloro-4,6-dibromoaniline, 4-bromo-2-chloroaniline, 2-chloro-4-thiocyanatoaniline, 2-chloro-5-methylaniline, 2,5-dichloroaniline, 4-chloroaniline, 3-chloroaniline, 2,4-dichloroaniline, 2,6-dichloroaniline, 2-chloro-4-methylaniline, 3,5-dichloroaniline, 2,4,6-trichloroaniline, 2,4-dichloro-6-iodoaniline.

[0014] Further, the quinoline derivative includes at least one of 8-hydroxyquinoline, 4-bromo-8-hydroxyquinoline, 8-hydroxyquinoline-4-carboxylic acid methyl ester, 5-chloro-8-hydroxyquinoline, 5-bromo-8-hydroxyquinoline, 5-nitro-8-hydroxyquinoline, 8-hydroxy-7-quinolinecarboxaldehyde, 6-bromo-3-chloro-8-hydroxyquinoline, 8-hydroxy-2-chloroquinoline, 8-hydroxy-6-nitroquinoline, 5,7-dibromo-8-hydroxyquinoline, 8-hydroxy-7-propylquinoline, 5,7-dimethyl-8-hydroxyquinoline, 5-fluoro-8-hydroxyquinoline, 5-octyloxymethyl-8-hydroxyquinoline, 8-hydroxyquinoline-5-carboxylic acid ethyl ester.

[0015] Further, the raw material aldehyde has a structure containing .

[0016] Further, the raw material aldehyde has one of the following structures: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 .

[0017] Furthermore, the purification method in step (1) is as follows: filtering the solution after the reaction, washing the precipitate with a hot first solvent, and removing the solvent under vacuum conditions to obtain the intermediate product.

[0018] Furthermore, the purification method in step (2) is as follows: filtering the insoluble matter, distilling the filtrate under reduced pressure, adding a third solvent to the system, stirring for a certain period of time, then starting to dropwise add a fourth solvent, stirring at room temperature until a precipitate appears, filtering, washing the precipitate with the fourth solvent, and removing the solvent under vacuum to obtain the product. The third solvent is a good solvent, and the fourth solvent is a poor solvent.

[0019] Furthermore, the first solvent is at least one of anhydrous methanol, anhydrous ethanol, ethylene glycol, isopropanol, acetone, and butanone; the second solvent is at least one of anhydrous chloroform, acetonitrile, 1,4-dioxane, tetrahydrofuran, and carbon tetrachloride; the base is at least one of anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous sodium bicarbonate, anhydrous cesium carbonate, anhydrous potassium bicarbonate, and anhydrous lithium carbonate; the third solvent is at least one of diethyl ether, ethyl methyl carbonate, ethyl acetate, butyl acetate, dimethyl carbonate, and benzene; and the fourth solvent is at least one of 1,2-dichloroethane, n-hexane, cyclohexane, n-heptane, butane, and methyl tert-butyl ether.

[0020] Design an Al 3+ The application of the detection reagent can detect aluminum ions qualitatively and quantitatively, with a detection limit of 2.24 × 10 -7 M.

[0021] Furthermore, the aluminum ion detection reagent of the present invention is used to detect aluminum ions in biological cells. The detection method is as follows: the biological cells are cultured with PBS buffer containing the aluminum ion detection reagent for 30 minutes, the aluminum ion detection reagent outside the biological cells is washed with PBS buffer, and the cells are irradiated with UV light with a wavelength of 365 nm. The color change is observed using an optical microscope.

[0022] The present invention has the following beneficial effects:

[0023] 1. The present invention adopts fluorescence sensing technology, which has the advantages of simplicity, fast response, good selectivity, high sensitivity, easy operation, and real-time detection. It introduces a fluorophore containing 8-hydroxyquinoline derivatives for the detection of Al in organic solutions and water systems. 3+ The synthesized fluorescent probe nearly meets the key characteristics of an intracellular fluorescent probe: an excitation wavelength of 340 nm to prevent UV-induced cell damage, and an emission wavelength close to 500 nm to avoid the natural fluorescence of the cells themselves, facilitating cell imaging experiments using fluorescence microscopy.

[0024] 2.The aluminum (III) ion reagent provided by the application has the performance of qualitatively and quantitatively detecting aluminum (III) ions in an aqueous solution, and has the application prospect of qualitatively and quantitatively detecting aluminum (III) ions, and the detection limit reaches 2.24 ×10 - 7 M; and the aluminum ion detection reagent of the application has a simple preparation process and a yield of 93.1%.

[0025] 3.The aluminum ion detection reagent of the application can be used for detecting aluminum ions in biological cells. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The fluorescence comparison chart of the Al 3+ ion and other metal ion test reagents.

[0027] Figure 2 The fluorescence data schematic diagram of the Al 3+ ion detection reagent added into the solutions containing different metal ions for determining each group of solutions.

[0028] Figure 3 The schematic diagram of the Al 3+ ion detection reagent of the application for detecting HeLa cells.

[0029] Figure 4 The fluorescence image of the Hela cells incubated with the Al 3+ ion detection reagent and Al 3+ In the figure, the cells are incubated with 20 μM L for 30 min (a and b), and then further incubated with 20 μM Al 3+ for 30 min (c and d); the left images (a and c) are observed by an optical microscope, and the right images (b and d) are taken by a fluorescence microscope.

[0030] Figure 5 The color change of the Al 3+ ion under natural light and under UV light (365 nm) of the application. DETAILED DESCRIPTION

[0031] In order to better illustrate the purpose, technical scheme and beneficial effects of the application, the application will be further described below in combination with specific examples. It should be noted that the following implementation of the method is a further explanation and description of the application, and should not be regarded as a limitation of the application.

[0032] Example 1

[0033] The synthesis route of the aluminum ion detection reagent is as follows:

[0034]

[0035] The specific synthesis process of the intermediate product is as follows: 2-chloroaniline (1.1 mmol) and 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) and reacted under reflux for 2 hours. The resulting yellow precipitate was then filtered and washed three times with hot CH3OH (8 mL). The solvent was removed under vacuum to obtain the intermediate product in a yield of 98%.

[0036] The specific synthesis process of the target product is as follows:

[0037] The intermediate product (1 mmol), anhydrous K2CO3 (1.5 mmol) and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL). The solution mixture was reacted under reflux for 12 h. The insoluble matter was filtered and the solvent was evaporated under reduced pressure. 25 mL of diethyl ether was added to the residue and stirred to dissolve. 1,2-dichloroethane was added dropwise until a precipitate was formed. The mixture was filtered and the filter cake was washed with 1,2-dichloroethane. The solvent was removed under vacuum to obtain the target product in a yield of 95%.

[0038] Characterization results of the target product:

[0039] 1) Infrared spectroscopy:

[0040] Use potassium bromide tableting method at 400~4000cm -1 The main infrared absorption peaks of the obtained compound are: 3074, 1609, 1493, 1442, 1306, 1191, 839, 790, 699 cm -1 .

[0041] 2) Nuclear magnetic resonance hydrogen spectrum determination:

[0042] Deuterated chloroform was used as solvent and tetramethylsilane as internal standard. The H NMR spectrum of the obtained compound was measured using a Bruker 400 NMR spectrometer. 1H NMR (CDCl3) δ 9.20(s, 1H),8.92(d, J = 8.0 Hz,2H),8.53 (d, J = 8.4 Hz, 2H),7.96(d, J = 8.0 Hz, 2H), 7.68(s, 1H) 7.67 (s,1H), 7.54 (d, J = 7.5 Hz, 2H),7.25(t, J = 8.0 Hz, 2H) 7.20 (d, J = 8.0 Hz,2H),7.23 (s, 1H), 7.03 (d, J = 6.9 Hz, 2H), 6.99 (d, J = 8.0 Hz, 2H), 6.95(s,H),

[0043] 3) Nuclear magnetic resonance carbon spectroscopy determination:

[0044] Deuterated dimethyl sulfoxide was used as solvent and tetramethylsilane was used as internal standard. The carbon spectrum was measured using a Bruker 400 nuclear magnetic resonance spectrometer. The carbon NMR spectrum of the obtained compound is 160.16,159.40,154.48,153.02,152.42,149.37,148.90,141.35,138.51,138.03,137.17,135.20,135.01,134.06,132.54,,131.55,130.18,129.23,128.03,127.51,126.87,125.55,125.14,123.86,122.74,121.43,120.35,119.82,117.11,115.40,113.12,112.82.

[0045] 4) Elemental analysis:

[0046] Elemental analysis was performed using a PE2400-11 elemental analyzer from PE Company, USA. The elemental analysis values ​​of the obtained compound were: Found C 79.88, H 4.56, N 8.77, O: 6.79.

[0047] 5) Mass spectrometry:

[0048] The mass spectrum was measured using a Bruker DataAnalysis mass spectrometer: the mass spectrum of the obtained compound was: [M+Na] + :490.15;(theoretical value), found:490.23.

[0049] Application of target product in detection of aluminum ions:

[0050] The aluminum ion detection reagent obtained in Example 1 was prepared into 3.0×10-5 mmol / L DMSO solution. + , K + , Ag + , Zn 2+ , Mg 2+ , Ba 2+ , Ca 2+ , Mn 2+ , Pb 2+ , Hg 2+ , Ni 2+ , Cd 2+ ,Co 2+ , Cu 2+ , Fe 2+ , Cr 3+ , Fe 3+ , Al 3+ and Eu 3+ The results showed that:

[0051] Before joining Al 3+ ions, the fluorescence of the test reagent increases, while the fluorescence of the test reagent remains almost unchanged when other metal ions are added, such as Figure 1 In the experiment, 3mLAl 3+ The ion detection reagent is added to the cuvette, and then added to the solution containing different types and concentrations of metal ions and mixed evenly, and the fluorescence data of each group of solutions is measured, such as Figure 2 As shown. After fluorescence titration and fitting calculation, it was determined that the detection limit can reach 2.24 × 10 -7 M( Figure 3 ), the aluminum ion detection reagent of the present invention can detect aluminum ions qualitatively and quantitatively.

[0052] Based on the above spectral experimental studies, it can be seen that the aluminum ion detection reagent can specifically and sensitively identify Al 3+ Therefore, in order to further expand the application scope of aluminum ion detection reagents, the Al ion content in human cervical cancer cell line HeLa cells was detected by laser confocal microscopy. 3+ Conduct testing.

[0053] This example studies the effect of 20 μM on Al 3+ Ion recognition effect. HeLa cells were cultured with PBS buffer containing aluminum ion detection reagent (10 μM) for 30 min, and the aluminum ion detection reagent outside the cells was washed with PBS buffer of the same concentration, and then the aluminum ion detection reagent was washed with Al 3+ ions (20 μM) in PBS buffer and incubate the cells for another 30 min. Figure 4 As shown, when adding Al 3+Before the addition of ions, no blue fluorescence was observed by optical microscopy, which indicates that the aluminum ion detection reagent can penetrate the cell wall and enter the cell. After the addition of Al 3+ After the addition of ions, the fluorescence was obviously enhanced by optical microscopy. The fluorescence images obtained by optical microscopy above indicate that the probe aluminum ion detection reagent has great potential for basic biological research.

[0054] Figure 5 It is shown that the excitation wavelength of the aluminum ion detection reagent of the present application is about 365 nm, which can prevent ultraviolet-induced damage to cells.

[0055] In other embodiments, 2-bromo-6-chloroaniline, 2-chloro-4,6-dibromoaniline, 4-bromo-2-chloroaniline, 2-chloro-4-thiocyanatoaniline, 2-chloro-5-methylaniline, 2,5-dichloroaniline, 4-chloroaniline, 3-chloroaniline, 2,4-dichloroaniline, 2,6-dichloroaniline, 2-chloro-4-methylaniline, 3,5-dichloroaniline, 2,4,6-trichloroaniline, 2,4-dichloro-6-iodoaniline are used instead of 2-chloroaniline in Embodiment 1;

[0056] 4-bromo-8-hydroxyquinoline, 8-hydroxyquinoline-4-carboxylic acid methyl ester, 5-chloro-8-hydroxyquinoline, 5-bromo-8-hydroxyquinoline, 5-nitro-8-hydroxyquinoline, 8-hydroxy-7-quinolinecarboxaldehyde, 6-bromo-3-chloro-8-hydroxyquinoline, 8-hydroxy-2-chloroquinoline, 8-hydroxy-6-nitroquinoline, 5,7-dibromo-8-hydroxyquinoline, 8-hydroxy-7-propylquinoline, 5,7-dimethyl-8-hydroxyquinoline, 5-fluoro-8-hydroxyquinoline, 5-octyloxymethyl-8-hydroxyquinoline, 8-hydroxyquinoline-5-carboxylic acid ethyl ester are used instead of 8-hydroxyquinoline in Embodiment 1;

[0057] The raw material aldehyde containing the following structure is used instead of 2-chlorobenzaldehyde in Embodiment 1:

[0058] , , , , , , , , , , , , , , , , , , , , , 、 、 、 、 .

[0059] An aluminum ion detection reagent having a corresponding chemical formula structure was obtained, and the results were similar to those of Example 1 after determination and application tests according to the characterization method of Example 1.

[0060] In some other embodiments, anhydrous ethanol, ethylene glycol, isopropanol, acetone, and butanone were used to replace the anhydrous methanol in Example 1; anhydrous chloroform, 1,4-dioxane, tetrahydrofuran, and carbon tetrachloride were used to replace the acetonitrile in Example 1; anhydrous sodium carbonate, anhydrous sodium bicarbonate, anhydrous cesium carbonate, anhydrous potassium bicarbonate, and anhydrous lithium carbonate were used to replace the anhydrous potassium carbonate in Example 1; ethyl methyl carbonate, ethyl acetate, butyl acetate, dimethyl carbonate, and benzene were used to replace the ether in Example 1; and 1,2-dichloroethane in Example 1 was replaced with n-hexane, cyclohexane, n-heptane, butane, and methyl tert-butyl ether; the aluminum ion detection reagent in Example 1 was also obtained, and the yield was close to that in Example 1.

[0061] In one experimental example, the steps for synthesizing the intermediate product were the same as those in Example 1. The intermediate product (1 mmol), anhydrous K₂CO₃ (1.5 mmol), and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH₃CN (25 mL) and anhydrous DMF (3 mL). The solution mixture was reacted under reflux for 12 hours. The solvent was evaporated under reduced pressure, and 25 mL of 5% saline solution was added to the residue. The mixture was extracted three times with CHCl₃ (25 mL). The organic layer was dried over anhydrous Na₂SO₄, and the solvent was removed in vacuo. The crude product was separated and purified by silica gel chromatography (ethyl acetate / petroleum ether = 1:9) to obtain the target product. The yield of the target product in this experimental example was only 85.5%, while the yield of the target product in Example 1 reached 93.1%. By comparison, the yield can be improved by using the method of Example 1.

[0062] The following examples use different raw materials to synthesize the corresponding aluminum ion detection reagents, and the synthesized products are measured by infrared spectroscopy to prove that the corresponding target products are synthesized:

[0063] Example 2:

[0064] 2-Bromo-6-chloroaniline (1.1 mmol) and 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) and reacted under reflux for 2 h. The resulting yellow precipitate was then filtered and washed three times with hot CH3OH (8 mL). The solvent was removed under vacuum to obtain the intermediate product in a yield of 97.8%.

[0065] The intermediate product (1 mmol), anhydrous K2CO3 (1.5 mmol), and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL). The solution mixture was reacted under reflux for 12 h. The insoluble matter was filtered, and the solvent was evaporated from the filtrate under reduced pressure. 25 mL of diethyl ether was added to the residue and stirred to dissolve. 1,2-dichloroethane was added dropwise until a precipitate formed. The mixture was filtered, and the filter cake was washed with 1,2-dichloroethane. The solvent was removed under vacuum to obtain the target product in a yield of 95.2%.

[0066] m . p.: 205-206℃. Infrared spectrum (cm -1 ): 3074 , 2957 , 1609 , 1617, 1493,1442, 790 , 699.

[0067] Example 3:

[0068] 4-Bromo-2-chloroaniline (1.1 mmol) and 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) and reacted under reflux for 2 h. The resulting yellow precipitate was then filtered and washed three times with hot CH3OH (8 mL). The solvent was removed under vacuum to obtain the intermediate product in a yield of 98.02%.

[0069] The intermediate product (1 mmol), anhydrous K2CO3 (1.5 mmol), and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL). The solution mixture was reacted under reflux for 12 h. The insoluble matter was filtered, and the solvent was evaporated from the filtrate under reduced pressure. 25 mL of diethyl ether was added to the residue and stirred to dissolve. 1,2-dichloroethane was added dropwise until a precipitate formed. The mixture was filtered, and the filter cake was washed with 1,2-dichloroethane. The solvent was removed under vacuum to obtain the target product in a yield of 95.04%.

[0070] m . p.: 205-206℃. Infrared spectrum (cm -1 ): 3074 , 2957 , 1609 , 1617, 1493,1442, 790 , 699.

[0071] Example 4: 2-Chloro-5-methylaniline (1.1 mmol) and 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) and reacted at reflux for 2 h. The resulting yellow precipitate was then filtered and washed three times with hot CH3OH (8 mL). The solvent was removed under vacuum to obtain the intermediate product in a yield of 97.5%.

[0072] To the intermediate product (1 mmol), anhydrous K2CO3(1.5 mmol) and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL), the solution mixture was reacted under reflux conditions for 12 h, the insoluble was filtered, the filtrate was evaporated under reduced pressure to remove the solvent, 25 mL of diethyl ether was added to the residue to stir and dissolve, 1,2-dichloroethane was started to drop until the precipitation was produced, filtered, the filter cake was washed with 1,2-dichloroethane, and the solvent was removed under vacuum to obtain the target product with a yield of 94.6%.

[0073] m. p.: 205-206℃. Infrared spectrum (cm -1 ): 3074, 2957, 1609, 1617, 1493,1442, 790, 699.

[0074] Example 5: 2-Chloro-4-methylaniline (1.1 mmol), 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) solution, and reacted under reflux conditions for 2 h. Then the yellow precipitate produced was filtered, washed with hot CH3OH (8 mL) three times, and the solvent was removed under vacuum to obtain the intermediate product with a yield of 97.8 %.

[0075] To the intermediate product (1 mmol), anhydrous K2CO3(1.5 mmol) and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL), the solution mixture was reacted under reflux conditions for 12 h, the insoluble was filtered, the filtrate was evaporated under reduced pressure to remove the solvent, 25 mL of diethyl ether was added to the residue to stir and dissolve, 1,2-dichloroethane was started to drop until the precipitation was produced, filtered, the filter cake was washed with 1,2-dichloroethane, and the solvent was removed under vacuum to obtain the target product with a yield of 94.6%.

[0076] m. p.: 204-205℃. Infrared spectrum (cm -1 ): 3074, 2957, 1609, 1617, 1493,1442, 790, 699.

[0077] Example 6: 3-Chloroaniline (1.1 mmol), 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) solution, and reacted under reflux conditions for 2 h. Then the yellow precipitate produced was filtered, washed with hot CH3OH (8 mL) three times, and the solvent was removed under vacuum to obtain the intermediate product with a yield of 98.3 %.

[0078] The intermediate product (1 mmol), anhydrous K2CO3 (1.5 mmol), and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL). The solution mixture was reacted under reflux for 12 h. The insoluble matter was filtered, and the solvent was evaporated under reduced pressure from the filtrate. 25 mL of diethyl ether was added to the residue and stirred to dissolve. 1,2-dichloroethane was added dropwise until a precipitate formed. The mixture was filtered, and the filter cake was washed with 1,2-dichloroethane. The solvent was removed under vacuum to obtain the target product in a yield of 95.4%.

[0079] m . p.: 204-205℃. Infrared spectrum (cm -1 ): 3074 , 2957 , 1609 , 1617, 1493,1442, 790 , 699.

[0080] Example 7: 3-Chloroaniline (1.1 mmol) and 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) and reacted at reflux for 2 h. The resulting yellow precipitate was then filtered and washed three times with hot CH3OH (8 mL). The solvent was removed under vacuum to obtain the intermediate product in a yield of 98.0%.

[0081] The intermediate product (1 mmol), anhydrous K2CO3 (1.5 mmol), and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL). The solution mixture was reacted under reflux for 12 h. The insoluble matter was filtered, and the solvent was evaporated from the filtrate under reduced pressure. 25 mL of diethyl ether was added to the residue and stirred to dissolve. 1,2-dichloroethane was added dropwise until a precipitate formed. The mixture was filtered, and the filter cake was washed with 1,2-dichloroethane. The solvent was removed under vacuum to obtain the target product in a yield of 94.7%.

[0082] m . p.: 204-205℃. Infrared spectrum (cm -1 ): 3074 , 2957 , 1609 , 1617, 1493,1442, 790 , 699.

Claims

1. An aluminum ion detection reagent, characterized in that The aluminum ion detection reagent contains the following structure:

2. The aluminum ion detection reagent according to claim 1, characterized in that Its synthetic route is as follows:

3. A method for preparing the aluminum ion detection reagent according to claim 1, characterized in that: The following steps are involved: (1) adding 2-chlorobenzaldehyde and 2-chloroaniline raw materials to a first solvent, heating under reflux for reaction, and then purifying to obtain an intermediate product; (2) Add a base, 8-hydroxyquinoline and a second solvent to the intermediate product, react at room temperature, and then purify to obtain the product.

4. The preparation method according to claim 3, characterized in that The purification method in step (1) is as follows: filtering the solution after the reaction, washing the precipitate with a hot first solvent, and removing the solvent under vacuum conditions to obtain the intermediate product.

5. The preparation method according to claim 4, characterized in that The purification method in step (2) is as follows: filter the insoluble matter, evaporate the filtrate under reduced pressure, add the third solvent to the system, stir for a certain period of time, then start adding the fourth solvent dropwise, stir at room temperature until a precipitate appears, filter, wash the precipitate with the fourth solvent, and remove the solvent under vacuum to obtain the target product.

6. The preparation method according to claim 5, characterized in that The first solvent is at least one of anhydrous methanol, anhydrous ethanol, ethylene glycol, isopropanol, acetone, and butanone; the second solvent is at least one of anhydrous chloroform, CH3CN, 1,4-dioxane, tetrahydrofuran, and carbon tetrachloride; the base is at least one of anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous sodium bicarbonate, anhydrous cesium carbonate, anhydrous potassium bicarbonate, and anhydrous lithium carbonate; the third solvent is at least one of diethyl ether, ethyl methyl carbonate, ethyl acetate, butyl acetate, dimethyl carbonate, and benzene; and the fourth solvent is at least one of 1,2-dichloroethane, n-hexane, cyclohexane, n-heptane, butane, and methyl tert-butyl ether.

7. Use of the aluminum ion detection reagent according to claim 1, characterized in that: Used to prepare reagents for qualitative and quantitative detection of aluminum ions.

8. The use of the aluminum ion detection reagent according to claim 7, characterized in that Used to prepare a reagent for detecting aluminum ions in biological cells. The detection method is as follows: the biological cells are cultured with PBS buffer containing the aluminum ion detection reagent, the aluminum ion detection reagent outside the biological cells is then washed with PBS buffer, and the color change is observed using an optical microscope after irradiation with UV light of a wavelength of 365nm.

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