CN114230494A - Synthesis of large Stokes shift near-infrared fluorescent probe and application thereof in detecting hydrogen sulfide - Google Patents

Synthesis of large Stokes shift near-infrared fluorescent probe and application thereof in detecting hydrogen sulfide Download PDF

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CN114230494A
CN114230494A CN202111635758.9A CN202111635758A CN114230494A CN 114230494 A CN114230494 A CN 114230494A CN 202111635758 A CN202111635758 A CN 202111635758A CN 114230494 A CN114230494 A CN 114230494A
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dimethylcyclohex
malononitrile
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尹鹏
洪赛
尹国兴
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Hunan Normal University
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Abstract

The invention discloses synthesis of a near-infrared fluorescent probe with large Stokes shift (223 nm) and application of the near-infrared fluorescent probe in detecting hydrogen sulfide (H)2S), the chemical structural formula of the molecular probe is as follows:
Figure 461320DEST_PATH_IMAGE001
. The fluorescent probe pair H2S has high specificity and no response to other active sulfur substances in organisms, and can be used for H in complex biological environments such as cells2And (4) detecting the specificity of S. Introduction of electron donating groups into the fluorophore further increases the probe detection H2Stokes shift of S(up to 223 nm), the near infrared fluorescence emission wavelength is up to 680 nm, and the interference of background fluorescence in biological imaging application can be greatly reduced. Probe response H2S has the advantages of high reaction rate, near-infrared emission, large Stokes shift and the like, is suitable for amplification synthesis and practical production application, and has huge application prospects in the technical fields of analytical chemistry, life science and the like.

Description

Synthesis of large Stokes shift near-infrared fluorescent probe and application thereof in detecting hydrogen sulfide
Technical Field
The invention belongs to the technical field of analytical chemistry, and particularly relates to synthesis of a large Stokes shift near-infrared fluorescent probe and application thereof in detection of hydrogen sulfide. The probe can be used for quantitative detection of H in environment2S, fluorescence imaging of endogenous H in cells2S, and has the advantages of large Stokes shift, near infrared fluorescence emission, high selectivity and the like.
Background
Hydrogen sulfide (H)2S) is a third gas signaling molecule, in addition to carbon monoxide (CO) and Nitric Oxide (NO), that plays an important role in the human nervous system. H2S can participate in physiological functions such as vasodilation, angiogenesis, cell growth, nerve regulation, insulin signal inhibition, inflammatory response and the like. Endogenous H2S is mainly synthesized by three enzymes, cysteine beta-synthetase (CBS), cystine gamma-lyase (CSE) and 3-mercaptopyruvate thiotransferase (3-MST) ((3-MST))Chem. Commun., 2014,50, 9185-9187)。H2Abnormal S levels can induce a variety of diseases, such as diabetes, liver cirrhosis, Alzheimer 'S disease, Down' S syndrome, and the like (New J. Chem., 2020,44, 20253-20258). It has been reported that intracellular H2S concentration is an important indicator of tumors. Therefore, for H in biological systems2The monitoring of the S level is very meaningful. The fluorescent probe is used as an effective detection means, and has the advantages of simple operation, high response speed and high sensitivity to H2S has the unique advantages of good selectivity and the like, and H in a visual biological system2The S aspect has great development potential. To date, a variety of assays for detecting H have been developed2Fluorescent probes for S, mostly H2S fluorescent probes have the disadvantages of small stokes shift, short emission wavelength, etc., which may lead to severe self-absorption of fluorescence, and when excited, the excitation light may interfere with the fluorescent signal, which may limit their application in biology and medicine. Compared with near infrared emission (NIR) fluorescent probes, the fluorescent probes are more suitable for in vivo imaging application, have small light damage, deep tissue penetration and strong capability of resisting background autofluorescence interference, and therefore, the near infrared emission and large Stokes shift H is developed2S fluorescent probes are urgently needed.
Disclosure of Invention
In view of the above, the present invention overcomes some of the deficiencies of the prior art and aims to provide a novel large stokes shift near infrared fluorescence emission H2Synthesis and application of S fluorescent probe capable of detecting H from multiple active sulfur substances in single mode2S。
The invention also aims to provide a synthesis and application method of the fluorescent molecular probe, which has the advantages of simple preparation method and low cost.
The specific technical scheme adopted for solving the problems is as follows: the synthesis of a large Stokes shift near infrared fluorescent probe and the application thereof in detecting hydrogen sulfide, wherein the chemical structural formula of the probe is as follows:
Figure 114023DEST_PATH_IMAGE001
。
the synthesis of the large Stokes shift near infrared fluorescent probe is characterized in that the preparation method of the fluorescent molecular probe comprises the following steps:
step 1. Synthesis of 3-methoxy-4-nitrobenzaldehyde
a. Adding appropriate amount of 3-hydroxy-4-nitrobenzaldehyde and methyl iodide into mixed solvent of anhydrous acetonitrile and N, N-Dimethylformamide (DMF), adding appropriate amount of potassium carbonate, reacting at room temperature for 24 hr, filtering to remove potassium carbonate, spin drying the solution,
b. adding a proper amount of deionized water into the spin-dried solution to precipitate a white solid, and filtering and spin-drying to obtain 3-methoxy-4-nitrobenzaldehyde;
step 2 Synthesis ofE) -2- (3- (3-methoxy-4-nitrostyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile
A. Dissolving appropriate amount of 3-methoxy-4-nitrobenzaldehyde and 2- (3, 5, 5-trimethylcyclohex-2-en-1-yl) malononitrile in acetonitrile, adding 2 drops of piperidine, stirring at room temperature for 12 hours,
B. filtering the reaction solution to obtain yellow solid, recrystallizing and purifying the crude product with acetonitrile to obtain (A), (B)E) -2- (3- (3-methoxy-4-nitrostyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile;
step 3 Synthesis ofE) -2- (3- (4-amino-3-methoxystyryl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile
i. Under the protection of argon gas, the proper amount of (A)E) -2- (3- (3-methoxy-4-nitrostyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile and stannous chlorideAdding into absolute ethyl alcohol, refluxing and reacting for 12 hours,
ii, filtering the reaction liquid to remove stannous chloride, and purifying the filtrate by column chromatography to obtain a purple solid (namely: (a)E) -2- (3- (4-amino-3-methoxystyryl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile;
step 4 Synthesis ofE) -N- (4- (2- (3- (dicyanomethylene) -5, 5-dimethylcyclohex-1-en-1-yl) vinyl-2-methoxyphenyl) -2, 4-dinitrobenzenesulfonamide
I. Under the protection of argon gas, the proper amount of (A)E) Dissolving (E) -2- (3- (4-amino-3-methoxystyryl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile and 2, 4-dinitrobenzenesulfonyl chloride in dichloromethane, adding triethylamine, stirring at room temperature for 8 hours,
II, purifying the reaction liquid by column chromatography to obtain a black solid (namely: (A)E) -N- (4- (2- (3- (dicyanomethylene) -5, 5-dimethylcyclohex-1-en-1-yl) vinyl-2-methoxyphenyl) -2, 4-dinitrobenzenesulfonamide.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the fluorescent probe of the present invention.
FIG. 2 is a fluorescence spectrum diagram of the fluorescent probe for detecting NaHS according to the present invention.
FIG. 3 shows the fluorescent probe imaging Hela cell endogenous H according to the invention2Fluorescence imaging of S.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
The synthetic route of the fluorescent molecular probe is shown as the following formula:
Figure 340605DEST_PATH_IMAGE002
。
EXAMPLE 1 Synthesis of 3-methoxy-4-nitrobenzaldehyde
a. 2.00 g (11.97 mmol) of 3-hydroxy-4-nitrobenzaldehyde and 6.79 g (47.87 mmol) of methyl iodide were added to a mixed solvent of 10 mL of anhydrous acetonitrile and 10 mL of N-Dimethylformamide (DMF), 1.65 g (11.97 mmol) of potassium carbonate was added thereto and reacted at room temperature for 24 hours, the potassium carbonate was removed by filtration, the solution was dried by spinning,
b. deionized water was added to the solution after the spin-drying to precipitate a white solid, which was filtered and spin-dried to obtain 1.85g of 3-methoxy-4-nitrobenzaldehyde with a yield of 85.35%.
Example 2 Synthesis ofE) -2- (3- (3-methoxy-4-nitrostyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile
A. 1.85g (10.21 mmol) of 3-methoxy-4-nitrobenzaldehyde and 2.09 g (11.23 mmol) of 2- (3, 5, 5-trimethylcyclohex-2-en-1-yl) malononitrile were added to 20 mL of anhydrous acetonitrile, 2 drops of piperidine were added, and the mixture was stirred at room temperature for 12 hours,
B. filtering the reaction solution to obtain yellow solid, recrystallizing and purifying the crude product with acetonitrile to obtain (A), (B)E) 1.51g of (E) -2- (3- (3-methoxy-4-nitrostyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile at 42.32% yield.
Example 3 Synthesis ofE) -2- (3- (4-amino-3-methoxystyryl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile
i. Under the protection of argon, 1.51g (4.32 mmol) of (E) Adding (E) -2- (3- (3-methoxy-4-nitrostyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile and 1.17 g (5.19 mmol) of stannous chloride into 15 mL of absolute ethanol, carrying out reflux reaction for 12 hours,
ii, filtering the reaction liquid to remove stannous chloride, and purifying the filtrate by column chromatography to obtain a purple solid (namely: (a)E) 721 mg of (E) -2- (3- (4-amino-3-methoxystyryl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile in 52.23% yield.
Example 4 Synthesis ofE) -N- (4- (2- (3- (dicyanomethylene) -5, 5-dimethylcyclohex-1-en-1-yl) vinyl-2-methoxyphenyl) -2, 4-dinitrobenzenesulfonamide
I. Under argon shield 721 mg (2.25 mmol) ((E) -2- (3- (4-amino-3-methoxystyryl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile and 722 mg (2.71 mmol) 2, 4-dinitrobenzenesulfonyl chloride were added to 10 mL of anhydrous dichloromethane, 228 mg (2.25 mmol) triethylamine was added, and the mixture was stirred at room temperature for 8 hours,
II, purifying the reaction liquid by column chromatography to obtain a black solid (namely: (A)E) 558 mg of (E) -N- (4- (2- (3- (dicyanomethylene) -5, 5-dimethylcyclohex-1-en-1-yl) vinyl-2-methoxyphenyl) -2, 4-dinitrobenzenesulfonamide in 44.98% yield.
Example 5 fluorescent molecular probes in vitro Environment detection H2Application of S
The open type fluorescent molecular probe spectrum property experiment of the invention comprises the following steps: the probe was dissolved in dimethyl sulfoxide (DMSO) to prepare a 1mM probe solution, and NaHS (H) was prepared at a concentration of 1mM2S exists primarily as a hydrogen sulfate salt under physiological conditions). The specific test mode is as follows: mu.L of 1mM probe solution, 180. mu.L of analytically pure DMSO, the required amount of 1mM NaHS in water and the required amount of PBS buffer in 2 mL sample tubes were taken, all tests maintaining a volume ratio of the organic and aqueous phases of 1:9 (total volume of 2 mL per test sample). For example, when the fluorescence intensity of the probe after reaction with NaHS is required to be measured at a concentration of 20. mu.M, the sample is prepared as follows: after 20. mu.L of 1mM probe solution, 180. mu.L of analytically pure DMSO, 1760. mu.L of PBS buffer solution and 40. mu.L of 1mM NaHS aqueous solution are shaken and shaken in a 2 mL sample tube at 37 ℃ for 30 minutes, the fluorescence emission intensity can be measured at 457nm excitation wavelength, and other testing procedures are similar to the above steps. The probe molecule realizes near infrared and large Stokes displacement detection H2S, has high sensitivity with the detection limit of 53.1nM, and is very suitable for the endogenous H of living cells2And (4) imaging and analyzing S.
Example 6 endogenous H in HeLa cells2S-fluorescence imaging analysis
The HeLa cells are subcultured in a confocal dish cell culture medium for 24 hours under standard growth conditions, then a proper amount of probe (5 mu M) is added to continue to be cultured for 30 minutes under the standard growth conditions, then photography is carried out under a confocal fluorescence microscope, and fluorescence imaging is carried out by using a red fluorescence channel to obtain the endogenous H of the Hela cells2S, as can be seen from FIG. 3, H of the present invention2Successfully realizing endogenous H in cells by using S fluorescent probe2The high-sensitivity fluorescence imaging analysis of S has great application value in the fields of biochemistry, analysis and detection and the like.
The invention discloses application of a near-infrared fluorescent probe with large Stokes displacement in detecting hydrogen sulfide, and provides application of the large Stokes displacement and the near-infrared fluorescent probe in H2The high-sensitivity detection of S has great practical application value in the fields of biochemistry, analysis and detection and the like. While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Thus, H having similar features to those described herein2S fluorescent probes, all fall within the scope of this patent.

Claims (4)

1. The large Stokes shift near infrared fluorescent probe is characterized in that the chemical structural formula of the fluorescent molecular probe is shown as (1):
Figure 914094DEST_PATH_IMAGE001
（1）。
2. the synthesis of the near-infrared fluorescent probe of claim 1, wherein the synthesis method of the fluorescent molecular probe comprises the following steps:
step 1. Synthesis of 3-methoxy-4-nitrobenzaldehyde
a. Adding appropriate amount of 3-hydroxy-4-nitrobenzaldehyde and methyl iodide into mixed solvent of anhydrous acetonitrile and N, N-Dimethylformamide (DMF), adding appropriate amount of potassium carbonate, reacting at room temperature for 24 hr, filtering to remove potassium carbonate, spin drying the solution,
b. adding a proper amount of deionized water into the spin-dried solution to precipitate a white solid, and filtering and spin-drying to obtain 3-methoxy-4-nitrobenzaldehyde;
step 2 Synthesis ofE) -2- (3- (3-methoxy-4-nitrostyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile
A. Dissolving appropriate amount of 3-methoxy-4-nitrobenzaldehyde and 2- (3, 5, 5-trimethylcyclohex-2-en-1-yl) malononitrile in acetonitrile, adding 2 drops of piperidine, stirring at room temperature for 12 hours,
B. filtering the reaction solution to obtain yellow solid, recrystallizing and purifying the crude product with acetonitrile to obtain (A), (B)E) -2- (3- (3-methoxy-4-nitrostyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile;
step 3 Synthesis ofE) -2- (3- (4-amino-3-methoxystyryl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile
i. Under the protection of argon gas, the proper amount of (A)E) Adding (E) -2- (3- (3-methoxy-4-nitrostyrene) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile and stannous chloride into absolute ethyl alcohol, carrying out reflux reaction for 12 hours,
ii, filtering the reaction liquid to remove stannous chloride, and purifying the filtrate by column chromatography to obtain a purple solid (namely: (a)E) -2- (3- (4-amino-3-methoxystyryl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile;
step 4 Synthesis ofE) -N- (4- (2- (3- (dicyanomethylene) -5, 5-dimethylcyclohex-1-en-1-yl) vinyl-2-methoxyphenyl) -2, 4-dinitrobenzenesulfonamide
I. Under the protection of argon gas, the proper amount of (A)E) Dissolving (E) -2- (3- (4-amino-3-methoxystyryl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile and 2, 4-dinitrobenzenesulfonyl chloride in dichloromethane, adding triethylamine, stirring at room temperature for 8 hours,
II, purifying the reaction liquid by column chromatography to obtain a black solid (namely: (A)E) -N- (4- (2- (3- (dicyanomethylene) -5, 5-dimethylcyclohex-1-en-1-yl) vinyl-2-methoxyphenyl) -2, 4-dinitrobenzenesulfonamide.
3. The synthesis of the near-infrared fluorescent probe of claim 2, wherein step I (I)E) The molar ratio of (E) -2- (3- (4-amino-3-methoxystyryl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile to 2, 4-dinitrobenzenesulfonyl chloride is 1: 1.2.
4. Use of the near-infrared fluorescent probe according to claim 1, characterized in thatThe fluorescent molecular probe can be prepared to quantitatively detect H in the environment2S, intracellular analysis and imaging H2Application of the device of S.
CN202111635758.9A 2021-12-29 2021-12-29 Synthesis of large Stokes shift near-infrared fluorescent probe and application thereof in detecting hydrogen sulfide Pending CN114230494A (en)

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CN118126022A (en) * 2024-03-05 2024-06-04 江苏蒙博生物工程科技有限公司 Near infrared ratio type fluorescent probe and preparation method and application thereof

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Application publication date: 20220325