Preparation method and application of BODIPY-based open-type fluorescent probe for detecting hypochlorous acid

Abstract

The invention discloses a BODIPY-based open-type fluorescent probe for detecting hypochlorous acid as well as a preparation method and application of the BODIPY-based open-type fluorescent probe. The fluorescent probe is a 2-(1, 3-dimethyl pyrimidine-2, 4, 6-triketone-5-methylene)-10-(furan-2-yl)-1, 3, 7, 9-tetramethyl-5H-dipyrroledifluoro borane complex (BODIPY-SBA for short), and is characterized in that the fluorescent probe has a structural formula shown in the description. The preparation method comprises the following steps: taking a 2-formyl-10-(furan-2-yl)-1, 3, 7, 9-tetramethyl dipyrrole difluoro borane complex as a raw material, and carrying out condensation reaction on the 2-formyl-10-(furan-2-yl)-1, 3, 7, 9-tetramethyl dipyrrole difluoro borane complex and 1, 3-dimethyl barbituric acid to obtain the probe compound BODIPY-SBA. After the probe solution encounters hypochlorous acid, the color of the solution is changed from light pink to yellow green under sunlight; under the irradiation of ultraviolet light with the wavelength of 365 nm, the fluorescence color of the solution is changed from colorless to green. The probe BODIPY-SBA can rapidly and sensitively detect the content of hypochlorous acid in a solution, the detection range is 0-150 [mu] M, the detection limit is 35 nM, the response time is short, and the probe BODIPY-SBA has the characteristics of high sensitivity, high response speed, good selectivity, wide detection range and the like. As an excellent-performance probe for detecting hypochlorous acid, the probe has a good application prospect in the fields of food safety and biological imaging.

Description

Technical Field

[0001] The invention belongs to the technical field of fine organic synthesis and relates to a preparation method and application of a BODIPY-based open-type fluorescent probe for detecting hypochlorous acid. Background Art

[0002] Hypochlorous acid is one of the most important reactive oxygen species in life. It is catalyzed by myeloperoxidase. - With H 2 O 2 Oxidation reaction produces. It plays an irreplaceable role in water treatment, food preservation, medical sterilization, etc. In water treatment, hypochlorous acid participates in oxidation disinfection, organic matter removal and microbial killing; in food preservation, hypochlorous acid is used to sterilize food processing equipment; in medical sterilization, hypochlorous acid plays a vital role in killing viruses and pathogens. In addition, hypochlorous acid is also involved in a large number of physiological activities in the human body, such as maintaining redox balance and transmitting inflammatory signals. However, due to the high reactivity of hypochlorous acid, a large amount of organic by-products are easily produced during the sterilization process, which are highly carcinogenic. Therefore, monitoring the level of hypochlorous acid in food and organisms plays a vital role.

[0003] At present, there are many methods for detecting hypochlorous acid, such as electrochemical analysis, liquid chromatography-mass spectrometry, mass spectrometry, chemical titration, etc. However, these technologies have their own disadvantages, including complex operation, high cost, low sensitivity, time-consuming, etc., which limit their application in rapid on-site detection or real-time monitoring. Fluorescent probes have been widely used in environmental science, life science and other fields due to their advantages such as fast detection speed, high sensitivity, good selectivity, simple operation and good biocompatibility. In particular, for the detection of hypochlorous acid, there are many reports on fluorescent probes with different mechanisms and fluorophores. Since the recognition mechanism mainly uses thioether or borate as a recognition group to react specifically with hypochlorous acid, the choice of fluorophore will have a significant impact on the optical properties and actual performance. Hypochlorous acid probes are usually composed of many common fluorophores, such as coumarin, fluoroborylpyrrole and rhodamine. Furfural was used as a raw material to synthesize a new BODIPY-based fluorescent probe BODIPY-SBA for the detection of hypochlorous acid. The probe BODIPY-SBA has dual detection functions of colorimetric and open-type, and has the advantages of wide detection range, high sensitivity and good selectivity, which is of great significance for the detection of hypochlorous acid. Summary of the invention

[0004] In view of the deficiencies in the prior art, the technical problem to be solved by the present invention is to provide a BODIPY-based open-type fluorescent probe for detecting hypochlorous acid, which can meet the use requirements of detecting hypochlorous acid. Another technical problem to be solved by the present invention is to provide a preparation method of a BODIPY-based open-type fluorescent probe for detecting hypochlorous acid. Another technical problem to be solved by the present invention is to provide an application of a BODIPY-based open-type fluorescent probe for detecting hypochlorous acid in detecting hypochlorous acid.

[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is:

[0006] A BODIPY-based open-type fluorescent probe for detecting hypochlorous acid, characterized in that its molecular formula is C 24 H 2 3BF 2 N 4 O 4 , whose structural formula is:

[0007]

[0008] The method for preparing a BODIPY-based open-type fluorescent probe for detecting hypochlorous acid specifically comprises the following steps:

[0009] 1) Dissolve 2-methylene-1,3-dimethylpyrimidinetrione-10-(furan-2-yl)-1,3,7,9-tetramethyl-5H-dipyrroledifluoroborane (0.5 mmol, 186 mg) and 1,3-dimethylbarbituric acid (0.5 mmol, 78 mg) in 10-20 mL of ethanol and add to a round-bottom flask. Reflux for 3-6 h under nitrogen protection until the reaction of the raw materials is complete (monitored by TLC).

[0010] 2) After the reaction is completed, the reaction solution is cooled to room temperature, and the precipitated solid is filtered through a sand core funnel. The obtained solid crude product BODIPY-SBA is washed with distilled water and ethanol, and dried to obtain a dark purple solid product BODIPY-SBA.

[0011] The fluorescent probe BODIPY-SBA solution reacts with hypochlorous acid, and the color of the solution changes from light pink to yellow-green under sunlight; under ultraviolet light with a wavelength of 365nm, the fluorescent color of the solution changes from colorless to green.

[0012] The fluorescent probe BODIPY-SBA is used to detect the hypochlorous acid content in the solution. The detection range is 0-150 μM, the detection limit is 35 nM, and the response time is very fast. It has the characteristics of high sensitivity, fast response speed, good selectivity, and wide detection range.

[0013] Beneficial effects: Compared with the prior art, the present invention uses 2-methylene-1,3-dimethylpyrimidinetrione-10-(furan-2-yl)-1,3,7,9-tetramethyl-5H-dipyrroledifluoroborane as a raw material, and undergoes a condensation reaction with 1,3-dimethylbarbituric acid. The prepared BODIPY-SBA can specifically identify hypochlorous acid and can quickly and sensitively detect the content of hypochlorous acid in a solution. The detection range is 0 to 150 μM, the detection limit is 35 nM, the response time is very fast, and the invention has the characteristics of high sensitivity, fast response speed, good selectivity, wide detection range, etc., and has good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 This is the fluorescence spectrum of the fluorescent probe BODIPY-SBA after reacting with hypochlorous acid of different concentrations;

[0015] Figure 2 This is the fluorescence spectrum of the fluorescent probe BODIPY-SBA interacting with different metal ions, anions and amino acids. DETAILED DESCRIPTION

[0016] The present invention will be further described below in conjunction with specific embodiments.

[0017] Example 1

[0018] Preparation of fluorescent probe BODIPY-SBA, the reaction formula is as follows:

[0019]

[0020] (1) 2-Methylene-1,3-dimethylpyrimidinetrione-10-(furan-2-yl)-1,3,7,9-tetramethyl-5H-dipyrroledifluoroborane (0.5 mmol, 186 mg) and 1,3-dimethylbarbituric acid (0.5 mmol, 78 mg) were dissolved in 10-20 mL of ethanol and added to a round-bottom flask. The mixture was refluxed for 3 h under nitrogen protection until the reaction of the raw materials was complete (monitored by TLC).

[0021] (2) After the reaction is completed, the reaction solution is cooled to room temperature, and the precipitated solid is filtered through a sand core funnel. The obtained solid crude product BODIPY-SBA is washed with distilled water and ethanol, and dried to obtain a dark purple solid product BODIPY-SBA. 1 HNMR (600 MHz, CDCl 3 )δ: 8.39 (s, 1H), 7.65 (s, 1H), 6.59-6.48 (m, 2H), 6.15 (s, 1H), 3.39 (s, 3H), 3.33 (s, 3H), 2.60 (s, 3H), 2.51 (s, 3H), 1.64 (s, 3H), 1.52 (s, 3H).13 C NMR (150 MHz, CDCl 3 )δ: 162.61, 162.38, 160.05, 157.44, 151.76, 150.03, 146.77, 144.69, 143.52, 142.55, 135.73, 132.36, 129. 51, 126.59, 124.02, 117.06, 112.52, 112.04, 77.58, 77.37, 77.16, 30.02, 29.12, 15.53, 15.09, 13.68, 13.02.

[0022] Example 2

[0023] BODIPY-SBA was prepared into 1×10 -5 M PBS buffer solution, dissolve sodium hypochlorite in PBS buffer to make concentrations of 0, 1.0×10 -5 , 2.0×10 -5 , 3.0×10 -5 , 4.0×10 -5 , 5.0×10 -5 , 6.0×10 -5 , 7.0×10 -5 , 8.0×10 -5 , 9.0×10 -5 , 1.0×10 -4 , 1.1×10 -4 , 1.2×10 -4 , 1.3×10 -4 , 1.4×10 -4 , 1.5×10 -4 The fluorescence emission spectra of BODIPY-SBA in the presence of different concentrations of HClO were measured on a fluorescence spectrophotometer using fluorescence spectrometry. Figure 1 As shown. The results show that as the concentration of hypochlorous acid in the solution gradually increases, the fluorescence emission intensity of the probe at 505nm gradually increases. This shows that the compound can be used as a fluorescent probe for sensitive detection of hypochlorous acid content in solution, and the detection limit of hypochlorous acid is as low as 35nM.

[0024] Example 3

[0025] BODIPY-SBA was prepared into 1×10 -5 M PBS buffer solution, and different metal ions, anions and amino acids were dissolved in PBS buffer to a concentration of 1.0×10 -4The fluorescence emission spectra of BODIPY-SBA in the presence of different metal ions, anions and amino acids were measured on a fluorescence spectrophotometer using fluorescence spectrometry. Figure 2 The results show that the addition of hypochlorous acid significantly increases the fluorescence emission intensity of the probe, while the fluorescence spectrum of the probe does not change significantly when metal ions, anions, and amino acids are added for comparison. This shows that the compound can be used as a fluorescent probe for the specific detection of hypochlorous acid.

Claims

1. A BODIPY-based open-type fluorescent probe for detecting hypochlorous acid, characterized in that: Its molecular formula is C 24 H 23 BF2N4O4, its structural formula is:

2. The method for preparing a BODIPY-based open-type fluorescent probe for detecting hypochlorous acid according to claim 1, characterized in that: 2-(1,3-dimethylpyrimidine-2,4,6-trione-5-methylene)-10-(furan-2-yl)-1,3,7,9-tetramethyl-5H-dipyrroledifluoroborane complex was prepared by condensation reaction of 2-formyl-10-(furan-2-yl)-1,3,7,9-tetramethyl-dipyrroledifluoroborane complex with 1,3-dimethylbarbituric acid, referred to as BODIPY-SBA.

3. The method for preparing a BODIPY-based open-type fluorescent probe for detecting hypochlorous acid according to claim 2, characterized in that: The specific steps include: 1) 2-Formyl-10-(furan-2-yl)-1,3,7,9-tetramethyldipyrroledifluoroborane (0.5 mmol, 186 mg) and 1,3-dimethylbarbituric acid (0.5 mmol, 78 mg) were dissolved in 10-20 mL of ethanol and added to a round-bottom flask. The mixture was refluxed for 3-6 h under nitrogen protection until the reaction of the raw materials was complete (monitored by TLC). 2) After the reaction is completed, the reaction solution is cooled to room temperature, and the precipitated solid is filtered through a sand core funnel. The obtained solid crude product BODIPY-SBA is washed with distilled water and ethanol, and dried to obtain a dark purple solid product BODIPY-SBA.

4. Use of a BODIPY-based open-type fluorescent probe for detecting hypochlorous acid according to claim 1 in detecting hypochlorous acid.

5. The use according to claim 4, characterized in that: The fluorescent probe BODIPY-SBA solution reacts with hypochlorous acid, and the color of the solution changes from light pink to yellow-green under sunlight; under ultraviolet light with a wavelength of 365nm, the fluorescent color of the solution changes from colorless to green.

6. The use according to claim 4, characterized in that: The fluorescent probe BODIPY-SBA can detect the hypochlorous acid content in the solution with a detection range of 0-150μM and a detection limit of 35nM. It has a fast response time and has the characteristics of high sensitivity, fast response speed, good selectivity and wide detection range.

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