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A kind of H2S fluorescent probe based on 4-styrene pyridinium salt long-wave emission recognition and its synthesis method and application

A fluorescent probe and probe technology, applied in luminescent materials, fluorescence/phosphorescence, chemical instruments and methods, etc., can solve the problems of long response time, large radiation energy, short emission wavelength, etc., to achieve easy separation and purification, good resistance Interference ability, effect of short response time

Active Publication Date: 2021-08-13
BOHAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Anal. Chem., (2018), 90, 7510-7516; Anal. Chem., (2015), 87, 1188-1195; J.Org.Chem., (2017), 82, 10234-10246; Chem.Commun .,(2012),48,10871-10837; Anal.Chem.,(2013),85,7875-7881, although these documents can specifically identify H 2 S, but the emission wavelength is short, it cannot be detected in the long wavelength region, and the synthesis route is complicated and the response time is long
As we all know, in the visible spectral region, biological samples have strong background fluorescence and self-absorption, which will interfere with detection and imaging and affect the accuracy of measurement.
At the same time, the wavelength of visible light is short, and the radiation energy is relatively large during fluorescence imaging, which is easy to cause photodamage to cells and biological tissues.

Method used

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  • A kind of H2S fluorescent probe based on 4-styrene pyridinium salt long-wave emission recognition and its synthesis method and application
  • A kind of H2S fluorescent probe based on 4-styrene pyridinium salt long-wave emission recognition and its synthesis method and application
  • A kind of H2S fluorescent probe based on 4-styrene pyridinium salt long-wave emission recognition and its synthesis method and application

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] (1) The specific synthetic steps of compound 1 are as follows:

[0030]

[0031] 4-Diethylamino salicylaldehyde (1.54g, 8.0mmol), 4-picoline salt (1.88g, 8.0mmol) and piperidine (0.8mmol) were dissolved in ethanol, heated to reflux for 12h, and the solvent was spun off. The crude product was purified by thin-layer column chromatography using CH 3 OH:CH 2 Cl 2 =1:50 (v / v) was used as eluent, and 2.05g of compound 1 was isolated with a yield of 62.5%;

[0032] 1 H NMR (400MHz, DMSO-d 6 )δ10.13(s,1H),8.59(d,J=6.5Hz,2H),8.03-7.93(m,3H), 7.49(d,J=9.0Hz,1H),7.15(d,J=16.0 Hz,1H),6.33(dd,J=9.0,2.4Hz,1H),6.21(d,J=2.4Hz,1H),4.15(s,3H),3.39(q,J=7.0Hz,4H), 1.15(t,J=7.0Hz,6H).

[0033] (2) The specific synthesis steps of fluorescent probe L are as follows:

[0034]

[0035] Compound 1 (410mg, 1mmol), 2,4-dinitrofluorobenzene (223mg, 1.2mmol), potassium carbonate (207mg, 1.5mmol), were dissolved in 10mL DMF, and reacted at room temperature for 6h. After the reaction, was...

Embodiment 2

[0039] (1) Synthesis of Compound 1

[0040] 4-Diethylamino salicylaldehyde (1.54g, 8.0mmol), 4-picoline salt (3.76g, 16.0mmol) and piperidine 16mmol were dissolved in ethanol, heated to reflux for 8h, and the solvent was spun off. The crude product was purified by thin-layer column chromatography using CH 3 OH:CH 2 Cl 2 =1: 100 (v / v) was used as the eluent to obtain compound 1;

[0041] (2) Synthesis of fluorescent probe L

[0042] Compound 1 (410mg, 1.0mmol), 2,4-dinitrofluorobenzene (278.5mg, 1.5mmol), potassium carbonate (276mg, 2.0mmol) were dissolved in 15mL DMF, and reacted at room temperature for 8h. After the reaction, wash with water, extract with ethyl acetate, dry over anhydrous sodium sulfate, spin out the solvent, and purify the crude product by thin-layer column chromatography, using CH 3 OH:CH 2 Cl 2 =1: 80 (v / v) was used as the eluent to obtain 420 mg of probe L with a yield of 72.9%. fluorescent probe L 1 H NMR spectrum as figure 1 as shown, 13 C N...

Embodiment 3

[0044] (1) Synthesis of Compound 1

[0045] 4-Diethylamino salicylaldehyde (1.54g, 8.0mmol), 4-picoline salt (9.4g, 40.0mmol) and piperidine 8mmol were dissolved in ethanol, heated to reflux for 16h, and the solvent was spun off. The crude product was purified by thin-layer column chromatography using CH 3 OH:CH 2 Cl 2 =1: 100 (v / v) was used as the eluent to obtain compound 1;

[0046] (2) Synthesis of fluorescent probe L

[0047] Compound 1 (410mg, 1.0mmol), 2,4-dinitrofluorobenzene (371mg, 2mmol), potassium carbonate (414mg, 3.0mmol) were dissolved in 15mL DMF, and reacted at room temperature for 10h. After the reaction, wash with water, extract with ethyl acetate, dry over anhydrous sodium sulfate, spin out the solvent, and purify the crude product by thin-layer column chromatography, using CH 3 OH:CH 2 Cl 2 =1:100 (v / v) was used as eluent to obtain fluorescent probe L. fluorescent probe L 1 H NMR spectrum as figure 1 as shown, 13 C NMR spectrum as figure 2 sho...

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Abstract

A method based on the long-wave emission of 4‑styrene pyridinium salts to identify H 2 S fluorescent probe and its synthetic method and application, its structural formula is as follows: preparation method is: take ethanol as solvent, 4-(diethylamino) salicylaldehyde, 4-picoline salt, piperidine carry out feeding, heating reflux reaction , the solvent was spun out, and the crude product was purified by silica gel column chromatography, and separated with methanol and dichloromethane as eluents to obtain compound 1. Using DMF as a solvent, compound 1, 2,4-dinitrofluorobenzene, and potassium carbonate were fed, stirred at room temperature, filtered to obtain a crude product, purified by silica gel column chromatography, and separated with an eluent to obtain a fluorescent Probe L. The advantages are: simple synthesis steps, easy separation and purification; fluorescent probes can recognize H 2 S, has good selectivity, high sensitivity and good anti-interference ability, and can be applied to detect H in actual water samples 2 S.

Description

technical field [0001] The invention relates to a method based on 4-styrene pyridinium salt long-wave emission recognition H 2 S fluorescent probes and their synthesis methods and applications. Background technique [0002] Hydrogen sulfide (H 2 S), a newly discovered gaseous signaling molecule, has become a research hotspot in the field of biology due to its diverse functions in physiological and pathological processes. h 2 S mainly comes from volcanic eruptions and mammalian cells themselves through cystathionine-β-synthase (CBS), cystathionine-γ-lyase (CSE), 3-mercaptopyruvate sulfur transferase (3-MST), etc. produced by the action of enzymes. Previous studies have shown that H 2 S plays an important role in regulating blood pressure, cardiovascular protection, regulating cell growth and stimulating angiogenesis. In addition, high levels of H in living systems 2 S can cause human diseases such as Alzheimer's disease, Down's syndrome, hypertension and liver cirrhosi...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D213/38C09K11/06G01N21/64
CPCC07D213/38C09K11/06C09K2211/1007C09K2211/1014C09K2211/1029G01N21/643
Inventor 钟克利汤立军曲秀莉侯淑华任欢欢李秋莹徐永霞边延江周诗怡
Owner BOHAI UNIV
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