CN115894421A

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

Info

Publication number: CN115894421A
Application number: CN202211402278.2A
Authority: CN
Inventors: 杨益琴; 武杨梅; 孟志远; 寇佳丽; 王晓媛; 钱铖; 周国诚; 王忠龙; 王石发
Original assignee: Nanjing Forestry University
Current assignee: Nanjing Forestry University
Priority date: 2022-11-09
Filing date: 2022-11-09
Publication date: 2023-04-04
Anticipated expiration: 2042-11-09
Also published as: CN115894421B

Abstract

The invention discloses a method for identifying Hg with high selectivity ²⁺ The flavonol thiocarbonate fluorescent probe and the preparation method and the application thereof. The invention takes N, N-diisopropylethylamine as a catalyst, and 4- (3-hydroxy-7-phenyl chromone-2-yl) methyl benzoate reacts with phenylchlorothiocarbamate to prepare the 4- (3- (phenoxyl thiocarboxygroup) -7-phenyl chromone-2-yl) methyl benzoate. Hg is added to the acetonitrile-water solution of 4- (3- (phenoxythiocarboxyloxy) -7-phenylchromone-2-yl) methyl benzoate under 365nm ultraviolet irradiation ²⁺ Then, the fluorescence color of the solution changes from colorless to orange yellow, and Hg can be selectively identified ²⁺ Can be used for detecting Hg ²⁺ Fluorescent probe of (2), for Hg ²⁺ Detection of (2)The limit reaches 3.25 multiplied by 10 ^‑8 mol/L, response time of 2min, and good application prospect.

Description

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

Technical Field

The invention belongs to the technical field of fluorescence detection, and particularly relates to high-selectivity Hg identification ²⁺ The flavonol thiocarbonate fluorescent probe and the preparation method and the application thereof.

Background

Mercury is a heavy metal element with bioaccumulation properties. With the wide use of mercury in the fields of industry, metallurgy, pharmacy, electronic equipment and the like, mercury and compounds thereof inevitably enter soil and water body environments. Under the action of microbes, the fat-soluble poison is converted into fat-soluble poison which enters the human body and spreads all over the organs of the human body, so that the immune system, the nervous system and the endocrine system of the human body are damaged. For example, methylmercury can cause brain damage after entering the human body, damage the cognitive and audiovisual abilities of the human body, and cause irreversible nerve damage. The water in the world once terrified is preferentially the neurotoxin methylmercury. Therefore, exploring a detection method for mercury ions would be beneficial for 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 the like. Although the methods can accurately detect mercury ions, the methods are difficult to popularize due to long time consumption, high instrument cost, complex sample preparation and the like, and cannot meet the requirements of real-time and conventional detection. In recent years, detection methods based on fluorescent probes have become increasingly popular. The fluorescent probe has the advantages of good selectivity, high sensitivity, convenient preparation, real-time monitoring and the like, and has wide application prospect for detection research of mercury ions.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a method for identifying Hg with high selectivity ²⁺ The flavonol thiocarbonate fluorescent probe meets Hg ²⁺ Detects the usage requirements. Another technical problem to be solved by the invention is to provide a method for identifying Hg with high selectivity ²⁺ The preparation method of the flavonol thiocarbonate fluorescent probe. Another technical problem to be solved by the present invention is to provide a method for identifying Hg with high selectivity ²⁺ The application of the flavonol thiocarbonate fluorescent probe.

In order to solve the technical problems, the invention adopts the technical scheme that:

hg is discerned to high selectivity ²⁺ The structural formula of the flavonol thiocarbonate fluorescent probe is as follows:

the high selectivity of Hg identification ²⁺ The preparation method of the flavonol thiocarbonate fluorescent probe takes N, N-diisopropylethylamine as a catalyst, and 4- (3-hydroxy-7-phenylchromone-2-yl) methyl benzoate reacts with phenylthiocarbamate to prepare 4- (3- (phenoxythio formyloxy) -7-phenylchromone-2-yl) methyl benzoate.

The high selectivity of Hg identification ²⁺ The preparation method of the flavonol thiocarbonate fluorescent probe specifically comprises the following steps: dissolving 0.5-2mmol of 4- (3-hydroxy-7-phenylchromone-2-yl) methyl benzoate in 30-60 mL of anhydrous dichloromethane, adding 0.2-0.8mLN and N-diisopropylethylamine under the protection of nitrogen, stirring for 10min, adding 0.75-3 mmol of phenyl thiocarbamate under ice bath, and reacting for 5h; after the reaction, the solvent was distilled off, and the residue was purified by column chromatography (ethyl acetate/petroleum ether 1: 10, v/v) to give methyl 4- (3- (phenoxythiocarboxyloxy) -7-phenylchromone-2-yl) benzoate as a white solid.

The high selectivity of Hg identification ²⁺ Application of flavonol thiocarbonate fluorescent probe in Hg detection ²⁺ The use of (1).

The application comprises adding Hg into a 4- (3- (phenoxythiocarbonyloxy) -7-phenylchromone-2-yl) methyl benzoate solution under 365nm ultraviolet irradiation ²⁺ After that, the fluorescence color of the solution changed from colorless to orange-yellow.

The use of, in Hg ²⁺ Up to 3.25 × 10 ^-8 mol/L and response time of 2min.

The application is that the solvent of the methyl 4- (3- (phenoxythiocarboxyloxy) -7-phenylchromone-2-yl) benzoate solution is acetonitrile water mixed solvent with the volume ratio of 1: 1.

Has the advantages that: compared with the prior art, the invention has the following main advantages:

1) The fluorescent probe TO-PCBM for detecting mercury ions provided by the invention is characterized in that Hg is added into an acetonitrile-water solution of the TO-PCBM under the irradiation of 365nm ultraviolet light ²⁺ Then, the fluorescence color of the solution changes from colorless to orange yellow against Hg ²⁺ Up to 3.25 × 10 ^-8 mol/L, response time of 2min, good specificity and high sensitivity, and can be used for detecting Hg ²⁺ The fluorescent probe has good application prospect.

2) The fluorescent probe TO-PCBM for detecting mercury ions provided by the invention is simple in synthesis method, good in selectivity and capable of rapidly identifying mercury ions.

Drawings

FIG. 1 is of TO-PCBM ¹³ A C NMR spectrum;

FIG. 2 is a HRMS map of TO-PCBM;

FIG. 3 shows the addition of Hg TO an acetonitrile-water solution of TO-PCBM ²⁺ Front and back fluorescence spectra;

FIG. 4 is a graph showing fluorescence spectra of an acetonitrile-water solution of TO-PCBM after addition of different metal ions;

FIG. 5 shows the addition of different concentrations of Hg TO an acetonitrile-water solution of TO-PCBM ²⁺ The subsequent fluorescence spectrogram;

FIG. 6 shows the addition of acetonitrile-water solution of TO-PCBMHg ²⁺ And (3) a graph showing the measurement results of the change of the fluorescence intensity with time.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.

Example 1

Hg is discerned to high selectivity ²⁺ The synthesis method of the flavonol thiocarbonate fluorescent probe has the following reaction formula:

the preparation method comprises the following specific steps:

dissolving 0.5mmol of MHPCB in 30mL of anhydrous dichloromethane, adding 0.2mL of N, N-diisopropylethylamine under the protection of nitrogen, stirring for 10min, adding 0.75mmol of phenyl thiocarbamate under the condition of ice bath, and reacting for 5h. After the reaction was completed, the solvent was distilled off, and the residue was purified by column chromatography (ethyl acetate: petroleum ether = 1: 10, v/v) TO obtain white solid TO-PCBM in 78% yield and 95.4% purity. 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：192.55，170.52，165.94，156.04，155.68，153.63，147.16，138.19，136.32，133.59，132.77，130.58，130.28，129.72，129.64，128.98，127.83，127.74，126.36，125.15，122.37，121.84，116.83，53.03.HRMS(m/z)：[M+H] ⁺ calcd for C ₃₀ H ₂₀ O ₆ S+H ⁺ 509.0981, found 509.1058.TO-PCBM ¹³ The C NMR spectrum and the HRMS spectrum are shown in FIGS. 1 and 2.

Example 2

TO-PCBM was dissolved in a mixed solvent of acetonitrile and water (acetonitrile: water = 1: 1, v/v) TO prepare a solution having a concentration of 5. Mu.MThe fluorescence emission spectrum of the solution was measured using a fluorescence spectrophotometer, and the result is shown in FIG. 3. The results showed that no Hg was added TO the TO-PCBM solution in acetonitrile-water (acetonitrile: water = 1: 1, v/v) ²⁺ When Hg is added, the solution is non-fluorescent ²⁺ Then, the fluorescence intensity of the solution sharply increased, and the maximum emission wavelength was 565nm (excitation wavelength was 365nm, excitation slit broadband was 5.0nm, and emission slit broadband was 4.5 nm).

TO-PCBM was dissolved in a mixed solvent of acetonitrile and water (acetonitrile: water = 1: 1, v/v) TO prepare a solution having a concentration of 5. Mu.M, 1 part of which was used as a blank, and Hg was added TO the remaining parts ²⁺ ，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 by a spectrofluorometer, and the results are shown in FIG. 4. As can be seen from FIG. 5, hg was added during the process ²⁺ Then, the maximum emission wavelength of the solution was 565nm, and the fluorescence intensity of the solution was significantly enhanced. Whereas the fluorescence intensity of the solution hardly changes when other analytes are added. This indicates TO-PCBM vs Hg ²⁺ Has good selectivity.

Dissolving TO-PCBM in acetonitrile-water (acetonitrile: water = 1: 1, v/v) mixed solvent TO obtain 5 μ M solution, and measuring the added Hg with fluorescence spectrophotometer by fluorescence spectrum titration method ²⁺ The fluorescence emission spectra of the post-ion solutions are shown in FIG. 5. The results show that Hg is related to Hg ²⁺ The gradual increase of the concentration and the gradual increase of the fluorescence intensity of the TO-PCBM at 565nm indicate that the TO-PCBM can be used for detecting Hg in the solution ²⁺ Concentration, to Hg ²⁺ Up to 3.25 × 10 ^- ⁸ mol/L。

TO-PCBM was dissolved in a mixed solvent of acetonitrile and water (acetonitrile: water = 1: 1, v/v) TO prepare a solution having a concentration of 5. Mu.M, and 50. Mu.M Hg was added thereto as measured by a fluorescence spectrophotometer ²⁺ The fluorescence intensity of the solution changes within 300s after ionization, and the result is shown in the figureAnd 6. Hg is added ²⁺ After ionization, the fluorescence intensity of the solution increased significantly within 40s, reached essentially the maximum response value after 2min, and remained essentially unchanged during the subsequent 5 min. This indicates that the probe TO-PCBM can rapidly detect Hg in solution ²⁺ Ions and can maintain a response signal for a certain time. Therefore, the probe TO-PCBM can be used for rapidly detecting Hg ²⁺ The fluorescent probe of (1).

Claims

1. Hg is discerned to high selectivity ²⁺ The flavonol thiocarbonate fluorescent probe is characterized in that the structural formula is as follows:

2. the highly selective identification of Hg as claimed in claim 1 ²⁺ The preparation method of the flavonol thiocarbonate fluorescent probe is characterized by comprising the following steps: using N, N-diisopropylethylamine as a catalyst, and reacting 4- (3-hydroxy-7-phenylchromone-2-yl) methyl benzoate with phenyl chlorothiocarbonate to prepare 4- (3- (phenoxyl thiocarboxygroup) -7-phenylchromone-2-yl) methyl benzoate.

3. The highly selective identification of Hg as claimed in claim 2 ²⁺ The preparation method of the flavonol thiocarbonate fluorescent probe is characterized by comprising the following steps: dissolving 0.5-2mmol of 4- (3-hydroxy-7-phenylchromone-2-yl) methyl benzoate in 30-60 mL of anhydrous dichloromethane, adding 0.2-0.8mL of N, N-diisopropylethylamine under the protection of nitrogen, stirring for 10min, adding 0.75-3 mmol of phenyl thiocarbamate under ice bath, and reacting for 5h; after the reaction, the solvent was distilled off, and the residue was purified by column chromatography (ethyl acetate/petroleum ether 1: 10, v/v) to give methyl 4- (3- (phenoxythiocarboxyloxy) -7-phenylchromone-2-yl) benzoate as a white solid.

4. The high selection of claim 1Sex identification of Hg ²⁺ Application of flavonol thiocarbonate fluorescent probe in detecting Hg ²⁺ The use of (1).

5. The use as claimed in claim 4, wherein Hg is added to a solution of methyl 4- (3- (phenoxythiocarboxyloxy) -7-phenylchromone-2-yl) benzoate in 365nm UV light ²⁺ After that, the fluorescence color of the solution changed from colorless to orange-yellow.

6. Use according to claim 4 or 5, characterized in that for Hg ²⁺ Up to 3.25 × 10 ^-8 mol/L and response time of 2min.

7. The use according to claim 4 or 5, wherein the solvent of the methyl 4- (3- (phenoxythiocarboxyloxy) -7-phenylchromon-2-yl) benzoate solution is a mixed solvent of acetonitrile and water in a volume ratio of 1: 1.