CN110724520B

CN110724520B - Fluorescent probe for detecting water content in heavy water and application thereof

Info

Publication number: CN110724520B
Application number: CN201910898737.2A
Authority: CN
Inventors: 林伟英; 董宝利; 卢雅如; 宋文辉; 孙亚茹
Original assignee: University of Jinan
Current assignee: University of Jinan
Priority date: 2019-09-23
Filing date: 2019-09-23
Publication date: 2020-11-17
Anticipated expiration: 2039-09-23
Also published as: CN110724520A

Abstract

The invention provides a method for detecting light water in heavy waterContent of fluorescent probe:

. The fluorescent probe provided by the invention takes the hydroxyl groups of coumarin and xanthene parts as response sites based on the difference of the pH values of heavy water and light water. The fluorescent probe for detecting the light water content in the heavy water can be obtained by chemical synthesis, the synthesis process is simple and feasible, the raw materials are cheap and easy to obtain, the preparation cost is low, and the popularization is easy. The probe has high sensitivity, is basically not interfered by other components in the process of detecting the light water content in corresponding heavy water, and has wide application prospect. The probe has good fluorescence emission spectrum characteristics, and can realize the purpose of quickly and accurately detecting the light water content in the heavy water.

Description

Fluorescent probe for detecting water content in heavy water and application thereof

Technical Field

The invention belongs to the field of organic small-molecule fluorescent probes, and particularly relates to a fluorescent probe for detecting water content in heavy water based on coumarin and xanthene structures.

Background

Heavy water (Deuterium oxide) is a compound consisting of Deuterium and oxygen, formula D₂O, relative molecular mass 20.0275, specific water (H)₂O) has a molecular weight 18.0153 about 11% higher, hence the name heavy water. In natural water, the content of heavy water is about 0.015%. Heavy water is also very similar to regular water because deuterium has very little difference in properties from hydrogen.

The special value of heavy water is reflected in the application of atomic energy technology, and heavy water is required to be used as a moderator in nuclear fission reaction for manufacturing powerful nuclear weapons. Where the solvent is water and the subject of investigation is hydrogen, heavy water may be used as the solvent in the nmr analysis. Neutron moderator: some nuclear reactors use heavy water to slow the neutrons down, giving them an opportunity to react with uranium. Light water can also be used as a moderator, but because light water absorbs neutrons, light water reactors must use enriched uranium instead of normal uranium, or the critical mass cannot be reached. Heavy water reactors can use not only ordinary uranium, but also uranium 238 to convert it to plutonium, which can be used to make nuclear bombs. Although heavy water has important use value, it is harmful to human beings, and microorganisms and fish in pure heavy water or water with heavy water (more than 80%) die in hours. In contrast, light water with particularly little heavy water, such as snow water, can stimulate biological growth.

Since heavy water is generally prepared by distillation from light water at present, and heavy water has strong hydrophilicity, a certain amount of light water is often contained in heavy water. The detection of the light water content in the heavy water is of great significance for the safe application of the heavy water. Compared with the traditional detection methods such as atomic absorption and nuclear magnetic resonance, the fluorescence analysis method has the advantages of high sensitivity, good selectivity, quick response, simple operation and the like, and is widely used for detecting various small molecules. Therefore, the development of a new fluorescent probe which has high sensitivity and light stability and can quickly detect the light water content in the heavy water in real time has important significance.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides the fluorescent probe for detecting the water content in the heavy water, which has the advantages of high response speed and strong anti-interference capability.

In order to achieve the purpose, the invention adopts the following technical scheme.

A fluorescent probe for detecting the content of light water in heavy water has a chemical structural formula shown as a formula (I):

formula (I).

The preparation method of the fluorescent probe comprises the following steps:

under the protection of nitrogen, 7-hydroxycoumarin-3-carboxylic acid and

in the presence of HOBT (1-hydroxy-benzo-triazole), EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimideAmine hydrochloride) and DIEA (N, N-diisopropylethylamine) in DMF (N, N-dimethylformamide), and separating and purifying to obtain the final product.

An application of the fluorescent probe in detecting the light water content in heavy water.

The mechanism of the invention is as follows:

the fluorescent probe provided by the invention takes the hydroxyl groups of coumarin and xanthene parts as response sites based on the difference of the pH values of heavy water and light water. Under the condition of low water content in the heavy water, hydroxyl of the coumarin is ionized into oxyanion, and the xanthene part is converted into a closed-loop structure, so that the fluorescent probe can emit blue fluorescence (the peak value is about 450 nm) of the coumarin part and green fluorescence (the peak value is about 550 nm) of the xanthene part.

The invention has the following advantages:

the fluorescent probe for detecting the light water content in the heavy water can be obtained by chemical synthesis, the synthesis process is simple and feasible, the raw materials are cheap and easy to obtain, the preparation cost is low, and the popularization is easy. The probe has high sensitivity, is basically not interfered by other components in the process of detecting the light water content in corresponding heavy water, and has wide application prospect. The probe has good fluorescence emission spectrum characteristics, and can realize the purpose of quickly and accurately detecting the light water content in the heavy water.

Drawings

FIG. 1 shows a fluorescent probe¹H NMR spectrum;

FIG. 2 is a fluorescence spectrum of a fluorescent probe in heavy water of different light water contents;

FIG. 3 is a fluorescence intensity ratio I of the solution₄₅₀The ratio relation with the light water content;

FIG. 4 is a fluorescence intensity ratio I of the solution₅₅₀The ratio relation with the light water content;

FIG. 5 shows fluorescence spectra of fluorescent probes after reaction with different substances.

Detailed Description

The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited to the following examples.

EXAMPLE 1 Synthesis of fluorescent Probe

Compound 1 (80 mg, 0.2 mmol), 7-hydroxycoumarin-3-carboxylic acid (40 mg, 0.2 mmol), HOBT (13.5 mg, 0.1 mmol), EDC (78 mg, 0.4 mmol) in 4 mL DMF was stirred at room temperature for 10 min, after which 200. mu.L DIEA was added and stirring continued for 5 h under nitrogen, which was then purified by column chromatography over CH₂Cl₂: CH₃OH = 10:1 (v/v) to obtain an orange fluorescent probe with a yield of 65%,¹the H NMR spectrum is shown in FIG. 1.

EXAMPLE 2 fluorescent detection of heavy Water with different light Water content by fluorescent Probe

5 mL of a 10. mu.M heavy aqueous solution of the probe containing 0.33% DMSO and containing 10% to 100% of light water was prepared in advance. Then fluorescence detection (lambda) was performed_Ex= 400 nm); calculating the fluorescence intensity in each system; the response performance of the probe to light water content was evaluated by analyzing the relationship between the fluorescence intensity at 450 nm and 550 nm and the light water content (see fig. 2, 3 and 4). FIGS. 2, 3 and 4 show that the ratio of fluorescence intensity I of the solution increases with the light water content₄₅₀And I₅₅₀Gradually decreases, and simultaneously, the light water content and the fluorescence intensity have a better linear relationship.

Example 3 selectivity of fluorescent probes for different ions

5 mL of a 10. mu.M probe-heavy aqueous solution containing 0.33% DMSO was prepared in advance, and 50. mu.L of 200. mu.M CuSO was sequentially added to the system₄、Na₂S、Na₂SO₃、H₂O₂、Cys、GSH、NaNO₂Etc. small molecule aqueous solution. Then fluorescence detection (lambda) was performed_Ex= 400 nm); the fluorescence intensity I in each system was calculated₅₅₀And I₄₄₀(ii) a The different substances were evaluated for their interference with the fluorescent probe solution (see FIG. 5). As can be seen from the figure, when CuSO was added to the probe solution₄、Na₂S is smallThe fluorescence of the solution is substantially unchanged when the molecule is used.

Claims

1. A fluorescent probe for detecting the content of light water in heavy water has a chemical structural formula shown as a formula (I):

formula (I).

2. A method of preparing a fluorescent probe according to claim 1, comprising the steps of:

under the protection of nitrogen, 7-hydroxycoumarin-3-carboxylic acid and

reacting in DMF in the presence of HOBT, EDC and DIEA, and separating and purifying to obtain the final product.

3. Use of the fluorescent probe of claim 1 for detecting light water content in heavy water.