Fluorescent small-molecule probe with CL-20 sensing function as well as preparation method and application method

Abstract

The invention discloses a fluorescent small-molecule probe with a CL-20 sensing function as well as a preparation method and an application method. The fluorescent small-molecule probe is 4-methyl piperazine-1,8-naphthalimide-gamma-cyclodextrin. The fluorescent small-molecule probe is prepared by firstly preparing paratoluensulfonyl-gamma-cyclodextrin with gamma-cyclodextrin and paratoluensulfonyl chloride, then preparing N3-gamma-cyclodextrin with paratoluensulfonyl-gamma-cyclodextrin and NaN3 and then reacting N3-gamma-cyclodextrin with N-propargyl-4-methyl piperazine-1,8-naphthalimide and Cu(PPh3)3Br. The fluorescent small-molecule probe is used for detecting CL-20. The small-molecule probe prepared by utilizing the 1,8-naphthalimide preparation material with higher fluorescence quantum yield has higher limit of detection and sensitivity. Click reaction can ensure the stability of the fluorescent material in water solutions, thus improving the detection sensitivity. The fluorescent small-molecule material provided by the invention has the characteristics of simplicity in synthesis and easiness in synthesis in quantity, thereby providing a technical support for eliminating deep potential terroristic threats.

Description

technical field

[0001] Embodiments of the present invention relate to the preparation of small molecule probes in the chemical industry, more specifically, embodiments of the present invention relate to a fluorescent small molecule probe capable of sensing CL-20 in aqueous solution and its preparation method and use method. Background technique

[0002] High-energy, high-density polyammonium nitrate compounds such as CL-20 are a new type of energetic material. Testing of CL-20 has important implications for homeland security, military operations and environmental testing. At present, there are many methods for the detection of CL-20, such as high performance liquid chromatography, mass spectrometry, capillary electrophoresis and so on. These methods exhibit good detection limits and a wide linear range, however, their use often requires expensive equipment or tedious sample pretreatment.

[0003] Fluorescent sensors based on fluorescence enhancement can be well used for t...

Examples

Embodiment 1

[0030] (1) Preparation of intermediate p-toluenesulfonyl-γ-cyclodextrin

[0031] Disperse γ-cyclodextrin (12.0 g, 6.4 mmol) in 100 mL of water, and slowly add 1 mL of aqueous sodium hydroxide solution (8.2 mol / L.) in an ice-water bath to completely dissolve the γ-cyclodextrin. At this time, p-toluenesulfonyl chloride (1.748g, 9.2mmol) was dissolved in 4mL of acetonitrile solution and slowly added dropwise to the above-mentioned solution in which γ-cyclodextrin was dissolved, and a white precipitate was formed during the dropwise addition. After the mixture was reacted at room temperature for 4 h, the pH value was adjusted to 5.8-6.2 with 3 mol / L hydrochloric acid solution, filtered, and recrystallized in water to obtain the target product.

[0032] (2) Using the intermediate p-toluenesulfonyl-γ-cyclodextrin to prepare N 3 -γ-cyclodextrin (6γCDN 3 )

[0033] p-toluenesulfonyl-γ-cyclodextrin (1.73g, 1.34mmol), NaN 3 (174mg, 2.68mmol) was dissolved in 10mL DMF, under the prot...

Embodiment 2

[0045] Disperse 12.8 mmol of γ-cyclodextrin in 180 mL of water, and slowly add 2 mL of 8.5 mol / L aqueous sodium hydroxide solution dropwise in an ice-water bath to completely dissolve the γ-cyclodextrin. Dissolve 19.2mmol of p-toluenesulfonyl chloride in 9mL of acetonitrile solution. The concentration of the acetonitrile solution of p-toluenesulfonyl chloride is not strictly controlled here, but the concentration when the p-toluenesulfonyl chloride is just completely dissolved in the acetonitrile solution is appropriate. The acetonitrile solution of p-toluenesulfonyl chloride was slowly added dropwise to the above mixed solution in which γ-cyclodextrin was dissolved, and a white precipitate was produced during the dropwise addition. After the mixture was reacted at room temperature for 3.5 h, the pH value was adjusted to 5.8-6.2 with 3.5 mol / L hydrochloric acid solution, filtered, and recrystallized in water to obtain p-toluenesulfonyl-γ-cyclodextrin.

[0046] 1.32mmol p-tolue...

Embodiment 3

[0052] Using the same preparation method as in Example 1 or Example 2, γ-cyclodextrin is 12.8mmol, 8mol / L sodium hydroxide aqueous solution 2mL, 17.92mmol p-toluenesulfonyl chloride is dissolved in 9mL acetonitrile solution and the mixture is prepared at room temperature After reacting for 4.5 hours, adjust the pH value to 5.8-6.2 with 2.5 mol / L hydrochloric acid solution, filter, and recrystallize in water to obtain p-toluenesulfonyl-γ-cyclodextrin.

[0053] 1.32mmol p-toluenesulfonyl-γ-cyclodextrin, 2mmol NaN 3 , 10 mL of a mixed solution of dimethylformamide was reacted at 108° C. for 3.5 h under the protection of nitrogen. After the reaction was completed, the solution was cooled to room temperature, and settled in acetone, and the solid was collected by filtration, and the collected solid was recrystallized in water to obtain 6γCDN 3 .

[0054] 10.8mmol 4-bromo-1,8-naphthalic anhydride, 25mL pyridine, 13mmol 4-methylpiperazine, 3mL triethylamine (about 0.003mmol). Afte...

technical field

[0001] Embodiments of the present invention relate to the preparation of small molecule probes in the chemical industry, more specifically, embodiments of the present invention relate to a fluorescent small molecule probe capable of sensing CL-20 in aqueous solution and its preparation method and use method. Background technique

[0002] High-energy, high-density polyammonium nitrate compounds such as CL-20 are a new type of energetic material. Testing of CL-20 has important implications for homeland security, military operations and environmental testing. At present, there are many methods for the detection of CL-20, such as high performance liquid chromatography, mass spectrometry, capillary electrophoresis and so on. These methods exhibit good detection limits and a wide linear range, however, their use often requires expensive equipment or tedious sample pretreatment.

[0003] Fluorescent sensors based on fluorescence enhancement can be well used for t...

Examples

Embodiment 1

[0030] (1) Preparation of intermediate p-toluenesulfonyl-γ-cyclodextrin

[0031] Disperse γ-cyclodextrin (12.0 g, 6.4 mmol) in 100 mL of water, and slowly add 1 mL of aqueous sodium hydroxide solution (8.2 mol / L.) in an ice-water bath to completely dissolve the γ-cyclodextrin. At this time, p-toluenesulfonyl chloride (1.748g, 9.2mmol) was dissolved in 4mL of acetonitrile solution and slowly added dropwise to the above-mentioned solution in which γ-cyclodextrin was dissolved, and a white precipitate was formed during the dropwise addition. After the mixture was reacted at room temperature for 4 h, the pH value was adjusted to 5.8-6.2 with 3 mol / L hydrochloric acid solution, filtered, and recrystallized in water to obtain the target product.

[0032] (2) Using the intermediate p-toluenesulfonyl-γ-cyclodextrin to prepare N 3 -γ-cyclodextrin (6γCDN 3 )

[0033] p-toluenesulfonyl-γ-cyclodextrin (1.73g, 1.34mmol), NaN 3 (174mg, 2.68mmol) was dissolved in 10mL DMF, under the prot...

Embodiment 2

[0045] Disperse 12.8 mmol of γ-cyclodextrin in 180 mL of water, and slowly add 2 mL of 8.5 mol / L aqueous sodium hydroxide solution dropwise in an ice-water bath to completely dissolve the γ-cyclodextrin. Dissolve 19.2mmol of p-toluenesulfonyl chloride in 9mL of acetonitrile solution. The concentration of the acetonitrile solution of p-toluenesulfonyl chloride is not strictly controlled here, but the concentration when the p-toluenesulfonyl chloride is just completely dissolved in the acetonitrile solution is appropriate. The acetonitrile solution of p-toluenesulfonyl chloride was slowly added dropwise to the above mixed solution in which γ-cyclodextrin was dissolved, and a white precipitate was produced during the dropwise addition. After the mixture was reacted at room temperature for 3.5 h, the pH value was adjusted to 5.8-6.2 with 3.5 mol / L hydrochloric acid solution, filtered, and recrystallized in water to obtain p-toluenesulfonyl-γ-cyclodextrin.

[0046] 1.32mmol p-tolue...

Embodiment 3

[0052] Using the same preparation method as in Example 1 or Example 2, γ-cyclodextrin is 12.8mmol, 8mol / L sodium hydroxide aqueous solution 2mL, 17.92mmol p-toluenesulfonyl chloride is dissolved in 9mL acetonitrile solution and the mixture is prepared at room temperature After reacting for 4.5 hours, adjust the pH value to 5.8-6.2 with 2.5 mol / L hydrochloric acid solution, filter, and recrystallize in water to obtain p-toluenesulfonyl-γ-cyclodextrin.

[0053] 1.32mmol p-toluenesulfonyl-γ-cyclodextrin, 2mmol NaN 3 , 10 mL of a mixed solution of dimethylformamide was reacted at 108° C. for 3.5 h under the protection of nitrogen. After the reaction was completed, the solution was cooled to room temperature, and settled in acetone, and the solid was collected by filtration, and the collected solid was recrystallized in water to obtain 6γCDN 3 .

[0054] 10.8mmol 4-bromo-1,8-naphthalic anhydride, 25mL pyridine, 13mmol 4-methylpiperazine, 3mL triethylamine (about 0.003mmol). Afte...

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