Micromolecular fluorescent probe for hydrazine hydrate detection, polyurethane fiber membrane and preparation method of polyurethane fiber membrane

Abstract

The invention provides a micromolecular fluorescent probe for hydrazine hydrate detection, a polyurethane fiber membrane and a preparation method of the polyurethane fiber membrane, and belongs to the technical field of polyurethane spinning and organic micromolecular fluorescent probes. The molecular formula of the small molecular fluorescent probe disclosed by the invention is C18H19N3O2S; the preparation method comprises the following steps: suspending 2-(3, 4-ethylenedioxythiophene) formaldehyde in dry acetonitrile, and cooling; the preparation method comprises the following steps: adding N-bromosuccinimide, stirring and reacting at room temperature, washing, evaporating in vacuum, recrystallizing, sequentially adding ethanol, malononitrile, glacial acetic acid and hexahydropyridine for reacting, adding sodium bicarbonate into the solution, adjusting the pH value, and purifying to obtain the N-bromosuccinimide. The preparation method comprises the following steps: firstly, preparing a product, uniformly mixing the product with 4-boric acid triphenylamine and tetrakis (triphenylphosphine) palladium in toluene, then adding a potassium carbonate aqueous solution, after the reaction is completed, extracting, removing moisture in the solution, and dissolving to obtain the probe EDOT-D. The probe has the characteristics of good hydrazine hydrate selectivity, strong anti-interference capability, low background interference and high sensitivity.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane spinning and organic small molecule fluorescent probes, and specifically relates to a small molecule fluorescent probe for hydrazine hydrate detection, a polyurethane fiber membrane and a preparation method thereof. Background Art

[0002] Hydrazine hydrate has the characteristic of high hydrogen content and has received extensive attention in the fuel field. In addition, hydrazine hydrate occupies an important position in the production of foaming agents and is the second largest market application. It has a wide range of applications in the fields of pesticide synthesis and the cleaning, refining, reducing agent, and antioxidant of precious metals. However, hydrazine hydrate itself has strong alkalinity and hygroscopicity. It can corrode glass, rubber, leather, cork, etc., and decompose into N at high temperature. 2 NH 3 and H 2 Etc. At the same time, hydrazine hydrate can also have negative impacts on the environment and organisms.

[0003] Currently, fluorescent probes are widely used in biological environmental monitoring due to their high selectivity, low biological toxicity, low operational difficulty, high sensitivity, and real-time detection. Recently, there have been reports on fluorescent probes for hydrazine hydrate, but few probes can react quickly and can be prepared into PU films for detection.

[0004] In recent years, electrospinning technology is an advanced technology for manufacturing nanofibers. Its advantage is that it can produce nanofibers with excellent properties, which are widely used in medical, environmental protection, energy, filtration and other fields. Electrospinning can produce nanofibers with excellent properties. Electrospinning technology uses high-voltage electric fields to atomize polymer solutions or melts and stretch them into nano-scale filaments to eventually form fibers. In this process, the polymer is subjected to high-energy treatment, which makes the fiber have a very high specific surface area and good mechanical properties, such as flexibility, wear resistance and deformability.

[0005] Electrospinning can achieve large-scale production. Electrospinning technology has the advantages of high efficiency and low cost, and can produce nanofibers on a large scale. In industrial production, by optimizing the ratio of spinning solution, electric field strength, spinning distance and other parameters, the production efficiency and fiber quality can be improved, thus achieving large-scale production.

[0006] Therefore, there is an urgent need to develop a highly sensitive, anti-interference, and selective fluorescent probe and combine it with electrospinning technology to achieve convenient, low-cost, and widespread detection of hydrazine hydrate. Summary of the invention

[0007] In view of this, the purpose of the present invention is to provide a small molecule fluorescent probe, a polyurethane fiber membrane and a preparation method thereof for the detection of hydrazine hydrate. The fluorescent probe prepared by the present invention has the characteristics of good selectivity, strong anti-interference ability, low background interference and high sensitivity. A probe spinning membrane for detecting hydrazine hydrate is prepared using the fluorescent probe, thereby achieving convenient, low-cost and extensive detection of hydrazine hydrate.

[0008] In order to achieve the above object, the present invention provides the following technical solutions:

[0009] In a first aspect, the present invention provides a small molecule fluorescent probe for detecting hydrazine hydrate, wherein the small molecule fluorescent probe is C 18 H 19 N 3 O 2 S, the structural formula is as follows:

[0010]

[0011] In a second aspect, the present invention provides a method for preparing the above-mentioned small molecule fluorescent probe, and the synthesis route is:

[0012]

[0013] Preferably, the above preparation method comprises the following preparation steps:

[0014] 1) 2-(3,4-ethylenedioxythiophene)formaldehyde is suspended in dry acetonitrile and cooled to 0°C; N-bromosuccinimide is added and the mixture is stirred at room temperature for 50 to 80 hours, the mixture is transferred to a separatory funnel together with ethyl acetate, first extracted with 10% Na2CO3 aqueous solution 2 to 3 times, 100 to 200 mL each time, then extracted with water 2 to 3 times, 100 to 200 mL each time, then anhydrous sodium sulfate (100 to 220 g) is added and stirred and dried for 1 to 2 hours, and then anhydrous sodium sulfate solids are removed by suction filtration with a Buchner funnel, and then petroleum ether and ethyl acetate (volume ratio of 40 to 60:1) are used as eluent columns, and compound 2 is obtained after chromatography purification;

[0015] 2) Product 2 is placed in a pressure tube, and then ethanol, malononitrile, glacial acetic acid and piperidine are placed in turn in an oil bath at 80-120° C. to react for 4-8 hours, and then sodium bicarbonate is added to the solution to neutralize the pH value to 7, and purified by column chromatography to obtain compound 3;

[0016] 3) Compound 3 was mixed evenly with 4-triphenylamine borate and tetrakis(triphenylphosphine)palladium in toluene, and then an aqueous potassium carbonate solution was added, and the mixture was reacted in a N2 atmosphere at 70 to 90°C for 20 to 30 hours. After the reaction was completed, the mixture was extracted with dichloromethane and water, and anhydrous sodium sulfate was added after extraction to remove moisture from the solution. The red fluorescent probe EDOT-D was obtained after purification by column chromatography.

[0017] Preferably, in step 1), the volume mass ratio of 2-(3,4-ethylenedioxythiophene)formaldehyde, acetonitrile and N-bromosuccinimide is 3-5 g: 80-120 mL: 3-5 g.

[0018] Preferably, in step 1), the amount of ethyl acetate used is 100-300 mL; the amount of reagent used in each extraction is 100-200 mL; and the amount of anhydrous sodium sulfate used is 100-220 g.

[0019] Preferably, in step 2), the volume mass ratio of compound 2, ethanol, malononitrile, glacial acetic acid and piperidine is 350-400 mg: 5-8 ml: 100-150 mg: 160-240 μL: 40-60 μL.

[0020] Preferably, in the step 3), the volume mass ratio of compound 3, 4-triphenylamine borate, tetrakis(triphenylphosphine)palladium, toluene and potassium carbonate aqueous solution is 100-200 mg: 100-200 mg: 90-140 mg: 5-7 ml: 0.3-0.7 ml; the potassium carbonate aqueous solution is prepared by mixing 100-150 mg of potassium carbonate with 0.3-0.6 ml of deionized water.

[0021] Preferably, the volume ratio of petroleum ether to ethyl acetate in step 3) is 40 to 60:1

[0022] In a third aspect, the present invention provides a method for preparing a polyurethane fiber membrane for hydrazine hydrate detection, comprising the following steps:

[0023] The small molecule fluorescent probe, N, N-dimethylformamide and polyurethane are uniformly mixed and stirred for 4 to 8 hours before being electrostatically spun in a spinning machine to obtain a polyurethane fiber membrane for hydrazine hydrate detection.

[0024] Preferably, the mass ratio of the small molecule fluorescent probe, N,N-dimethylformamide, and polyurethane is 3-5 μg: 5-7 mg: 1-3 g.

[0025] Contains at least the following beneficial technical effects:

[0026] (1) The fluorescent probe prepared by the present invention has the characteristics of good selectivity, strong anti-interference ability, low background interference and high sensitivity.

[0027] (2) The present invention further utilizes fluorescent probes to prepare probe spinning membranes for detecting hydrazine hydrate, thereby achieving convenient, low-cost, and extensive detection of hydrazine hydrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 is the 1H NMR spectrum of the small molecule fluorescent probe in Example 1;

[0029] Figure 2 Absorption and fluorescence spectra of small molecule fluorescent probes in different solvents;

[0030] Figure 3 Selectivity map data for small molecule fluorescent probes;

[0031] Figure 4 Imaging of hydrazine hydrate in cells as a small molecule fluorescent probe;

[0032] Figure 5 It is a membrane made of small molecule fluorescent probes by electrospinning;

[0033] Figure 6 This is the fluorescence spectrum of the small molecule fluorescent probe spun membrane and its effect under UV. DETAILED DESCRIPTION

[0034] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] The term "include" or "comprising" in the present invention is an open description containing the specified components or steps described, and other specified components or steps that will not be substantially affected.

[0036] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0037] If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased through regular channels.

[0038] Example 1

[0039] This embodiment provides a method for preparing a small molecule fluorescent probe for hydrazine hydrate detection, the steps are as follows:

[0040] 1) 4.04 g of 2-(3,4-ethylenedioxythiophene) formaldehyde was suspended in 100 mL of dry acetonitrile and cooled to 0°C; 4.36 g of N-bromosuccinimide was added and the mixture was stirred at room temperature for 60 hours. The mixture was transferred to a separatory funnel together with 150 mL of ethyl acetate and firstly precipitated with 10% Na 2 CO 3 The mixture was extracted twice with 100 mL of aqueous solution each time, and then extracted twice with 100 mL of water each time, and then anhydrous sodium sulfate (200 g) was added and stirred to dry for 1 hour, and then the anhydrous sodium sulfate solid was removed by suction filtration using a Buchner funnel, and then petroleum ether and ethyl acetate (volume ratio of 50:1) were used as eluent columns, and compound 2 was obtained after chromatography purification. ;

[0041] 2) 371.9 mg of product 2 was placed in a pressure tube, and then 6.0 mL of ethanol, 132.1 mg of malononitrile, 200.0 μL of glacial acetic acid and 20.0 μL of piperidine were added in sequence and reacted in an oil bath at 100° C. for 5 hours, and then sodium bicarbonate was added to the solution to neutralize the pH value to 7, and purified by column chromatography to obtain compound 3;

[0042] 3) 148.6 mg of compound 3, 144.6 mg of 4-triphenylamine borate, and 115.6 mg of tetrakis(triphenylphosphine)palladium were mixed in 6 ml of toluene, and then a mixture of 138.2 mg of potassium carbonate and 0.5 ml of deionized water was added, and then heated to N 2 atmosphere and react at 80° C. for 24 hours. After the reaction is completed, it is extracted with dichloromethane and water. After extraction, anhydrous sodium sulfate is added to remove the water in the solution. After purification by column chromatography, the red fluorescent probe EDOT-D is obtained.

[0043] The NMR data are as follows:

[0044] 1 HNMR (400 MHz, DMSO-d 6 ,)δ8.14(s,1H),7.67(d,J=8.8Hz,2H),7.35(dJ=8.3Hz,4H),7.11(dd,J=15.9,7.4Hz,6H),6.97(d J=8.8Hz,2H),4.51(s,2H),4.41(s,2H).

[0045] Example 2

[0046] This embodiment provides a method for preparing a small molecule fluorescent probe for hydrazine hydrate detection, the steps are as follows:

[0047] 1) 3 g of 2-(3,4-ethylenedioxythiophene) formaldehyde was suspended in 80 mL of dry acetonitrile and cooled to 0°C; 3 g of N-bromosuccinimide was added and the mixture was stirred at room temperature for 50 hours. The mixture was transferred to a separatory funnel together with 100 mL of ethyl acetate and firstly heated with 10% Na 2 CO 3 The mixture was extracted twice with 150 mL of aqueous solution each time, and then extracted twice with 150 mL of water each time, and then anhydrous sodium sulfate (100 g) was added and stirred to dry for 2 hours, and then the anhydrous sodium sulfate solid was removed by suction filtration using a Buchner funnel, and then petroleum ether and ethyl acetate (volume ratio of 40:1) were used as eluent columns, and compound 2 was obtained after chromatography purification. ;

[0048] 2) 350 mg of product 2 was placed in a pressure tube, and then 5.0 mL of ethanol, 100 mg of malononitrile, 160 μL of glacial acetic acid and 40.0 μL of piperidine were added in sequence and reacted in an oil bath at 80° C. for 6 hours, and then sodium bicarbonate was added to the solution to neutralize the pH value to 7, and purified by column chromatography to obtain compound 3;

[0049] 3) 100 mg of compound 3, 100 mg of 4-triphenylamine borate and 90 mg of tetrakis(triphenylphosphine)palladium were mixed in 5 ml of toluene, and then a mixture of 100 mg of potassium carbonate and 0.3 ml of deionized water was added. 2 atmosphere and react at 70° C. for 20 hours. After the reaction is completed, it is extracted with dichloromethane and water. After extraction, anhydrous sodium sulfate is added to remove water in the solution. After purification by column chromatography, the red fluorescent probe EDOT-D is obtained.

[0050] Example 3

[0051] This embodiment provides a method for preparing a small molecule fluorescent probe for hydrazine hydrate detection, the steps are as follows:

[0052] 1) 5 g of 2-(3,4-ethylenedioxythiophene) formaldehyde was suspended in 120 mL of dry acetonitrile and cooled to 0°C; 5 g of N-bromosuccinimide was added and the mixture was stirred at room temperature for 80 hours. The mixture was transferred to a separatory funnel together with 200 mL of ethyl acetate and firstly heated with 10% Na 2 CO 3The mixture was extracted twice with 200 mL of aqueous solution each time, and then extracted twice with 100 mL of water each time, and then anhydrous sodium sulfate (200 g) was added and stirred to dry for 2 hours, and then the anhydrous sodium sulfate solid was removed by filtration using a Buchner funnel, and then petroleum ether and ethyl acetate (volume ratio of 60:1) were used as eluent columns, and compound 2 was obtained after chromatography purification. ;

[0053] 2) 400 mg of product 2 was placed in a pressure tube, and then 8.0 mL of ethanol, 150 mg of malononitrile, 240.0 μL of glacial acetic acid and 60.0 μL of piperidine were added in sequence and reacted in an oil bath at 100° C. for 5 hours, and then sodium bicarbonate was added to the solution to neutralize the pH value to 7, and purified by column chromatography to obtain compound 3;

[0054] 3) 200 mg of compound 3, 200 mg of 4-triphenylamine borate and 140 mg of tetrakis(triphenylphosphine)palladium were mixed in 7 ml of toluene, and then a mixture of 150 mg of potassium carbonate and 0.6 ml of deionized water was added. 2 atmosphere and react at 90° C. for 30 hours. After the reaction is completed, it is extracted with dichloromethane and water. After extraction, anhydrous sodium sulfate is added to remove water in the solution. After purification by column chromatography, the red fluorescent probe EDOT-D is obtained.

[0055] Example 4

[0056] Take 0.2 mg of the small molecule fluorescent probe EDOT-D prepared in Example 1, 6 mg of N,N-dimethylformamide, and 2 g of polyurethane (HDW-3020), mix them evenly, stir for 5 hours, and then perform electrospinning in a spinning machine to obtain a polyurethane fiber membrane for hydrazine hydrate detection (negative voltage: -7 V; positive voltage: 26 V).

[0057] Experimental Example 1

[0058] Absorption and fluorescence spectra of probe EDOT-D in different solvents;

[0059] The probe EDOT-D prepared in Example 1 was dissolved in dimethyl sulfoxide (DMSO) to prepare a 1 mmol / L stock solution. 20 μL of the stock solution was taken each time and added to 2 mL of different solvents for fluorescence ultraviolet absorption testing. Figure 2 As shown, Figure 2 a is the fluorescence spectrum, Figure 2 b is the UV absorption spectrum.

[0060] Experimental Example 2

[0061] Probe EDOT-D selectivity profile data

[0062] The probe EDOT-D prepared in Example 1 was dissolved in dimethyl sulfoxide (DMSO) to prepare a 1 mmol / L stock solution. Deionized water was used to prepare all 10 mmol / L interference solutions. Each time, 20 μL of the stock solution was taken and added to 2 mL of PBS buffer solutions with different pH values. The fluorescence spectra were as follows: Figure 3 As shown. Figure 3 It can be seen that after adding the probe EDOT-D, the fluorescence intensity does not change much when the pH changes, and the influence of various interfering solvents on the probe is also very small. Figure 3 .

[0063] Experimental Example 3

[0064] Imaging of hydrazine hydrate in cells using the probe EDOT-D

[0065] Take Example 1 and add EDOT-D (10 μM) to the culture medium of HELA cells (2×105 cells / cm2) and culture for 30 minutes. Add 0, 5, 20, and 40 μL of hydrazine hydrate solution (10 μM) to the HELA cells and continue to culture for 30 minutes. Confocal imaging of the four groups of cells was performed under two different excitations. The EDOT-D green channel image λex=405nm, λem=480-530nm, and the EDOT red channel image λex=405nm, λem=640-680nm, see Figure 4 .

[0066] Experimental Example 4

[0067] The probe EDOT-D was made into a membrane by electrospinning

[0068] Take Example 1 and mix EDOT-D (0.2 mg) with N, N-dimethylformamide (DMF) (6 mg) and polyurethane (HDW-3020) (2 g) evenly. After stirring for 5 hours, electrospinning was performed in a spinning machine (negative voltage: -7 V; positive voltage: 26 V) to prepare a polyurethane EDOT-D fluorescent probe spinning membrane. Figure 5 .

[0069] Experimental Example 5

[0070] Fluorescence spectrum of probe EDOT-D spinning membrane and its effect under UV light

[0071] Take the prepared EDOT-D spinning membrane and cut out two pieces of similar size and mass (20 mg). Put one piece into PBS solution (100 ml) and the other into hydrazine hydrate solution (200 mM) prepared by PBS. Take pictures of the illumination effect under UV light at the same time period (0, 1, 2, 3, 5, 16 hours) and take out to test the change of fluorescence intensity. Figure 6 .

[0072] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A small molecule fluorescent probe for hydrazine hydrate detection, characterized in that: The small molecule fluorescent probe is C 18 H 19 N3O2S, the structural formula is as follows:

2. The method for preparing the small molecule fluorescent probe according to claim 1, characterized in that: The synthetic route is:

3. The preparation method according to claim 2, characterized in that: The method comprises the following preparation steps: 1) 2-(3,4-ethylenedioxythiophene)formaldehyde was suspended in dry acetonitrile and cooled to 0°C; N-bromosuccinimide was added and the mixture was stirred at room temperature for 50 to 80 hours, the mixture was transferred to a separatory funnel together with ethyl acetate, and extracted with 10% Na2CO3 aqueous solution 2 to 3 times each time, and then extracted with water 2 to 3 times each time, and then anhydrous sodium sulfate was added and stirred and dried for 1 to 2 hours, and then anhydrous sodium sulfate solids were removed by suction filtration with a Buchner funnel, and then petroleum ether and ethyl acetate were used as eluent columns, and compound 2 was obtained after chromatography purification; 2) Product 2 is placed in a pressure tube, and then ethanol, malononitrile, glacial acetic acid and piperidine are placed in turn in an oil bath at 80-120° C. to react for 4-8 hours, and then sodium bicarbonate is added to the solution to neutralize the pH value to 7, and purified by column chromatography to obtain compound 3; 3) Compound 3 was mixed evenly with 4-triphenylamine borate and tetrakis(triphenylphosphine)palladium in toluene, and then an aqueous potassium carbonate solution was added, and the mixture was reacted in a N2 atmosphere at 70 to 90°C for 20 to 30 hours. After the reaction was completed, the mixture was extracted with dichloromethane and water, and anhydrous sodium sulfate was added after extraction to remove moisture from the solution. The red fluorescent probe EDOT-D was obtained after purification by column chromatography.

4. The preparation method according to claim 3, characterized in that: In the step 1), the volume mass ratio of 2-(3,4-ethylenedioxythiophene)formaldehyde, acetonitrile and N-bromosuccinimide is 3-5 g: 80-120 mL: 3-5 g.

5. The preparation method according to claim 3, characterized in that: In the step 1), the amount of ethyl acetate used is 100-300 mL; the amount of reagent used in each extraction is 100-200 mL; and the amount of anhydrous sodium sulfate used is 100-220 g.

6. The preparation method according to claim 3, characterized in that: In the step 2), the volume mass ratio of compound 2, ethanol, malononitrile, glacial acetic acid and piperidine is 350-400 mg: 5-8 ml: 100-150 mg: 160-240 μL: 40-60 μL.

7. The preparation method according to claim 3, characterized in that: In the step 3), the volume mass ratio of compound 3, 4-triphenylamine borate, tetrakis(triphenylphosphine)palladium, toluene and potassium carbonate aqueous solution is 100-200 mg: 100-200 mg: 90-140 mg: 5-7 ml: 0.3-0.7 ml; the potassium carbonate aqueous solution is prepared by mixing 100-150 mg of potassium carbonate with 0.3-0.6 ml of deionized water.

8. The preparation method according to claim 3, characterized in that: In the step 3), the volume ratio of petroleum ether to ethyl acetate is 40-60:

1.

9. A method for preparing a polyurethane fiber membrane for hydrazine hydrate detection, characterized in that: The following steps are involved: The small molecule fluorescent probe, N, N-dimethylformamide and polyurethane are uniformly mixed and stirred for 4 to 8 hours before being electrostatically spun in a spinning machine to obtain a polyurethane fiber membrane for hydrazine hydrate detection.

10. The preparation method according to claim 9, characterized in that: The mass ratio of the small molecule fluorescent probe, N,N-dimethylformamide and polyurethane is 3-5 μg: 5-7 mg: 1-3 g.

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