CN-122010836-A - Novel quinoline H2S fluorescent probe and preparation method thereof

Abstract

The invention relates to the technical field of fluorescence detection, in particular to a novel quinoline H 2 S fluorescent probe and a preparation method thereof. The invention adopts a reaction strategy of reducing nitroso into amino, and uses quinoline derivatives as fluorescent groups to design and synthesize a novel quinoline H 2 S fluorescent probe. The aminoquinoline fluorophore has good optical performance, and the synthesis method has the advantages of low cost of raw materials, simple reaction, mild reaction conditions and the like. After the probe reacts with hydrogen sulfide, nitroso is reduced into hydroxylamine groups and amino groups, the fluorescence of the compound is enhanced, and the effective detection of H 2 S can be realized.

Inventors

• HUANG PEI
• HU YUANYUAN
• ZHANG CHENGRUI
• WANG QIN
• LI QIAN

Assignees

• 陕西理工大学
• 四川省生态环境监测总站

Dates

Publication Date

20260512

Application Date

20260130

Claims (6)

1. 1. The novel quinoline H 2 S fluorescent probe is characterized by comprising the following structural formula: 。
2. 2. A method for preparing the novel quinoline H 2 S fluorescent probe according to claim 1, comprising the steps of: s1, dissolving 4, 4-trifluoro-1- (p-tolyl) butane-1, 3-dione and m-phenylenediamine in chloroform, carrying out oil bath and stirring reflux reaction, carrying out rotary evaporation concentration, then carrying out recrystallization, washing, carrying out suction filtration and drying to obtain an intermediate product; S2, mixing an intermediate product with dichloromethane to obtain a mixed solution, dissolving sodium bisulfate in distilled water to obtain a potassium bisulfate aqueous solution, dropwise adding the potassium bisulfate aqueous solution into the mixed solution, stirring at normal temperature for reaction, extracting with an extractant for three times after the reaction is finished, separating and combining the obtained lower organic layers, drying, filtering, performing rotary evaporation concentration, and performing column chromatography separation and purification to obtain the novel quinoline H 2 S fluorescent probe.
3. 3. The method according to claim 2, wherein the amount ratio of 4, 4-trifluoro-1- (p-tolyl) butane-1, 3-dione, m-phenylenediamine and chloroform in S1 is 1.00 g:0.50~1.00 g:15~25 mL.
4. 4. The method according to claim 2, wherein the temperature of the oil bath in S1 is 80 ℃, the stirring reflux reaction time is 12 h, the solvent for recrystallization is chloroform, and the washing solution is n-hexane.
5. 5. The process according to claim 2, wherein the ratio of the intermediate, methylene chloride, sodium persulfate and distilled water used in S2 is 0.5 mmol:5~15 mL:2.5~5.0 mmol:10~20 mL.
6. 6. The method according to claim 2, wherein the stirring reaction time in S2 is 24 h, the stirring reaction speed is 1000 r/min, the extractant is dichloromethane, the drying agent is anhydrous Na 2 SO 4 , and the eluent for column chromatography is petroleum ether: ethyl acetate=2:1.

Description

Novel quinoline H 2 S fluorescent probe and preparation method thereof Technical Field The invention belongs to the technical field of fluorescence detection, and particularly relates to a novel quinoline H 2 S fluorescent probe and a preparation method thereof. Background Hydrogen sulfide (H 2 S) is an important endogenous gas signaling molecule involved in regulating various physiological activities such as immunity, nerves, cardiovascular and endocrine. Under physiological pH conditions, H 2 S mainly exists in the form of HS -, the homeostasis of the H 2 S is critical for maintaining normal functions, and concentration abnormality has been proved to be closely related to the occurrence and development of various diseases such as Alzheimer' S disease, diabetes, liver cirrhosis and the like. Therefore, technology capable of efficiently detecting H 2 S in living cells, tissues and living bodies is developed, and the technology has important scientific value for revealing the action mechanism of the technology in physiological and pathological processes. To achieve detection of H 2 S, various methods have been developed, including colorimetry, electrochemical analysis, chromatography, metal sulphide precipitation, and the like. However, these conventional methods generally have some inherent limitations, such as insufficient sensitivity, complex sample pretreatment, difficulty in achieving in-situ real-time monitoring of cells, etc., which greatly limit the application thereof in complex biological systems. The fluorescent probe method has the advantages of high sensitivity, good selectivity, high resolution, small invasion of biological samples and the like, and becomes an important tool for detecting trace active molecules in organisms. Based on this, the design of fluorescent probes for H 2 S has been widely studied. Currently, H 2 S fluorescent probes are reported to be mainly based on two reaction mechanisms, namely nucleophilic reaction and reduction reaction. Among them, the probe design strategies based on nucleophilic reaction include thiolysis of aromatic nitro groups, exchange of disulfide (selenium) bonds, nucleophilic addition to unsaturated bonds, serial michael addition, and the like. The probe based on H 2 S reducibility is generally used for reducing azide, nitro, hydroxylamine and the like into amino, so that obvious fluorescent signal change is initiated, and the detection purpose is realized. Despite the variety of mechanisms, existing probes still face challenges in performance and application. In particular, H 2 S fluorescent probes based on a new reaction path of nitroso reduction to amino groups have been reported to a very limited extent. For example, chen et al recently reported an H 2 S probe with benzopyran dye as fluorophore and nitroso as recognition group. However, such probes generally have the problems of insufficient sensitivity, unsatisfactory selectivity and the like, and are difficult to meet the requirement of high-precision biological detection. In addition, the synthesis route of most probes is complex, the steps are complicated, and the large-scale preparation and practical popularization and application are not facilitated. Therefore, the development of the H 2 S fluorescent probe which is simple and convenient to synthesize, quick in response, high in sensitivity and good in selectivity, particularly a high-performance probe based on a nitroso reduction mechanism, has urgent practical significance for promoting the research of H 2 S related biology and disease diagnosis. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a novel quinoline H 2 S fluorescent probe and a preparation method thereof, adopts a reaction strategy of reducing nitroso into amino, takes quinoline derivatives as fluorescent groups, and designs and synthesizes the novel quinoline H 2 S fluorescent probe. The probe has a simple synthesis route, has a certain anti-interference capability for H 2 S with a short response time, ensures that the detection process is quicker and more reliable, and can be put into H 2 S detection application. The invention provides a novel quinoline H 2 S fluorescent probe, which has the structural formula: 。 The invention also provides a preparation method of the novel quinoline H 2 S fluorescent probe, which comprises the following steps: s1, dissolving 4, 4-trifluoro-1- (p-tolyl) butane-1, 3-dione and m-phenylenediamine in chloroform, carrying out oil bath and stirring reflux reaction, carrying out rotary evaporation concentration, then carrying out recrystallization, washing, carrying out suction filtration and drying to obtain an intermediate product; S2, mixing an intermediate product with dichloromethane to obtain a mixed solution, dissolving sodium bisulfate in distilled water to obtain a potassium bisulfate aqueous solution, dropwise adding the potassium bisulfate aqueous solution into the mixed solution, stirring at normal t