A hetero[4]aromatic macrocyclic compound, a preparation method thereof, and applications in detecting silver ions and iron ions

Abstract

The present invention discloses a hetero[4]arene macrocyclic compound, a preparation method thereof, and an application thereof in detecting silver ions and iron ions, belonging to the technical field of analytical chemistry. The present invention uses the hetero[4]arene macrocyclic compound as a detection material for iron ions and silver ions. The detection process is simple to operate, requires low equipment, and reduces the cost of detecting iron ions and silver ions; moreover, during the detection process of iron ions and silver ions, it is possible to directly judge whether iron ions and silver ions are present by the naked eye, which is conducive to the rapid detection of iron ions and silver ions.

Description

Technical Field

[0001] The present invention belongs to the technical field of analytical chemistry, and particularly relates to a hetero[4]aromatic macrocyclic compound, a preparation method thereof, and applications in detecting silver ions and iron ions. Background Art

[0002] With the acceleration of the industrialization and urbanization processes, heavy metal pollution has become a hot issue of concern in environmental science today. Among them, silver ions, as one of the most important bioactive cations, exhibit excellent antibacterial activity in a low concentration range and are widely used in fields such as water purification, skin care products, daily necessities, and medicine. However, high-concentration silver ions are toxic to the human body, and excessive intake of silver ions can cause damage to the digestive system, liver, and kidneys of the body, leading to metabolic disorders and endangering human health. In addition, iron ions are necessary to maintain the normal physiological functions or tissue structures of the human body, are important components in hemoglobin, myosin, and cytochromes, and are one of the essential trace elements for the human body. However, excessive intake of iron ions can cause symptoms of physical discomfort such as bacterial infection, pigmentation, and iron poisoning. Therefore, it is very important to accurately and rapidly identify the contents of silver ions and iron ions in various foods, water, and biological samples.

[0003] The patent with the publication number CN 219121805 U discloses an iron ion detection device for domestic sewage. This device samples domestic sewage at the sewer by setting a small water pump, a suction hose, a corrugated expansion pipe, and a transmission pipe, and then quickly mixes the sewage with sodium hydroxide solution by setting a motor, a rotating shaft, and mixing blades, so as to quickly detect whether there are iron ions in the sewage. However, this detection method requires the use of large instruments, which are costly and cannot meet the development needs.

[0004] The patent with the publication number CN 110698500 A discloses a preparation method and application of a gold alkynyl complex for silver ion sensing and recognition. In this invention, silver ions affect the center of the gold alkynyl complex and the electron cloud density and energy level of the ligand to change its excited state properties, thereby causing a change in the emission properties. Therefore, the mixed solution of the complex and silver ions can emit bright blue visible light when excited under ultraviolet light, thus realizing the rapid detection of silver ions. However, this detection method has problems such as high prices of synthetic raw materials, many reaction steps, and complex post-reaction treatment, which are not conducive to practical applications.

[0005] Therefore, researching and developing an efficient method for detecting iron ions and silver ions has become an important topic that needs to be urgently studied at present. Summary of the Invention

[0006] In view of the defects of the existing detection of iron ions and silver ions, such as high cost and cumbersome process, the purpose of the present invention is to provide a hetero[4]arene macrocyclic compound, its preparation method and its application in the detection of silver ions and iron ions. The present invention can efficiently detect iron ions and silver ions, with obvious effects, low cost and simple process.

[0007] The purpose of the present invention is achieved in the following way:

[0008] The present invention provides a hetero[4]arene macrocyclic compound capable of detecting silver ions and iron ions, and the structure of the hetero[4]arene macrocyclic compound is shown as follows:

[0009]

[0010] On the other hand, the present invention provides a preparation method of the above-mentioned hetero[4]arene macrocyclic compound, which includes the following steps:

[0011] (1) Add 1 equivalent of 2,6-diethoxynaphthalene, 1 equivalent of 1,3-dimethoxybenzene, 1 - 3 equivalents of paraformaldehyde and the catalyst trifluoroacetic acid to reflux in an organic solvent, monitor the reaction by thin-layer chromatography. After the reaction is completed, neutralize trifluoroacetic acid, and the obtained product is purified by column chromatography to obtain a hetero[4]arene;

[0012] (2) Add the hetero[4]arene obtained in step (1) to an organic solvent, heat to completely dissolve, place at 0 - 5 °C for 10 - 24 h, filter and collect the crystals to obtain a hetero[4]arene macrocyclic compound;

[0013] (3) Activate the hetero[4]arene macrocyclic compound obtained in step (2) at 100 - 140 °C for 5 - 20 h.

[0014] Based on the above technical solution, further, the organic solvent in step (1) is chloroform; saturated sodium carbonate aqueous solution is used to neutralize trifluoroacetic acid.

[0015] Based on the above technical solution, further, the organic solvents in step (2) include acetone, n-hexane, cyclohexane, and tetrahydrofuran.

[0016] Based on the above technical solution, further, the activation temperature in step (3) is 120 °C and the activation time is 9 h.

[0017] The present invention also provides the application of the above-mentioned hetero[4]arene macrocyclic compound in the detection of iron ions and silver ions.

[0018] Based on the above technical solution, further, the specific process of the application is as follows: Prepare a solution to be detected, add the hetero[4]aromatic macrocyclic compound, and after mixing evenly, when an obvious color change occurs in the solution, detect it with a UV-visible spectrophotometer. If an absorption peak appears at 590 - 610 nm, it indicates that the solution to be detected contains silver ions; if an absorption peak appears at 690 - 710 nm, it indicates that the solution to be detected contains iron ions.

[0019] Based on the above technical solution, further, the specific process of the application is as follows: Prepare a solution to be detected, add the hetero[4]aromatic macrocyclic compound, and after mixing evenly, place it under light with a wavelength of 360 - 370 nm for irradiation. If the fluorescence quenches, it indicates that the solution to be detected contains silver ions and / or iron ions.

[0020] Based on the above technical solution, further, the final concentration of the hetero[4]aromatic macrocyclic compound is 0.1 - 1 mM.

[0021] Based on the above technical solution, further, the solvents for preparing the solution to be detected include dichloromethane and chloroform.

[0022] The beneficial effects of the present invention compared with the prior art are as follows:

[0023] The present invention uses a hetero[4]aromatic macrocyclic compound as a detection material for iron ions and silver ions. The detection process is simple to operate, requires low equipment, and reduces the cost of detecting iron ions and silver ions; and during the detection process of iron ions and silver ions, it is possible to directly judge whether iron ions and silver ions exist with the naked eye, which is beneficial to the rapid detection of iron ions and silver ions. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention, the drawings related to the embodiments will be briefly introduced below.

[0025] Figure 1 It is the nuclear magnetic resonance hydrogen spectrum of the hetero[4]aromatic macrocyclic compound;

[0026] Figure 2 It is the UV-visible absorption spectra of the hetero[4]aromatic macrocyclic compound after complexing with silver ions (a) and iron ions (b) respectively;

[0027] Figure 3 It is the fluorescence titration spectra of the hetero[4]aromatic macrocyclic compound after complexing with silver ions (a) and iron ions (b) respectively (the concentrations of iron ions and silver ions increase from top to bottom in sequence);

[0028] Figure 4 It is the non-linear fitting graph of the fluorescence titration spectra of the hetero[4]aromatic macrocyclic compound after complexing with iron ions (a) and silver ions (b) respectively.

[0029] Figure 5 Fluorescence spectra of the complexation of hetero[4]aromatic macrocyclic compounds with iron ions, silver ions, sodium ions, magnesium ions, aluminum ions, copper ions, and zinc ions (a), and (b) Fluorescence columnar comparison chart of the detection of iron ions and silver ions by hetero[4]aromatic macrocyclic compounds under the interference of other ions. Detailed implementation manners

[0030] The present invention will be described in detail below in conjunction with embodiments, but the implementation manners of the present invention are not limited thereto. Obviously, the embodiments described below are only partial embodiments of the present invention. For those skilled in the art, without creative efforts, obtaining other similar embodiments will fall within the protection scope of the present invention.

[0031] In the following embodiments, the test methods are conventional methods unless otherwise specified; the reagents and materials can be obtained from commercial channels unless otherwise specified.

[0032] Example 1

[0033] Preparation of hetero[4]aromatic macrocyclic compounds:

[0034] (1) A mixture of 1 equivalent of 2,6 - diethoxynaphthalene, 1 equivalent of 1,3 - dimethoxybenzene, 2 equivalents of paraformaldehyde, and the catalyst trifluoroacetic acid was refluxed in chloroform, and the reaction process was monitored by thin - layer chromatography. After the reaction was completed, saturated sodium carbonate aqueous solution was added to neutralize trifluoroacetic acid, and the product was purified by column chromatography to obtain a white solid, namely hetero[4]arene, with a yield of 50%;

[0035] (2) Weigh 2 g of hetero[4]arene and place it in 20 mL of acetone, heat it to boiling, and then continue to add acetone until the hetero[4]arene is completely dissolved. The solution is stored at 0 °C overnight, and the precipitated crystals are collected by filtration. The obtained crystals are activated at 120 °C for 9 h to obtain a white powder, denoted as H.

[0036] The nuclear magnetic resonance hydrogen spectrum of the hetero[4]aromatic macrocyclic compound prepared in this example is as Figure 1 shown, and the characterization data are as follows:

[0037] 11H NMR (500 MHz, CDCl3, 293 K) (ppm): 7.27 (d, J = 10 Hz, 4H), 6.82 (d, J = 10 Hz, 4H), 6.61 (s, 2H), 5.81 (s, 2H), 4.57 (s, 2H), 4.55 (s, 2H), 3.99 (s, 12H), 3.93 - 3.89 (m, 4H), 3.86 - 3.82 (m, 4H), 3.74 (s, 2H), 3.71 (s, 2H), 1.23 (t, J = 15 Hz, 12H).

[0038] Example 2

[0039] Color changes and UV - Vis absorption spectra of hetero[4]arene macrocyclic compounds after complexation with iron ions and silver ions respectively

[0040] Take three 20 - mL culture flasks, and add 3.4 mg of silver hexafluoroantimonate (AgSbF6), 1.6 mg of iron(III) chloride (FeCl3), and 8.6 mg of hetero[4]arene macrocyclic compound (H) respectively. Add 20 mL of dichloromethane to the above three 20 - mL culture flasks to prepare 0.5 mM AgSbF6, FeCl3, and H solutions. The solutions are clear and transparent, bright yellow, and clear and transparent respectively. Then weigh two portions of 8.6 mg of H and add them to the above AgSbF6 and FeCl3 solutions respectively, denoted as H@AgSbF6 and H@FeCl3. At this time, both the AgSbF6 and FeCl3 solutions turn blue - black. The iron ions and silver ions in the solutions are successfully detected by observing the color changes. In addition, in view of the color changes of the solutions, use a UV - Vis spectrophotometer to detect 0.5 mM H, H@AgSbF6, and H@FeCl3 solutions respectively. After H is complexed with AgSbF6, a new absorption peak appears at about 600 nm in the UV - Vis spectrum; similarly, after H is complexed with FeCl3, a new absorption peak appears at about 700 nm in the UV - Vis spectrum (as Figure 2 shown). The UV - Vis spectral results indicate that the hetero[4]arene macrocyclic compound has successfully complexed with iron ions and silver ions respectively.

[0041] Example 3

[0042] Fluorescence changes and fluorescence titration of hetero[4]arene macrocyclic compounds after complexation with iron ions and silver ions respectively

[0043] 0.5 mM solutions of H, H@AgSbF6, and H@FeCl3 were irradiated under a 365 nm fluorescent lamp. The H solution exhibited fluorescence (with a naphthalene unit), while the H@AgSbF6 and H@FeCl3 solutions showed fluorescence quenching. Therefore, the change in solution fluorescence can be used to detect the presence of iron ions and silver ions. In addition, fluorescence titrations were performed on the complexation behavior of the hetero[4]arene macrocycle with iron ions and silver ions respectively. Take a 20 mL culture flask, add 8.6 mg of H to it and add 20 mL of dichloromethane to prepare a 0.5 mM H solution. Meanwhile, weigh 12 portions of 6.8 mg of AgSbF6 and add the 12 portions of 6.8 mg of AgSbF6 to the 0.5 mM H solution in sequence, so that the AgSbF6 in the 0.5 mM H solution is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 mM in turn, and measure their fluorescence spectra respectively. Similarly, prepare another 20 mL of 0.5 mM H solution, weigh 9 portions of 3.2 mg of FeCl3, and add the 9 portions of 3.2 mg of FeCl3 to the 0.5 mM H solution in sequence, so that the FeCl3 in the 0.5 mM H solution is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 mM in turn, and measure their fluorescence spectra respectively. It was found from the fluorescence spectra that H showed a fluorescence emission peak at about 390 nm, and the fluorescence intensity gradually decreased after adding AgSbF6 and FeCl3 in sequence (as Figure 3 shown). In addition, the results of the fluorescence titrations were non-linearly fitted, and the complexation constants of H with AgSbF6 and FeCl3 were (4 ± 0.6)×10 4 M -1 and (9 ± 0.6)×10 3 M -1 (as Figure 4 shown).

[0044] Example 4

[0045] Fluorescence changes of the hetero[4]arene macrocycle with other metal ions

[0046] Take five 20-mL culture flasks respectively, add 8.6 mg of H to each of them and add 20 mL of dichloromethane to prepare a 0.5 mM H solution. Then add 0.6 mg of NaCl, 1.0 mg of MgCl2, 1.3 mg of AlCl3, 1.3 mg of CuCl2, and 1.4 mg of ZnCl2 to each of them in turn, so that the metal ions are all 0.5 mM in the H solution. Place the above five groups of solutions under a 365-nm fluorescent lamp for irradiation, and it is found that the solutions added with the above metals still show fluorescence, which is the same as that of the pure 0.5 mM H solution. In addition, add 3.4 mg of AgSbF6 to each of the above five groups of solutions respectively, and then place them under a 365-nm fluorescent lamp for irradiation, and it is found that the fluorescence quenching phenomenon occurs in the solutions. Similarly, prepare the above five groups of solutions containing other metal ions, then add 1.6 mg of FeCl3 to each of the five groups of solutions respectively, and then place them under a 365-nm fluorescent lamp for irradiation, and it is found that the fluorescence quenching phenomenon occurs in the solutions. The above results show that hetero[4]arenes cannot be used to detect other metal ions, and other metal ions do not interfere with the detection of silver ions and iron ions by hetero[4]arenes (as Figure 5 shown).

[0047] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. Application of hetero[4]aromatic macrocyclic compounds in detecting iron ions, characterized in that: The structure of the hetero[4]arene macrocyclic compound is shown below:

2. The use according to claim 1, characterized in that: The method for preparing the hetero[4]arene macrocyclic compound comprises the following steps: (1) adding 1 equivalent of 2,6-diethoxynaphthalene, 1 equivalent of 1,3-dimethoxybenzene, 1-3 equivalents of polyformaldehyde and a catalyst of trifluoroacetic acid to an organic solvent and refluxing, monitoring the reaction by thin layer chromatography, neutralizing the trifluoroacetic acid after the reaction, and purifying the obtained product by column chromatography to obtain hetero[4]arene; (2) adding the hetero[4]arene obtained in step (1) to an organic solvent, heating until completely dissolved, placing at 0 to 5° C. for 10 to 24 hours, filtering and collecting crystals to obtain a hetero[4]arene macrocyclic compound; (3) activating the hetero[4]arene macrocyclic compound obtained in step (2) at 100-140° C. for 5-20 h.

3. The use according to claim 2, characterized in that: The organic solvent described in step (1) is chloroform; trifluoroacetic acid is neutralized with saturated sodium carbonate aqueous solution.

4. The use according to claim 2, characterized in that: The organic solvent described in step (2) includes acetone, n-hexane, cyclohexane, and tetrahydrofuran.

5. The use according to claim 2, characterized in that: The activation temperature in step (3) is 120° C. and the activation time is 9 h.

6. The use according to claim 1, characterized in that: The specific process of the application is: prepare the solution to be detected, add the hetero[4]aromatic macrocyclic compound, mix evenly, and then expose it to light with a wavelength of 360 to 370 nm. If the fluorescence is quenched, it means that the solution to be detected contains iron ions.

7. The use according to claim 6, characterized in that: The final concentration of the hetero[4]aromatic macrocyclic compound is 0.1-1 mM.

8. The use according to claim 6, characterized in that: The solvents used to prepare the test solution include dichloromethane and chloroform.

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