A ketone amine-based fluorescent probe covalent organic framework and a synthesis method and application thereof

Abstract

The application provides a ketone amine fluorescent probe covalent organic framework and a synthesis method and application thereof, and is prepared by using dimethylacetamide and mesitylene as mixed solvents, 2,4,6-trihydroxybenzene-1,3,5-triformaldehyde and 2,6-diaminoanthraquinone in a catalytic reaction under the catalysis of an acid catalyst, washing, sooting, drying and obtaining the ketone amine fluorescent covalent organic framework. In a tetrahydrofuran solution of the fluorescent probe covalent organic framework, a series of amine compound solutions are added, and only the addition of p-phenylenediamine can completely quench the fluorescence of the probe covalent organic framework, and the minimum detection limit can reach 3.5*10 ‑7 mol L ‑1 The ketone amine fluorescent probe covalent organic framework synthesized by the application has strong stability, reversibility and fluorescence.

Description

Technical Field

[0001] This invention relates to the fields of organic chemical synthesis, functional materials and chemical analysis, and particularly to the synthesis and application of a covalent organic framework with ketamine fluorescent probes. Background Technology

[0002] p-Phenylenediamine is a widely used intermediate in the preparation of azo dyes and polymers. Despite the wide range of applications, amines have unclear properties and, when present in excess, are highly toxic, posing a threat to human health and the environment. Therefore, developing real-time, selective, rapid, and efficient amine detection systems and new materials is not only an urgent need in the field of public safety but also crucial for environmental protection. To date, many fluorescent materials have been reported for the detection of amine compounds, but most of these materials distinguish between aliphatic and aromatic amines over a broad spectrum, and few achieve selective recognition of amine compounds. In recent years, covalent organic frameworks (COFs) have emerged as promising fluorescent materials, playing a significant role in realizing fluorescence sensing of amine compounds.

[0003] Covalent organic frameworks (COFs) possess diverse crystal structures and, in principle, multiple identical binding sites within a scalable framework, allowing for the efficient transmission and amplification of analyte-as-guest sensing signals. Furthermore, the two-dimensional porous crystal structure provides a large specific surface area, enabling ample interaction between the analyte and the recognition site, thereby improving selectivity and sensitivity. For these reasons, synthesizing covalent organic frameworks with ketamine fluorescent probes for the recognition of p-phenylenediamine has significant research and application value. Summary of the Invention

[0004] The purpose of this invention is to provide a covalent organic framework with a ketamine fluorescent probe for the recognition of p-phenylenediamine.

[0005] The covalent organic framework of the ketamine fluorescent probe exhibits fluorescence for amine compounds: A 1×10⁻⁶ solution of the fluorescent probe covalent organic framework was prepared in tetrahydrofuran solvent at room temperature. -4 mol L -1 Fluorescence detection was performed by adding a tetrahydrofuran solution containing amine compounds.

[0006] Another objective of the invention is to provide a covalent organic framework for a ketamine-based fluorescent probe, with the following structural formula: Another object of the present invention is to provide a method for synthesizing the above-mentioned covalent organic framework of ketamine fluorescent probe, specifically comprising the following steps: S1. Using dimethylacetamide and mesitylene as a mixed solvent, and 2,4,6-trihydroxybenzene-1,3,5-tricarboxaldehyde and 2,6-diaminoanthraquinone as raw materials, the reaction is carried out at 100-120 °C under an acidic catalyst. S2. After the reaction is complete, the product is washed, extracted, and vacuum dried to obtain a covalent organic framework with ketamine groups.

[0007] Preferably, in S1, the molar ratio of 2,4,6-trihydroxybenzene-1,3,5-tricarboxaldehyde and 2,6-diaminoanthraquinone is 3 to 4:5.

[0008] Preferably, in S1, the reaction is carried out at 120 °C for 3 days.

[0009] Preferably, in S1, the catalyst is 6 mol L. -1 AcOH.

[0010] Preferably, in S2, vacuum drying is carried out at 0.02–0.06 MPa and 100 °C.

[0011] Preferably, in S3, the concentration of the tetrahydrofuran solution of the amine compound is 0.01 mol / L. -1 .

[0012] Preferably, in S2, the washing process involves centrifuging and washing three times each with distilled water and tetrahydrofuran.

[0013] Preferably, in S2, the extraction is performed by re-extraction with distilled water and tetrahydrofuran for 48 hours.

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows: The ketamine-based fluorescent probe covalent organic framework synthesized in this invention exhibits strong stability, reversibility, and fluorescence. Adding the fluorescent probe covalent organic framework to p-phenylenediamine completely quenches the fluorescence of the probe covalent organic framework. The fluorescent probe covalent organic framework of this invention enables precise detection of p-phenylenediamine, with a detection limit as low as 3.5 × 10⁻⁶. - 7 mol L -1 . Attached Figure Description

[0015] Figure 1 This is the powder X-ray diffraction pattern of the fluorescent covalent organic framework synthesized in this invention; Figure 2 The solid-state NMR spectrum of TD-COF; Figure 3 The infrared spectrum of TD-COF; in, Figure 3 a corresponds to TD-COF, Figure 3b corresponds to 2,6-diaminoanthraquinone. Figure 3 c corresponds to 2,4,6-trihydroxybenzene-1,3,5-tricarboxaldehyde; Figure 4 The fluorescence spectrum of TD-COF is quenched by p-phenylenediamine. Detailed Implementation

[0016] The synthesis and application of the fluorescent probe of the present invention will be described in detail below through specific embodiments. The preferred embodiments described herein are only for illustration and explanation of the present invention and are not intended to limit the present invention.

[0017] Example 1 A method for synthesizing the above-mentioned ketamine-based fluorescent probe covalent organic framework involves mixing 2,4,6-trihydroxybenzene-1,3,5-tricarboxaldehyde and 2,6-diaminoanthraquinone in an organic solvent at a molar ratio of 3:4 to 3:5, and then reacting the mixture under the catalysis of acetic acid to obtain the ketamine-based fluorescent covalent organic framework named TD-COF.

[0018] Synthesis of TD-COF, a covalent organic framework for ketamine fluorescent probes: Example 2 A method for synthesizing the above-mentioned covalent organic framework of a ketamine fluorescent probe involves weighing 20.0 mg of 2,4,6-trihydroxybenzene-1,3,5-tricarboxaldehyde and 34.0 mg of 2,6-diaminoanthraquinone and adding them to a 10 mL sealing tube. Then, 0.90 mL of dimethylacetamide and 0.30 mL of mesitylene solvent are added, and the mixture is sonicated for 5 minutes. Finally, 0.05 mL of acetic acid (6 mol / L) is added as a catalyst. -1 The sealed tube was thawed and degassed three times using a refrigeration pump, then sealed and placed in an oven at 120 °C for three days. After the reaction, a solid was produced at the bottom of the sealed tube. The solid was transferred to a centrifuge tube and washed three times each with distilled water and tetrahydrofuran. The solid was then extracted with distilled water and tetrahydrofuran for three days. The solid was dried at 100 °C to obtain a red solid powder, TD-COF. Figure 1 The image shown is the powder X-ray diffraction pattern of the covalent organic framework synthesized in Example 1 of this invention. Figure 4 The fluorescence spectrum of TD-COF is quenched by p-phenylenediamine. Figure 2 The solid-state NMR spectrum of TD-COF indicates that the framework material was successfully prepared. Figure 3 The infrared spectrum of TD-COF shows that the two monomers successfully underwent a condensation reaction, indicating that the framework material was successfully prepared.

[0019] Example 3 Fluorescence effect of fluorescent probe covalent organic framework on amine compounds: A solution of fluorescent probe covalent organic framework (1×10⁻⁶) was prepared in tetrahydrofuran solvent at room temperature. -4 mol L -1 ), respectively added tetrahydrofuran solutions (0.01 mol / L) of p-phenylenediamine, 2,4,6-trimethylaniline, o-phenylenediamine, m-phenylenediamine, aniline, 4-bromoaniline, p-methoxyaniline, 4-tert-butylaniline, 4-n-butylaniline, benzylamine, cyclohexylamine, 1,2-cyclohexanediamine, n-propylamine, n-butylamine, diethylamine, triethylamine, and tert-butylamine. -1 The fluorescence changes in each solution were observed. The results showed that only the addition of p-phenylenediamine could completely quench the fluorescence of the probe, while the addition of other amine compounds could not elicit a fluorescence response in the probe material.

[0020] Titration experiments showed that the probe's limit of detection for p-phenylenediamine could reach 3.5 × 10⁻⁶. -7 mol L -1 .

[0021] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. 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. The application of a covalent organic framework with a ketamine fluorescent probe in the detection of p-phenylenediamine, characterized in that: The structural formula of the ketamine covalent organic framework is as follows: ； A solution of 1×10⁻⁶ was prepared in tetrahydrofuran solvent at room temperature. -4 mol L -1 Fluorescence detection was performed on a tetrahydrofuran solution containing amine compounds, and p-phenylenediamine showed a fluorescent effect.

2. The application as described in claim 1, characterized in that: The ketamine covalent organic framework is synthesized according to the following steps: S1. Using dimethylacetamide and mesitylene as a mixed solvent, and 2,4,6-trihydroxybenzene-1,3,5-tricarboxaldehyde and 2,6-diaminoanthraquinone as raw materials, the reaction is carried out at 100-120 °C under an acidic catalyst. S2. After the reaction is complete, the material is washed, extracted, and vacuum dried to obtain a covalent organic framework material with ketamine groups.

3. The application as described in claim 2, characterized in that: In S1, the molar ratio of 2,4,6-trihydroxybenzene-1,3,5-tricarboxaldehyde to 2,6-diaminoanthraquinone is 3 to 4:

5.

4. The application as described in claim 2, characterized in that: In S1, the reaction was carried out at 120 °C for 3 days.

5. The application as described in claim 2, characterized in that: In S1, the catalyst is 6 mol L. -1 AcOH.

6. The application as described in claim 2, characterized in that: In S2, vacuum drying is carried out at 0.02–0.06 MPa and 100 °C.

7. The application as described in claim 1, characterized in that: The concentration of the tetrahydrofuran solution of the amine compound is 0.01 mol / L. -1 .

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