CN111777573A

CN111777573A - Fluorescent probe responding to mercury and preparation method thereof

Info

Publication number: CN111777573A
Application number: CN202010711288.9A
Authority: CN
Inventors: 郑开波; 王丽红
Original assignee: China Three Gorges University CTGU
Current assignee: China Three Gorges University CTGU
Priority date: 2020-07-22
Filing date: 2020-07-22
Publication date: 2020-10-16

Abstract

The invention discloses a preparation method and application of a ratio type bivalent mercury fluorescent probe. The structural formula of the bivalent mercury fluorescent probe is as follows:

the invention also provides a preparation method of the probe. The fluorescent probe provided by the invention shows blue fluorescence in a buffer solution, and can perform specific reaction with mercuric chloride to generate a product with yellow fluorescence, so that specific response to mercury is realized. The probe also has good selectivity to the bivalent mercury.

Description

Fluorescent probe responding to mercury and preparation method thereof

Technical Field

The invention discloses a fluorescent probe capable of detecting heavy metal bivalent mercury ions and a synthesis method and application thereof, particularly relates to a fluorescent probe capable of detecting heavy metal bivalent mercury ions through different emission wavelengths, and belongs to the technical field of chemical analysis and detection.

Background

The heavy metal ions play an extremely important role in the fields of natural environment, physics, chemistry and the like, wherein the mercury ions are chemical substances with strong toxicity, have the characteristics of durability, easy mobility, high biological enrichment and the like, become one of the most interesting environmental pollutants in the whole world at present, can cause the central nervous system of a human to be weakened, cause nervous disorder and also form the parts of kidney, liver, digestive system and hematopoietic systemCertain threats. Since mercury is oxidized into mercury ions soon after entering human body, the mercury ions can be combined with enzymes and proteins in the body, so that a plurality of metabolic pathways in cells are affected, and the functions and the growth of the cells are affected, and the mercury ions are just because of the Hg²⁺Has high toxicity, low development and development cost, quick response and easy realization, and can be applied to natural environment and biological system²⁺The detection means is particularly important.

At present, there are various methods for detecting mercury ions including atomic absorption spectrometry, such as differential pulse anodic stripping voltammetry, capillary electrophoresis, and the like. However, these methods have the disadvantages of complicated apparatus, complicated operation, difficult and time-consuming pretreatment, and difficulty in popularization.

Disclosure of Invention

The invention relates to a fluorescent probe capable of detecting heavy metal bivalent mercury, and the molecular formula is C₂₇H₁₆N₂O₂S₃The structural formula is as follows:

the invention relates to a fluorescent probe capable of detecting heavy metal bivalent mercury, which is realized by the following method:

fluorescent probes responsive to mercury

The ratio type fluorescent probe capable of detecting bivalent mercury is realized by the following method:

adding the compound 2, 5-bis (benzo [ d ] thiazole-2-yl) phenol and triethylamine into a reaction bottle, simultaneously adding dry dichloromethane serving as a solvent, and adding the required dosage of phenyl thiocarbonate under the ice bath condition. After stirring for 0.5-1 h, the reaction was monitored by TLC plates until the starting material was reacted completely and the target product was obtained by column chromatography with an eluent ratio of PE: DCM to 2: 3.

The mol ratio of the compound 2, 5-bis (benzo [ d ] thiazole-2-yl) phenol, triethylamine and phenyl thiocarbamate is 1: 1.2-3: 1.2-3.

The mol ratio of the compound 2, 5-bis (benzo [ d ] thiazole-2-yl) phenol, triethylamine and phenyl thiocarbamate is 1: 1.5: 1.5.

the fluorescent molecular probe compound is applied to detecting bivalent mercury.

The invention has the advantages that the synthesis of the probe can be completed only by one step, and the post-treatment process is simple. The probe has good selectivity and high sensitivity. Shows good selectivity to heavy metal bivalent mercury and good anti-interference capability to other coexisting ions.

Drawings

FIG. 1 shows the probe in example 1¹HNMR atlas.

FIG. 2 is the fluorescence spectrum of the probe for detecting mercury in example 2.

FIG. 3 is the selective fluorescence spectrum of the probe for detecting mercury in example 2.

Detailed Description

Example 1

50mg (0.14mmol) of 2, 5-bis (benzo [ d ] thiazol-2-yl) phenol and 28.3mg (0.28mmol) of triethylamine are added into a reaction bottle, 3ml of dry redistilled dichloromethane is added as a solvent, 35.9mg (0.21mmol) of phenyl thiocarbamate is added under an ice bath condition for reaction for 0.5h, the reaction is monitored by a TLC point plate until the raw materials are completely reacted, and the target product is obtained by passing through a column according to the eluent ratio of PE: DC ═ 2:3, wherein the yield is 38%, and the reaction formula is as follows:

example 2

50mg (0.14mmol) of 2, 5-bis (benzo [ d ] thiazol-2-yl) phenol and 21.2mg (0.21mmol) of triethylamine are added into a reaction bottle, 3ml of dry redistilled dichloromethane is added as a solvent, 35.9mg (0.21mmol) of phenyl thiocarbamate is added under an ice bath condition for reaction for 0.5h, the reaction is monitored by a TLC point plate until the raw materials are completely reacted, and the target product is obtained by passing through a column according to the eluent ratio of PE: DC ═ 2:3, wherein the yield is 49 percent and the reaction formula is as follows:

example 3

50mg (0.14mmol) of 2, 5-bis (benzo [ d ] thiazol-2-yl) phenol and 21.2mg (0.21mmol) of triethylamine are added into a reaction bottle, 5ml of dry redistilled dichloromethane is added as a solvent, 35.9mg (0.21mmol) of phenyl thiocarbamate is added under an ice bath condition for reaction for 0.5h, the reaction is monitored by a TLC point plate until the raw materials are completely reacted, and the target product is obtained by passing through a column according to the eluent ratio of PE: DC ═ 2:3, wherein the yield is 42 percent and the reaction formula is as follows:

EXAMPLE 4 Selective detection of divalent Mercury by Probe

The fluorescent probe compound prepared in example 1 was dissolved in a DMSO solution to prepare a 500. mu. mol probe stock solution, and mercuric chloride was dissolved in water to prepare a 10mmol mercury stock solution. Preparing acetonitrile: heps buffer (0.01mM, pH 7.4) 1: 1, 3mL per tube. mu.L (1. mu.M) of the probe stock solution was removed and added to each tube, and different volumes of mercury stock solution were taken in the tubes containing 3mL of the spectroscopic solution and probe. After 40 minutes of reaction, the probe was tested for changes in fluorescence spectra with a fluorescence spectrometer using an excitation wave at 350nm with different concentrations of mercury (0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 250, 300, 350 μ M). The fluorescence spectrum changes as shown in FIG. 2. The results show that with the addition of different concentrations of mercury ions, the fluorescence emission decreases at 405nm and increases at 525 nm.

EXAMPLE 5 Selective detection of divalent Mercury by Probe

The fluorescent probe compound prepared in example 1 was dissolved in a DMSO solution to prepare a 500. mu. mol probe stock solution, and mercuric chloride was dissolved in water to prepare a 10mmol mercury stock solution. Preparing acetonitrile: heps buffer (0.01mM, pH 7.4) 1: 1, 3mL per tube. mu.L (1. mu.M) of the resulting solution was added to each tube, and the same concentration of the different ion stocks was added to the tubes containing 3mL of the spectroscopic solution and probe. After 40 minutes of reaction, the probe and different ion mother liquor (Hg) with the same concentration are tested by a fluorescence spectrometer by adopting an excitation wave of 350nm²⁺、Na⁺、K⁺、Mg²⁺、Zn²⁺、Ca² ⁺、Fe³⁺、Cu²⁺、Cd²⁺、Cr³⁺、Co²⁺、Ni²⁺、Pb²⁺Blank) as shown in FIG. 3. The results show that only divalent mercury has higher responsiveness to the probe with the addition of different ion mother liquors of the same concentration.

Claims

1. A fluorescent probe responsive to mercury characterized by the molecular formula: c₂₇H₁₆N₂O₂S₃(ii) a The structural formula is as follows:

2. the method for synthesizing a fluorescent probe responsive to mercury according to claim 1, comprising the steps of:

adding 2, 5-bis (benzo [ d ] thiazole-2-yl) phenol and triethylamine into a reaction bottle, adding dry dichloromethane as a solvent, adding phenyl thiocarbamate under an ice bath condition, stirring at normal temperature for reaction, monitoring the reaction by a TLC (thin layer chromatography) dot plate until the raw materials completely react, and carrying out column chromatography to obtain the target product.

3. The method of synthesizing a fluorescent probe responsive to mercury according to claim 2, wherein: the mol ratio of the compound 2, 5-bis (benzo [ d ] thiazole-2-yl) phenol, triethylamine and phenyl thiocarbamate is 1: 1.2-3: 1.2-3.

4. The method of synthesizing a fluorescent probe responsive to mercury according to claim 2, wherein: the mol ratio of the compound 2, 5-bis (benzo [ d ] thiazole-2-yl) phenol, triethylamine and phenyl thiocarbamate is 1: 1.5: 1.5.

5. use of a fluorescent probe responsive to mercury according to claim 1 for the selective detection of divalent mercury.