Preparation method of pyrenyl fluorescent covalent triazine framework material and fluorescence detection application of pyrenyl fluorescent covalent triazine framework material
By preparing AIE covalent triazine skeleton material with pyrene functional groups, the complex and expensive problems of existing antibiotic detection methods are solved, and the rapid, selective and efficient fluorescence detection of a variety of antibiotics is achieved, which is suitable for environmental pollution treatment.
Patent Information
- Application Number
- CN202411403976.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-09
- Publication Date
- 2024-12-27
AI Technical Summary
Most existing antibiotic detection methods are complex, expensive and difficult to quickly and easily detect antibiotics in water, especially nitrofurans, which makes it difficult to effectively deal with environmental pollution and health threats.
Develop a novel covalent triazine framework material with AIE fluorescence effect of pyrene functional groups by 1,4-terephthalidamimidine, 1,3,6,8-tetrade(4-aldehydephenylphenyl)pyrene, Cesium carbonate reacts with dimethyl sulfoxide under specific conditions to prepare CTF-PTTB material for efficient fluorescence detection of antibiotics.
It realizes rapid, selective and efficient fluorescence detection of a variety of antibiotics, has high chemical stability and a simple preparation process, is suitable for the treatment of environmental pollution problems, and has better detection performance than traditional methods.
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Abstract
Description
Technical Field
[0001] The invention relates to a preparation method of a novel covalent triazine skeleton material with AIE fluorescence effect of a pyrene functional group, which is aimed at specific detection of antibiotics and belongs to the field of new materials. Background Art
[0002] For decades, the abuse of antibiotics has led to water pollution and has become a public problem that seriously threatens human health. In particular, nitrofurans (NFs) are widely used in food processing, aquaculture, and medical fields. Due to the accumulation of NFs in surface water, groundwater, and even drinking water, they can cause human health problems such as allergies, hearing loss, nausea, and pancreatitis. In addition, due to their high toxicity and difficulty in degradation, the detection of NFs is crucial to the environment and human health. Although there are many methods for detecting antibiotics, such as high-performance liquid chromatography (HPLC), gas chromatography-mass spectrometry (GC-MS), surface-enhanced Raman spectroscopy (SERS), and liquid chromatography-tandem mass spectrometry (LC-MS / MS), there is still a need to develop fast, simple, efficient, and inexpensive detection technologies. Fluorescence sensing technology has the advantages of fast sensing speed, high selectivity, and easy use. It is a promising technology. The development of advanced sensing materials for specific analytes is the core goal of fluorescence sensing technology. Therefore, the development of fluorescent materials for detecting antibiotics is of great significance for the treatment of environmental pollution.
[0003] Covelant triazine frameworks (CTFs) are a new type of porous organic polymer with triazine ring units. They not only have stable and controllable porosity, but also are easy to design in terms of structure and performance. In addition, CTFs have extremely high water stability and chemical stability, and can maintain stability even under acidic or alkaline conditions. These advantages make fluorescent CTFs an excellent fluorescent probe for the detection of antibiotics in water. At the same time, pyrene is a special type of fluorescent small molecule probe, namely aggregation-induced emission groups (AIEgens). Although it cannot emit fluorescence in a dissolved state, it can exhibit luminescence characteristics in a solid due to the limitation of the intramolecular rotation process in an aggregated state. Therefore, we constructed the pyrene group in the framework of CTFs and prepared CTF materials with AIE effect, which have reliable fluorescence properties and are used for the selective detection of NFs. Summary of the invention
[0004] For the fluorescence detection of antibiotics, the present invention provides a preparation method of a new CTF with pyrene groups, and the fluorescent CTF material can be used for selective fluorescence detection of NFs, and the target antibiotics are nitrofurazone (NZF), nitrofurantoin (NFT), furazolidone (FZD), celnidazole (SCZ), ronidazole (RNZ), metronidazole (MDZ), dimetronidazole (DTZ), ornidazole (ODZ), sulfadiazine (SDZ), sulfadiazine (SMZ), chloramphenicol (CAP), and thiamphenicol (THI). The present invention can not only provide a new pyrene-based CTF fluorescent probe, but also efficiently detect antibiotics.
[0005] The technical solution of the present invention is as follows: A novel pyrene-based CTF fluorescent material is prepared according to the following method: Put 1,4-tert-butylenediamine, 1,3,6,8-tetrakis(4-formylphenyl)pyrene (PTTB), cesium carbonate, water and dimethyl sulfoxide (DMSO) into a 100 ml round-bottom flask and stir for a while until homogeneous. Then heat the round-bottom flask in an oil bath for a while. After the reaction is completed, cool and filter, wash with DMF and ethanol several times, and vacuum dry at 120°C to obtain yellow CTF-PTTB. The volume of the DMSO is 10-100 ml; The volume ratio of water to DMSO is 1:1-50; The molar ratio of 1,3,6,8-tetrakis(4-formylphenyl)pyrene to 1,4-terephthalamidine is 1:1-6; The concentration of 1,3,6,8-tetrakis(4-formylphenyl)pyrene dissolved in DMSO is 0.001-0.01 mol / L; The concentration of cesium carbonate in DMSO is 10-40 mg / ml; The reaction temperature is 80°C-180°C; The reaction time is 1-5 days.
[0006] Compared with the prior art, the present invention has the following substantial advantages: (1) Short preparation cycle, suitable for large-scale preparation; (2) The synthesis method is simple and the synthesis conditions are mild; (3) CTF-PTTB has high chemical stability and excellent fluorescence properties, and can be detected under various conditions; (4) CTF-PTTB has a selective and efficient detection performance for NFs and is suitable for dealing with related environmental pollution problems. BRIEF DESCRIPTION OF THE DRAWINGS
[0007] Figure 1is a BET schematic diagram of CTF-PTTB in Example 1 of the present invention; Figure 2 is a schematic diagram of TGA of CTF-PTTB in Example 1 of the present invention; Figure 3 It is the quenching efficiency of CTF-PTTB on different antibiotics in Example 1 of the present invention. DETAILED DESCRIPTION
[0008] The present invention is described in detail below in conjunction with specific embodiments, but the present invention is not limited to the following embodiments. Without departing from the content and scope of the present invention, changes in implementation should be included in the technical scope of the present invention.
[0009] Example 1: Preparation of CTF-PTTB 1,4-Benzenediamidine (1 mmol, 235.2 mg), 1,3,6,8-tetrakis(4-formylphenyl)pyrene (0.25 mmol, 154.7 mg), cesium carbonate (2.2 mmol, 716.8 mg), water (2 ml) and dimethyl sulfoxide (50 ml) were placed in a 100 ml round-bottom flask and stirred for a while until homogeneous. The round-bottom flask was then reacted at 120 °C in an oil bath for 3 days. After the reaction was completed, the mixture was cooled and filtered, washed with DMF 3 times, washed with ethanol 3 times, and dried in vacuo at 120 °C to obtain yellow CTF-PTTB.
[0010] Example 2: Preparation of CTF-PTTB 1,4-Benzenediamidine (1 mmol, 235.2 mg), 1,3,6,8-tetrakis(4-formylphenyl)pyrene (0.25 mmol, 154.7 mg), cesium carbonate (2.2 mmol, 716.8 mg), water (2 ml) and dimethyl sulfoxide (100 ml) were placed in a 100 ml round-bottom flask and stirred for a while until homogeneous. The round-bottom flask was then reacted at 120 °C in an oil bath for 3 days. After the reaction was completed, it was cooled and filtered, washed with DMF 3 times, washed with ethanol 3 times, and dried in vacuo at 120 °C to obtain yellow CTF-PTTB.
[0011] Example 3: Preparation of CTF-PTTB 1,4-Benzenediamidine (1 mmol, 235.2 mg), 1,3,6,8-tetrakis(4-formylphenyl)pyrene (0.25 mmol, 154.7 mg), cesium carbonate (2.2 mmol, 716.8 mg), water (5 ml) and dimethyl sulfoxide (50 ml) were placed in a 100 ml round-bottom flask and stirred for a while until homogeneous. The round-bottom flask was then reacted at 120°C in an oil bath for 3 days. After the reaction was completed, the mixture was cooled and filtered, washed with DMF 3 times, washed with ethanol 3 times, and dried in vacuo at 120°C to obtain yellow CTF-PTTB.
[0012] Example 4: Preparation of CTF-PTTB 1,4-Benzenediamidine (0.5 mmol, 117.6 mg), 1,3,6,8-tetrakis(4-formylphenyl)pyrene (0.25 mmol, 154.7 mg), cesium carbonate (2.2 mmol, 716.8 mg), water (2 ml) and dimethyl sulfoxide (50 ml) were placed in a 100 ml round-bottom flask and stirred for a while until homogeneous. The round-bottom flask was then reacted at 120°C in an oil bath for 3 days. After the reaction was completed, the mixture was cooled and filtered, washed with DMF 3 times, washed with ethanol 3 times, and dried in vacuo at 120°C to obtain yellow CTF-PTTB.
[0013] Example 5: Preparation of CTF-PTTB 1,4-Benzenediamidine (2 mmol, 470.4 mg), 1,3,6,8-tetrakis(4-formylphenyl)pyrene (0.5 mmol, 309.4 mg), cesium carbonate (2.2 mmol, 716.8 mg), water (2 ml) and dimethyl sulfoxide (50 ml) were placed in a 100 ml round-bottom flask and stirred for a while until homogeneous. The round-bottom flask was then reacted at 120°C in an oil bath for 3 days. After the reaction was completed, the mixture was cooled and filtered, washed with DMF 3 times, washed with ethanol 3 times, and dried in vacuo at 120°C to obtain yellow CTF-PTTB.
[0014] Example 6: Preparation of CTF-PTTB 1,4-Benzenediamidine (1 mmol, 235.2 mg), 1,3,6,8-tetrakis(4-formylphenyl)pyrene (0.25 mmol, 154.7 mg), cesium carbonate (4.4 mmol, 1433.6 mg), water (2 ml) and dimethyl sulfoxide (50 ml) were placed in a 100 ml round-bottom flask and stirred for a while until homogeneous. The round-bottom flask was then reacted at 120 °C in an oil bath for 3 days. After the reaction was completed, it was cooled and filtered, washed with DMF 3 times, washed with ethanol 3 times, and dried in vacuo at 120 °C to obtain yellow CTF-PTTB.
[0015] Example 7: Preparation of CTF-PTTB 1,4-Benzenediamidine (1 mmol, 235.2 mg), 1,3,6,8-tetrakis(4-formylphenyl)pyrene (0.25 mmol, 154.7 mg), cesium carbonate (2.2 mmol, 716.8 mg), water (2 ml) and dimethyl sulfoxide (50 ml) were placed in a 100 ml round-bottom flask and stirred for a while until homogeneous. The round-bottom flask was then reacted at 180°C in an oil bath for 3 days. After the reaction was completed, it was cooled and filtered, washed with DMF 3 times, washed with ethanol 3 times, and dried in vacuo at 120°C to obtain yellow CTF-PTTB.
[0016] Example 8: Preparation of CTF-PTTB 1,4-Benzenediamidine (1 mmol, 235.2 mg), 1,3,6,8-tetrakis(4-formylphenyl)pyrene (0.25 mmol, 154.7 mg), cesium carbonate (2.2 mmol, 716.8 mg), water (2 ml) and dimethyl sulfoxide (50 ml) were placed in a 100 ml round-bottom flask and stirred for a while until homogeneous. The round-bottom flask was then reacted at 120°C in an oil bath for 5 days. After the reaction was completed, the mixture was cooled and filtered, washed with DMF 3 times, washed with ethanol 3 times, and dried in vacuo at 120°C to obtain yellow CTF-PTTB.
[0017] Example 9: Detection of antibiotics by CTF-PTTB The CTF-PTTB sample (10 mg) was weighed, ground and added to a cuvette containing water (20 ml). After sufficient sonication, the CTF-PTTB suspension (2 ml) was taken out for fluorescence detection experiments. Antibiotic (NZF, NFT, FZD, SCZ, SDZ, RNZ, MDZ, DTZ, ODZ, SDZ, SMZ, CAP, THI) solutions (1 mM, 20 μL each time) were added to the suspension one by one. The fluorescence intensity of the CTF-PTTB suspension (2 ml) was measured once every time the antibiotic solution was added, for a total of 10 times. During the entire fluorescence detection experiment, the mixed solution was stirred at a constant rate to maintain its uniformity. Through the fluorescence detection experiment, it can be concluded that the quenching efficiency of the CTF-PTTB on NFs (NZF, NFT and FZD) reached 95%, 94% and 92%, respectively, which far exceeds the detection performance of other fluorescent materials on NFs. This patent not only develops a new type of pyrene-based covalent triazine skeleton sensor, but also has efficient fluorescence detection performance for NFs.
[0018] Of course, the above specific embodiments are only detailed explanations of the corresponding technical solutions of the present invention, and are not limited to the above implementation methods. For those skilled in the art, various changes or modifications can still be made on the basis of the above embodiments. All implementation methods are not listed here, and all changes or modifications derived from the above principles or mechanisms are within the protection scope of the present invention.
Claims
1. A novel pyrene-based CTF fluorescent material, characterized in that: The novel pyrene-based CTF fluorescent material is prepared according to the following method: Put 1,4-tert-butylenediamine, 1,3,6,8-tetrakis(4-formylphenyl)pyrene, cesium carbonate, water and dimethyl sulfoxide (DMSO) into a 100 ml round-bottom flask and stir for a while until it becomes homogeneous. Then heat the round-bottom flask in an oil bath for a while. After the reaction is completed, cool and filter, wash with DMF and ethanol several times, and vacuum dry at 120°C to obtain yellow CTF-PTTB.
2. The novel pyrene-based CTF fluorescent material according to claim 1, characterized in that: The volume of the DMSO is 10-100 ml.
3. The novel pyrene-based CTF fluorescent material according to claim 1, characterized in that: The volume ratio of water to DMSO is 1:1-50.
4. The novel pyrene-based CTF fluorescent material according to claim 1, characterized in that: The molar ratio of 1,3,6,8-tetrakis(4-formylphenyl)pyrene to 1,4-terephthalamidine is 1:1-6.
5. The novel pyrene-based CTF fluorescent material according to claim 1, characterized in that: The concentration of 1,3,6,8-tetrakis(4-formylphenyl)pyrene dissolved in DMSO is 0.001-0.01 mol / L.
6. The novel pyrene-based CTF fluorescent material according to claim 1, characterized in that: The concentration of cesium carbonate in DMSO is 10-40 mg / ml.
7. The novel pyrene-based CTF fluorescent material according to claim 1, characterized in that: The reaction temperature is 80°C-180°C.
8. The novel pyrene-based CTF fluorescent material according to claim 1, characterized in that: The reaction time is 1-5 days.
9. The use of the novel pyrene-based CTF fluorescent material according to claim 1 in the detection of various antibiotic solutions, characterized in that: The quenching efficiency of the CTF-PTTB on NFs (NZF, NFT and FZD) reached 95%, 94% and 92%, respectively.