Selenium-containing atomic fluorescence probe as well as preparation method and application thereof

Abstract

The invention relates to the technical field of organic synthetic chemistry, in particular to a selenium-containing atomic fluorescence probe as well as a preparation method and application thereof, the structural formula of the probe is as follows: # imgabs0 #, the preparation method comprises the following steps: step 1, stirring and reacting hemicyanine as shown in a formula A and beta-chloroacrolein as shown in a formula B for 15-20 hours under an illumination condition; and 2, continuously stirring and reacting the compound obtained in the step 1 and m-aminobenzene selenol as shown in a formula C under illumination for 20-30 hours to obtain a target compound 1, namely the fluorescent probe disclosed by the invention. The probe is simple in synthetic route, mild in condition, low in production cost and the like. Se = O double bonds are formed under the action of selenium atoms and hypochlorite ions, and fluorescence change is generated. The probe can realize high-selectivity and high-sensitivity detection of hypochlorous acid, and has important application value in the fields of biosensing, environmental monitoring and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthetic chemistry, and particularly to a selenium atom-containing fluorescent probe, a preparation method thereof and an application thereof. Background Art

[0002] A fluorescent probe is an important tool for qualitative or quantitative analysis of specific targets through color or fluorescence changes. It has significant advantages such as high sensitivity, high selectivity, rapid response and simple operation, and thus has been increasingly widely used in fields such as environmental pollution monitoring and life science research.

[0003] Hypochlorous acid (HClO), as a typical reactive oxygen species, has a wide range of applications in daily life, including drinking water disinfection, cold water treatment, household bleaches and antibacterial agents. However, existing fluorescence detection methods for hypochlorite ions, such as chemiluminescence methods and electron spin resonance methods, generally have problems such as insufficient sensitivity, limited practicality and difficulty in synthesis. Therefore, developing technologies based on fluorescent probes to real-time monitor the concentration changes of hypochlorous acid in biological samples has important scientific significance and application value for in-depth research and regulation of pathophysiological processes related to HClO. Summary of the Invention

[0004] The purpose of the present invention is to solve the above problems, and to propose a selenium atom-containing fluorescent probe, a preparation method thereof and an application thereof. The prepared fluorescent probe can achieve highly selective and sensitive detection of hypochlorous acid, and has important application value in fields such as biosensing and environmental monitoring.

[0005] To achieve the above purpose, the present invention provides the following technical solutions:

[0006] A selenium atom-containing fluorescent probe, the structural formula of the fluorescent probe is:

[0007]

[0008] The present invention also provides a preparation method of a selenium atom-containing fluorescent probe, including the following steps:

[0009] Step 1: Stir and react hemicyanine shown in formula A and β-chloroacrolein shown in formula B under light for 15 hours;

[0010] Step 2: Continue to stir and react the compound obtained in Step 1 and m-aminophenylselenol shown in formula C under light for 20 hours to generate Compound 1, which is the fluorescent probe; the reaction structural formula is as follows:

[0011]

[0012] Preferably, the reaction solvent is nitromethane.

[0013] Preferably, in the first step, the reaction temperature is room temperature and the reaction time is 15 to 20 h.

[0014] Preferably, in the second step, the reaction temperature is room temperature and the reaction time is 20 to 30 h.

[0015] Preferably, in the first step and the second step, the irradiation light source for the reaction is a blue LED lamp.

[0016] Preferably, the molar ratio of semi-cyanine, β-chloroacrolein and m-aminophenylselenol is 1:1:1.

[0017] Preferably, after the reaction is completed, the reaction solution is concentrated under reduced pressure, and the concentrate is separated by column chromatography using a mixed solution of petroleum ether and ethyl acetate as the eluent, wherein the volume ratio of dichloromethane to methanol is (1 to 20):1. The eluate is collected and the solvent is rotary evaporated to obtain Compound 1.

[0018] An application of a selenium atom-containing fluorescent probe obtained by the above preparation method in detecting hypochlorite ions, specifically, a hypochlorite detection reagent prepared from the above selenium atom-containing fluorescent probe.

[0019] Compared with the prior art, the beneficial effects of the present invention are:

[0020] 1. The synthesis method of the present invention has simple steps, mild conditions and low production cost.

[0021] 2. The fluorescent probe containing selenium atoms prepared by the present invention forms a Se=O double bond by introducing selenium atoms and using the interaction between selenium atoms and hypochlorite ions, resulting in fluorescence changes and achieving a lower detection limit. Specific Embodiments

[0022] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0023] Example 1

[0024] Semicarbocyanine A (1 mmol), β-chloropropenal (1 mmol) and anhydrous nitromethane (5 mL) were added to a 20 mL reaction tube. After the addition, the reaction was carried out at room temperature under visible light irradiation for 15 hours. Then m-aminophenylselenol C (1 mmol) was added, and the reaction was continued at room temperature under visible light irradiation for 20 hours. Then the solvent was removed by concentration under reduced pressure, and the residue was purified by silica gel column (silica gel specification: 200 mesh - 300 mesh, eluent: dichloromethane / methanol = 20 / 1) to obtain the target compound 1, which is the fluorescent probe described above, with a yield of 28%.

[0025] The NMR spectral data of the obtained compound 1 are as follows: 1 H NMR (400 MHz, CDCl3): δ8.14 (d, J = 13.9 Hz, 1H), 7.68 (d, J = 7.6 Hz, 1H), 7.54 - 7.43 (m, 4H), 7.38 - 7.35 (m, 1H), 6.85 (d, J = 2.1 Hz, 1H), 6.79 (dd, J = 8.6, 2.2 Hz, 1H), 6.40 (d, J = 14.0 Hz, 1H), 4.29 (q, J = 7.2 Hz, 2H), 3.35 (q, J = 7.2 Hz, 4H), 2.70 (t, J = 6.0 Hz, 2H), 2.66 (t, J = 6.3 Hz, 2H), 1.80 (p, J = 5.8 Hz, 2H), 1.72 (s, 6H), 1.32 (t, J = 7.2 Hz, 3H), 1.17 (t, J = 7.2 Hz, 6H). 13 C NMR (100 MHz, CDCl3): δ173.1, 153.9, 150.1, 141.0, 140.7, 140.8, 138.6, 136.5, 132.6, 128.5, 127.6, 125.2, 124.1, 122.1, 118.3, 114.9, 110.7, 105.9, 101.5, 47.8, 45.9, 30.9, 27.0, 25.1, 18.7, 11.8, 10.3。

[0026] In summary, the preparation method of the selenium atom-containing fluorescent probe of the present invention is very mild and simple, and the prepared selenium atom-containing fluorescent probe can achieve highly selective and sensitive detection of hypochlorous acid.

[0027] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A selenium-containing atomic fluorescence probe, characterized in that: The structural formula of the fluorescent probe is:

2. The method for preparing a selenium-containing atomic fluorescence probe according to claim 1, characterized in that: The steps include: Step 1: stirring the hemicyanine represented by formula A and β-chloroacrolein represented by formula B for reaction under light conditions for 15 to 20 hours; Step 2: The compound obtained in step 1 and m-aminophenylselenol shown in formula C are stirred and reacted for 20 to 30 hours under light to generate compound 1, which is the fluorescent probe; the reaction structure is as follows:

3. The method for preparing a selenium-containing atomic fluorescence probe according to claim 2, characterized in that: The reaction solvent was nitromethane.

4. The method for preparing a selenium-containing atomic fluorescence probe according to claim 2, characterized in that: In the step 1, the reaction temperature is room temperature and the reaction time is 15 hours.

5. The method for preparing a selenium-containing atomic fluorescence probe according to claim 2, characterized in that: In the step 2, the reaction temperature is room temperature and the reaction time is 20 hours.

6. The method for preparing a selenium-containing atomic fluorescence probe according to claim 2, characterized in that: In step 1 and step 2, the irradiation light source for the reaction is a blue LED light.

7. The method for preparing a selenium-containing atomic fluorescence probe according to claim 2, characterized in that: The molar ratio of hemicyanine, β-chloroacrolein and m-aminophenylselenol is 1:1:

1.

8. The method for preparing a selenium-containing atomic fluorescence probe according to claim 2, characterized in that: After the reaction, the reaction solution was concentrated under reduced pressure, and the concentrate was separated by column chromatography using a mixture of petroleum ether and ethyl acetate as eluent, wherein the volume ratio of dichloromethane:methanol was (1-20):1, and the eluate was collected and the solvent was rotary evaporated to obtain compound 1.

9. Use of a selenium-containing atomic fluorescent probe obtained by the preparation method according to any one of claims 2 to 8 in detecting hypochlorite ions.

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