CN115894421A - Hg is discerned to high selectivity 2+ Flavonol thiocarbonate fluorescent probe and preparation method and application thereof - Google Patents

Abstract

The invention discloses a flavonol thiocarbonate fluorescent probe for highly selective recognition of Hg ²⁺ , a preparation method and application thereof. The present invention uses N, N-diisopropylethylamine as a catalyst, and 4-(3-hydroxy-7-phenylchromanone-2-yl) methyl benzoate reacts with phenyl thiochloroformate to prepare 4- Methyl (3-(phenoxythioformyloxy)-7-phenylchromanone-2-yl)benzoate. Under 365nm ultraviolet light irradiation, add Hg ²⁺ After that, the fluorescent color of the solution changed from colorless to orange yellow, which can selectively recognize Hg ²⁺ , and can be used as a fluorescent probe for detecting Hg ²⁺ , with a detection limit of 3.25×10 ^‑8 mol/L for Hg ²⁺ , The response time is 2 minutes, which has a good application prospect.

Description

A flavonol thiocarbonate fluorescent probe for highly selective recognition of Hg2+ and its preparation method and application

technical field

The invention belongs to the technical field of fluorescence detection, and in particular relates to a flavonol thiocarbonate fluorescent probe for highly selective recognition of Hg ²⁺ , a preparation method and application thereof.

Background technique

Mercury is a bioaccumulative heavy metal element. With the widespread use of mercury in industry, metallurgy, pharmaceuticals, electronic equipment and other fields, mercury and its compounds will inevitably enter the soil and water environment. Under the action of microorganisms, it is converted into fat-soluble poisons and enters the human body, spreading throughout the organs of the human body, causing damage to the human immune system, nervous system, and endocrine system. For example, when methylmercury enters the human body, it will cause brain damage, damage people's cognition and audio-visual ability, and cause irreversible nerve damage. The Minamata disease that once shocked the world was caused by the neurotoxin methylmercury. Therefore, exploring the detection method of mercury ions will be beneficial to environmental and health risk assessment.

There are many methods for detecting mercury ions, such as atomic absorption spectrometry, atomic emission spectrometry, inductively coupled plasma mass spectrometry, colorimetry, chemiluminescence and so on. Although these methods can accurately detect mercury ions, they are difficult to popularize due to time-consuming, high instrument cost, and complicated sample preparation, and cannot meet the needs of real-time and routine detection. In recent years, detection methods based on fluorescent probes have become more and more popular. Fluorescent probes have the advantages of good selectivity, high sensitivity, convenient preparation, and real-time monitoring, and have broad application prospects for the detection and research of mercury ions.

Contents of the invention

Aiming at the deficiencies in the prior art, the technical problem to be solved by the present invention is to provide a flavonol thiocarbonate-based fluorescent probe for highly selective recognition of Hg ²⁺ to meet the detection and use requirements of Hg ²⁺ . Another technical problem to be solved by the present invention is to provide a preparation method of a flavonol thiocarbonate fluorescent probe for highly selective recognition of Hg ²⁺ . Another technical problem to be solved by the present invention is to provide an application of a flavonol thiocarbonate fluorescent probe for highly selective recognition of Hg ²⁺ .

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

A flavonol thiocarbonate fluorescent probe for highly selective recognition of Hg ²⁺ , the structural formula is:

The preparation method of the flavonol thiocarbonate fluorescent probe with high selectivity to recognize Hg ²⁺ uses N,N-diisopropylethylamine as a catalyst, and 4-(3-hydroxyl-7-phenyl color Proketone-2-yl) methyl benzoate reacts with phenyl thiochloroformate to give 4-(3-(phenoxythioformyloxy)-7-phenylchromanone-2-yl) Methyl benzoate.

The preparation method of the flavonol thiocarbonate fluorescent probe for highly selective recognition of Hg ²⁺ is specifically: adding 0.5 to 2 mmol 4-(3-hydroxyl-7-phenylchromone-2-yl) Dissolve methyl benzoate in 30-60mL of anhydrous dichloromethane, add 0.2-0.8mL N,N-diisopropylethylamine under nitrogen protection, stir for 10min, then add 0.75-3mmol sulfur under ice bath Phenyl chloroformate, reacted for 5h; after the reaction, the solvent was evaporated, and the residue was purified by column chromatography (ethyl acetate/petroleum ether: 1:10, v/v) to obtain a white solid 4-(3- Methyl (phenoxythioformyloxy)-7-phenylchromanon-2-yl)benzoate.

The application of the flavonol thiocarbonate fluorescent probe with high selectivity for recognizing Hg ²⁺ in detecting Hg ²⁺ .

Said application, under 365nm ultraviolet light irradiation, in 4-(3-(phenoxythioformyloxy)-7-phenylchromone-2-yl) methyl benzoate solution, add Hg ² After ⁺ , the fluorescent color of the solution changed from colorless to orange-yellow.

In said application, the detection limit for Hg ²⁺ reaches 3.25×10 ^-8 mol/L, and the response time is 2 minutes.

Described application, the solvent of 4-(3-(phenoxythioformyloxy)-7-phenylchromone-2-yl) methyl benzoate solution is that the volume ratio is 1: 1 acetonitrile water mixing solvent.

Beneficial effect: compared with prior art, main advantage of the present invention is as follows:

1) The fluorescent probe TO-PCBM for detecting mercury ions provided by the present invention, under 365nm ultraviolet light irradiation, after adding Hg ²⁺ in the acetonitrile-water solution of TO-PCBM, the fluorescent color of the solution changes from colorless to orange Yellow, the detection limit for Hg ²⁺ reaches 3.25×10 ^-8 mol/L, and the response time is 2 minutes. It has the characteristics of good specificity and high sensitivity, and has a good application prospect as a fluorescent probe for detecting Hg ²⁺ .

2) The fluorescent probe TO-PCBM for detecting mercury ions provided by the present invention has a simple synthesis method, good selectivity and can quickly identify mercury ions.

Description of drawings

Figure 1 is the ¹³ C NMR spectrum of TO-PCBM;

Figure 2 is the HRMS spectrum of TO-PCBM;

Figure 3 is the fluorescence spectrum before and after adding Hg ²⁺ to the acetonitrile-water solution of TO-PCBM;

Fig. 4 is the fluorescence spectrogram of the acetonitrile-water solution of TO-PCBM after adding different metal ions;

Fig. 5 is the fluorescence spectrogram of the acetonitrile-water solution of TO-PCBM after adding different concentrations of Hg ²⁺ ;

Fig. 6 is a measurement result diagram of the change of fluorescence intensity with time after the acetonitrile-water solution of TO-PCBM is added with Hg ²⁺ .

Detailed ways

In order to make the above objects, features and advantages of the present invention more obvious and comprehensible, the specific implementation manners of the present invention will be described in detail below in conjunction with the embodiments of the specification.

Example 1

A kind of synthetic method of the flavonol thiocarbonate fluorescent probe of highly selective recognition Hg ²⁺ , reaction formula is as follows:

Concrete preparation steps are:

Dissolve 0.5mmol MHPCB in 30mL anhydrous dichloromethane, add 0.2mL N,N-diisopropylethylamine under nitrogen protection, stir for 10min, then add 0.75mmol phenyl thiochloroformate under ice bath , Reaction 5h. After the reaction, the solvent was evaporated, and the residue was purified by column chromatography (ethyl acetate:petroleum ether=1:10, v/v) to obtain TO-PCBM as a white solid with a yield of 78% and a purity of 95.4%. ¹ H NMR (600MHz, DMSO-d6) δ: 8.25(d, J=8.5Hz, 2H), 8.23-8.17(m, 2H), 8.15(d, J=8.5Hz, 2H), 7.93(d, J =8.3Hz, 1H), 7.89(d, J=7.0Hz, 2H), 7.59-7.47(m, 5H), 7.39(t, J=7.4Hz, 1H), 7.26(d, J=7.5Hz, 2H ), 3.93(s, 3H). ¹³ C NMR (151MHz, DMSO-d ₆ ) δ: 192.55, 170.52, 165.94, 156.04, 155.68, 153.63, 147.16, 138.19, 136.32, 133.59, 132.77, 130.58, 1329.272, 129.64, 128.98, 127.83, 127.74, 126.36, 125.15, 122.37, 121.84, 116.83, 53.03. HRMS (m/z): [M+H] ⁺ calcd for C ₃₀ H ₂₀ O ₆ S+H ⁺ 509.0981, found 509.1058 . The ¹³ C NMR spectrum and HRMS spectrum of TO-PCBM are shown in Figures 1 and 2 .

Example 2

Dissolve TO-PCBM in acetonitrile-water (acetonitrile: water = 1: 1, v/v) mixed solvent, configure it into a solution with a concentration of 5 μM, and measure the fluorescence emission spectrum of the solution with a fluorescence spectrophotometer. The results are shown in the figure 3. The results showed that in TO-PCBM acetonitrile-water (acetonitrile:water=1:1, v/v) solution, when no Hg ²⁺ was added, the solution had no fluorescence, and when Hg ²⁺ was added, the fluorescence intensity of the solution was sharp Enhanced, the maximum emission wavelength is 565nm (the excitation wavelength is 365nm, the excitation slit broadband is 5.0nm, and the emission slit broadband is 4.5nm).

Dissolve TO-PCBM in acetonitrile-water (acetonitrile: water = 1:1, v/v) mixed solvent to prepare a solution with a concentration of 5 μM, one of which is used as a blank sample, and Hg ²⁺ is added to the remaining several, K ⁺ , Na ⁺ , Ag ⁺ , Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , Zn ²⁺ , Mn ²⁺ , pb ²⁺ , Co ²⁺ , Cd ²⁺ , Cu ²⁺ , Ni ²⁺ , Al ³⁺ , Cr ³⁺ , Fe ³⁺ and La ³⁺ , the fluorescence emission spectrum of the solution was measured with a fluorescence spectrophotometer, and the results are shown in Figure 4. It can be seen from Figure 5 that after adding Hg ²⁺ , the maximum emission wavelength of the solution is 565nm, and the fluorescence intensity of the solution is significantly enhanced. When other analytes were added, the fluorescence intensity of the solution hardly changed. This shows that TO-PCBM has good selectivity to Hg ²⁺ .

Dissolve TO-PCBM in acetonitrile-water (acetonitrile: water = 1:1, v/v) mixed solvent, configure it into a solution with a concentration of 5 μM, and measure the concentration of Hg with different concentrations by using a fluorescence spectrometry titration method with a fluorescence spectrophotometer. The fluorescence emission spectrum of the solution after ²⁺ ions is shown in Figure 5. The results showed that the fluorescence intensity of TO-PCBM at 565nm gradually increased with the gradual increase of Hg ²⁺ concentration, indicating that TO-PCBM could be used to detect the concentration of Hg ²⁺ in solution, and the detection limit of Hg ²⁺ reached 3.25 ×10 ^{- 8} mol/L.

Dissolve TO-PCBM in acetonitrile-water (acetonitrile: water = 1:1, v/v) mixed solvent, and configure it into a solution with a concentration of 5 μM. Use a fluorescence spectrophotometer to measure the concentration within 300 seconds after adding 50 μM Hg ²⁺ ions The fluorescence intensity of the solution changes, and the results are shown in Figure 6. After adding Hg ²⁺ ions, the fluorescence intensity of the solution increased significantly within 40s, reached the maximum response value after 2min, and remained basically unchanged in the following 5min. This shows that the probe TO-PCBM can quickly detect Hg ²⁺ ions in solution and maintain the response signal for a certain period of time. Therefore, the probe TO-PCBM can be used as a fluorescent probe for rapid detection of Hg ²⁺ .

Claims (7)

1. a kind of highly selective recognition Hg The flavonol thiocarbonate fluorescent probe of ^Hg is characterized in that, structural formula is:

2. the preparation method of the flavonol thiocarbonate fluorescent probe of high selectivity recognition Hg described in claim ¹ , it is characterized in that: take N, N-diisopropylethylamine as catalyzer, 4- (3-Hydroxy-7-phenylchromone-2-yl)methyl benzoate reacts with phenyl thiochloroformate to obtain 4-(3-(phenoxythioformyloxy)-7- Methyl phenylchromon-2-yl)benzoate. 3. the preparation method of the flavonol thiocarbonate fluorescent probe of highly selective recognition Hg according to claim ² , is characterized in that, specifically: 0.5～2mmol 4-(3-hydroxyl-7 -Phenylchromone-2-yl)methyl benzoate was dissolved in 30~60mL of anhydrous dichloromethane, under nitrogen protection, 0.2~0.8mL N,N-diisopropylethylamine was added, and after stirring for 10min , under ice bath, add 0.75～3mmol phenyl thiochloroformate, react for 5h; ) to give methyl 4-(3-(phenoxythioformyloxy)-7-phenylchromanon-2-yl)benzoate as a white solid. 4. the application of the flavonol thiocarbonate fluorescent probe for highly selective recognition of Hg according to claim 1 in ^the detection of Hg ²⁺ . 5. application according to claim 4, is characterized in that, under 365nm ultraviolet light irradiation, in 4-(3-(phenoxythioformyloxy group)-7-phenyl chromone-2-yl ) After adding Hg ²⁺ to the methyl benzoate solution, the fluorescent color of the solution changed from colorless to orange-yellow. 6. The application according to claim 4 or 5, characterized in that the detection limit for Hg ²⁺ reaches 3.25×10 ^-8 mol/L, and the response time is 2 minutes. 7. according to the application described in claim 4 or 5, it is characterized in that, 4-(3-(phenoxythioformyloxy)-7-phenylchromone-2-yl) methyl benzoate solution The solvent is a mixed solvent of acetonitrile and water with a volume ratio of 1:1.

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