A Fluorescent Probe for Hydrazine Detection with a Binaphthol Matrix Structure, Its Preparation Method and Application

Abstract

The present invention provides a fluorescent probe for detecting hydrazine with a binaphthol matrix structure, its preparation method and application. The target probe is 1,10-dioxime dioxanthene anthracene, and its chemical structural formula is: #imgabs0#. The present invention also gives the specific preparation method of the target probe. The present invention synthesizes the target probe 1,10-dioxime dioxanthene anthracene from 1,10-dialdehyde dioxanthene anthracene in one step. The synthesis route is simple, and the raw materials are cheap and easily available. The oxime group on the conjugate structure of the target probe can be used as an identification site to achieve specific detection of hydrazine. The target probe has a short response time, obvious phenomenon, and high sensitivity to hydrazine, realizing selective and rapid detection of hydrazine, and can be applied to a wide pH range and quantitative detection.

Description

Technical Field

[0001] The present invention relates to the technical field of fluorescent probes, and particularly to a fluorescent probe for detecting hydrazine with a binaphthol matrix structure, and a preparation method and application thereof. Background Art

[0002] Hydrazine (N2H4) is a very important chemical substance. Due to its strong alkalinity, reducibility and flammability, it has been widely used in industrial manufacturing, agricultural production, aerospace and other fields. However, N2H4 is considered highly toxic and potentially carcinogenic. Due to its wide application and excellent water solubility, N2H4 can easily enter the environmental system, causing serious environmental pollution. In addition, N2H4 can easily enter and accumulate in the human body through the food chain, thereby causing serious damage to the human respiratory tract, kidneys, liver and central nervous system. Therefore, the development and research of a rapid, effective, convenient and accurate N2H4 detection method is of great significance to the healthy development of mankind.

[0003] At present, the detection methods of hydrazine mainly include spectrophotometry, electrochemistry, chemiluminescence, chromatographic analysis, titrimetric analysis, surface enhanced Raman spectroscopy, etc. In the application of these methods, the sample preparation process is complex, the detection process causes great damage to the sample, and these methods cannot achieve real-time in-situ detection. Among them, fluorescent probes have received extensive attention because of their high sensitivity, good selectivity, fast response speed, and the ability to achieve real-time in-situ detection, which just solves the problems that cannot be solved by traditional detection methods.

[0004] However, among the existing fluorescent probes, there are few fluorescent probes for detecting hydrazine, and they have some defects. These fluorescent probes often have disadvantages such as long response time, poor anti-interference ability, narrow pH range, and poor photostability. Summary of the Invention

[0005] In view of the above-mentioned disadvantages of the prior art, the purpose of the present invention is to provide a fluorescent probe for detecting hydrazine with a binaphthol matrix structure, which is used to solve the problems that there are few fluorescent probes for detecting hydrazine in the prior art, and the response time is long, the anti-interference ability is poor, the pH range is narrow, and the photostability is poor. At the same time, the present invention will also provide a preparation method of a fluorescent probe for detecting hydrazine with a binaphthol matrix structure; in addition, the present invention will also provide an application of a fluorescent probe for detecting hydrazine with a binaphthol matrix structure.

[0006] To achieve the above object and other related objects, the present invention provides the following technical solutions:

[0007] In the first aspect of the present invention, there is provided a fluorescent probe for detecting hydrazine with a binaphthol matrix structure, whose chemical name is: 1,10-dioxime dioxanthene anthracene, and its chemical structural formula is: .

[0008] In a second aspect of the present invention, a method for preparing a fluorescent probe for hydrazine detection with a binaphthol parent structure is provided, comprising the following steps:

[0009] S1. Using the racemate of binaphthol as a substrate, anhydrous potassium carbonate as a base, copper chloride as a catalyst, and N-methylimidazole as a ring-closing agent, synthesize dioxanthroanthracene;

[0010] S2. Using the dioxanthroanthracene obtained in step S1 as a substrate, react with POCl3 to introduce aldehyde groups at its 1,10 positions to obtain a probe precursor, namely 1,10-dialdehyde dioxanthroanthracene;

[0011] S3. React 1,10-dialdehyde dioxanthroanthracene with hydroxylamine to obtain the target probe, namely 1,10-dioxime dioxanthroanthracene;

[0012] The reaction formula of this preparation process is as follows: .

[0013] In an embodiment of the present invention, step S1 is completed by the following method: Add the racemate of binaphthol, copper chloride, and anhydrous potassium carbonate to a solvent, stir well to dissolve it, and after the solution becomes transparent, slowly add N-methylimidazole, heat under reflux at 120 °C for 20 hours, distill off the solvent under reduced pressure, then purify by column chromatography, and spin-dry to obtain a yellow crystal, namely dioxanthroanthracene, whose chemical structural formula is: .

[0014] Among them, the solvent is selected from m-xylene or DMF; preferably DMF is used as the solvent for subsequent extraction. The eluent of the column chromatography is selected from petroleum ether / dichloromethane (PE / DCM) with a volume ratio of 19:1.

[0015] In an embodiment of the present invention, the racemate of binaphthol is prepared by the following method: Add powdered 2-naphthol to an aqueous FeCl3 solution to obtain a suspension, heat the suspension with sufficient stirring, filter after cooling, dissolve the separated solid in CH2Cl2, wash, decolorize, dry, filter, and remove the solvent under vacuum for the obtained solution, obtain a solid crude product, vacuum-dry the crude product at room temperature, and recrystallize with toluene to obtain the racemate of binaphthol in the form of white needles, whose chemical structural formula is: .

[0016] In one embodiment of the present invention, the step S2 is completed by the following method: Add POCl3 to the DMF solvent, add the dioxanthra[2,3-b:2',3'-f]anthracene prepared in step S1 during stirring, slowly raise the temperature to 60 ± 2 °C, stop after reacting for a period of time; adjust the pH to neutral with saturated sodium carbonate solution to obtain a red flocculent precipitate, filter it by suction, wash, dry, purify it by chromatography column, and rotary evaporate to obtain a red powdery solid, namely 1,10-dialdehyde dioxanthra[2,3-b:2',3'-f]anthracene. Preferably, add POCl3 to the DMF solvent, add the dioxanthra[2,3-b:2',3'-f]anthracene prepared in step S1 during stirring, slowly raise the temperature to 60 °C, and stop after reacting for 12 h.

[0017] Among them, the eluent of the chromatography column is selected from petroleum ether / dichloromethane (PE / DCM) with a volume ratio of 19:1.

[0018] Further, in step S2, 1 - 2 ml of POCl3 and 300 mg of dioxanthra[2,3-b:2',3'-f]anthracene are added to every 20 - 30 ml of DMF solvent. Preferably, 1 - 2 ml of POCl3 and 300 mg of dioxanthra[2,3-b:2',3'-f]anthracene are added to every 25 ml of DMF solvent.

[0019] In one embodiment of the present invention, the step S3 is completed by the following method: Add hydroxylamine hydrochloride and sodium bicarbonate to the DMF solvent, stir well to dissolve them, then add the 1,10-dialdehyde dioxanthra[2,3-b:2',3'-f]anthracene obtained in step S2, raise the temperature to 60 °C, stop the reaction after heating for 1 h, add water, and after extraction, purification by chromatography column, and rotary evaporation, obtain a pale yellow powdery solid, which is the target probe 1,10-dioxime dioxanthra[2,3-b:2',3'-f]anthracene.

[0020] Further, in step S3, 200 mg of purified 1,10-dialdehyde dioxanthra[2,3-b:2',3'-f]anthracene, 160 - 180 mg of hydroxylamine hydrochloride, and 180 - 220 mg of sodium bicarbonate are added to every 20 - 30 ml of DMF solvent.

[0021] Furthermore, in every 25 ml of DMF solvent, add 167 mg of hydroxylamine hydrochloride and 200 mg of sodium bicarbonate, stir magnetically to dissolve, and then add 200 mg of purified 1,10-dialdehyde dioxanthra[2,3-b:2',3'-f]anthracene.

[0022] Among them, dichloromethane is selected for extraction, and the number of extraction times is two to three times. The eluent of the chromatography column is selected from petroleum ether / ethyl acetate (PE / EA) with a volume ratio of 2:1.

[0023] The reaction formula of the specific preparation process is as follows:

[0024] .

[0025] In the third aspect of the present invention, there is provided an application of a fluorescent probe for detecting hydrazine with a binaphthol matrix structure. The target probe prepared by the above preparation method can be used for the specific detection of hydrazine.

[0026] Its detection mechanism is as follows: Under alkaline conditions after adding hydrazine to the target probe, the oxime group is deprotonated and becomes more reactive. Since the target probe contains two oxime groups, one of the groups reacts with hydrazine preferentially, resulting in a poor symmetry of the target probe, which to a certain extent destroys its conjugated structure and leads to a decrease in fluorescence. In addition, there is a certain dynamic equilibrium between the target probe and the probe precursor. The bisaldehyde group of the probe precursor reacts with hydrazine to form a bis-hydrazone structure, causing a change in the emission wavelength of the system and a corresponding decrease in the fluorescence at 465 nm. Refer to Figure 10A 、 10B and 11, and the mass spectrometry and nuclear magnetic resonance results before and after the reaction well confirm this principle.

[0027] Among them, the recognition mechanism of the target probe for hydrazine is as follows: ;

[0028] The recognition mechanism of the probe precursor for hydrazine is as follows: .

[0029] As described above, a fluorescent probe for detecting hydrazine with a binaphthol matrix structure of the present invention, its preparation method and application have the following beneficial effects:

[0030] 1. The present invention uses 1,10-dialdehyde dioxanthrene-embedded anthracene as a probe precursor, and on this basis, the target probe 1,10-dioxime dioxanthrene-embedded anthracene is synthesized in one step. The oxime group on the conjugated structure of the target probe can be used as a recognition site to achieve the specific detection of hydrazine.

[0031] 2. The excitation wavelength of the target probe 1,10-dioxime dioxanthrene-embedded anthracene is 420 nm, which is very suitable for detection in competitive media, and it has strong fluorescence intensity and good photostability, and can be widely used in research fields such as organic optoelectronic materials and biological visualization.

[0032] 3. The target probe can detect hydrazine within 25 s, with a rapid reaction and obvious phenomenon; and the target probe has a high sensitivity to N2H4 and strong anti-interference ability, realizing the selective and rapid detection of hydrazine; at the same time, the target probe can be applied to a wide pH range and quantitative detection.

[0033] 4. The present invention synthesizes the target probe in one step from 1,10-dialdehyde dioxanthrene-embedded anthracene. The synthesis route is simple, the raw materials are cheap and easy to obtain, the reaction conditions are mild, the purification method is simple, and the reaction selectivity and yield are both high. Brief Description of the Drawings

[0034] Figure 1 It is a linear relationship graph showing the change of fluorescence intensity of the target probe for hydrazine detection with the change of hydrazine concentration.

[0035] Figure 2 It is a graph showing the time-dependent fluorescence intensity change of the target probe (5 μM) in DMF solution in the presence of 150 eq hydrazine (λex = 420 nm).

[0036] Figure 3 It is an absorption spectrum graph of the target probe (5 μM) in the absence and presence of hydrazine in DMF solution.

[0037] Figure 4 It is a fluorescence titration spectrum graph of the target probe (5 μM) for different concentrations of hydrazine (0 - 100 eq) (DMF, pH = 7, 25 °C, λem / ex = 535 / 420 nm).

[0038] Figure 5A It is a bar graph showing the ratio of the fluorescence intensity when different cations are added during the recognition of hydrazine (10 eq) by the target probe (5 μM) to the fluorescence intensity without adding cations.

[0039] Figure 5B It is a bar graph showing the ratio of the fluorescence intensity when different cations are added during the recognition of hydrazine (10 eq) by the probe precursor (5 μM) to the fluorescence intensity without adding cations.

[0040] Figure 6A It is a bar graph showing the ratio of the fluorescence intensity when different anions are added during the recognition of hydrazine (10 eq) by the target probe (5 μM) to the fluorescence intensity without adding anions.

[0041] Figure 6B It is a bar graph showing the ratio of the fluorescence intensity when different anions are added during the recognition of hydrazine (10 eq) by the probe precursor (5 μM) to the fluorescence intensity without adding anions.

[0042] Figure 7 It is a graph showing the influence of different pH values on the fluorescence intensity during the recognition of hydrazine by the target probe (10 μM).

[0043] Figure 8A It is a graph showing the color change observed with the naked eye before and after the probe precursor recognizes hydrazine, changing from dark yellow to light yellow.

[0044] Figure 8B It is a graph showing the color change under fluorescence irradiation before and after the probe precursor recognizes hydrazine, changing from yellow to green.

[0045] Figure 9A It is a graph showing the color change observed with the naked eye before and after the target probe recognizes hydrazine, changing from light yellow to dark yellow.

[0046] Figure 9B It is a color change diagram of the target probe before and after identifying hydrazine under fluorescence irradiation, changing from dark green to light green.

[0047] Figure 10A It is the mass spectrum of the target probe before reacting with hydrazine.

[0048] Figure 10B It is the mass spectrum of the target probe after reacting with hydrazine.

[0049] Figure 11 It is the NMR spectrum of the target probe before and after reacting with hydrazine. Specific implementation mode

[0050] The following specific embodiments illustrate the implementation mode of the present invention. Those familiar with this technology can easily understand other advantages and effects of the present invention from the content disclosed in this specification.

[0051] Example 1

[0052] Preparation of dioxanthracene-embedded anthracene:

[0053] Add 1.44 g of the racemate of binaphthol, 1 g of cuprous chloride and 1.38 g of anhydrous potassium carbonate to a round-bottom flask. Add 20 ml of m-xylene at room temperature, heat and stir well to dissolve it. After the solution becomes transparent, slowly add 1 ml of methylimidazole and reflux at 120 °C for 20 hours. Then distill off the solvent under reduced pressure, scrape out the solid in the round-bottom flask, purify it through a chromatographic column (PE:DCM = 19:1), and obtain yellow crystals after rotary evaporation, namely dioxanthracene-embedded anthracene, MS(ESI,m / z): C 20 H 10 O2, found [M] 282.

[0054] Example 2

[0055] Preparation of the probe precursor 1,10-dialdehyde dioxanthracene-embedded anthracene:

[0056] Add 25 mL of DMF to a round-bottom flask, add 2 mL of POCl3 thereto, start magnetic stirring and add 300 mg of the dioxanthrenoanthracene prepared in Example 1. Slowly raise the temperature to 60 °C, stop the reaction after 12 h; pour the solution in the round-bottom flask into a beaker, adjust the pH to neutral with saturated sodium carbonate solution to obtain a red flocculent precipitate. Filter it by suction using a Buchner funnel, wash it with distilled water two to three times, and dry it to obtain the crude product. Purify the crude product through a chromatographic column (PE:DCM = 19:1), spin-dry to obtain a red powdery solid, namely 1,10-diformyldioxanthrenoanthracene. 1H NMR (400 MHz, Chloroform-d) δ 13.94(s, 2H), 12.62 – 12.55 (m, 5H), 12.05 (d, J = 8.9 Hz, 2H), 11.94 (dddd, J =26.1, 8.3, 6.8, 1.4 Hz, 5H), 11.66 (dd, J = 8.5, 1.3 Hz, 2H), 7.27 – 7.21 (m,12H), 6.82 (s, 1H), 5.97 (s, 1H). MS(ESI,m / z): C 22 H 10 O 4， found[M]338。

[0057] Example 3

[0058] Preparation of the target probe 1,10-dioximido-dioxanthrenoanthracene:

[0059] 25 mL of DMF was poured into a round-bottom flask, and 167 mg of hydroxylamine hydrochloride and 200 mg of sodium bicarbonate were added. The mixture was dissolved by electromagnetic stirring, and then 200 mg of 1,10-dialdehyde dioxanthene-embedded anthracene prepared in Example 2 was added. The temperature was raised to 60 °C, and the reaction was stopped after heating for 1 h. Then water was added, and the mixture was extracted with dichloromethane two to three times and purified by a chromatographic column (PE:EA = 2:1). The solvent was evaporated to dryness to obtain a yellowish-brown powdery solid, which was the target probe 1,10-dioxime dioxanthene-embedded anthracene. 1H NMR (400 MHz, Chloroform-d) δ 12.47 (t, J = 8.2 Hz, 2H), 11.91 (d, J = 8.8 Hz, 1H), 11.83 (t, J = 7.3 Hz, 1H), 11.75 (t, J = 7.6 Hz, 1H), 11.60 (d, J = 8.6 Hz, 1H), 8.15 (q, J = 7.0 Hz, 7H), 6.49 (d, J = 14.6 Hz, 1H), 5.76 (t, J = 6.9 Hz, 5H). MS(ESI, m / z): C 22 H 12 O4N2, found [M+1] 369.

[0060] Example 4

[0061] The target probe prepared in Example 3 and the probe precursor prepared in Example 2 were experimentally tested, and the test results are as Figures 1 to 11 shown. Among them, all aqueous solutions were prepared using deionized water. All measurements were carried out in a DMF solution. All pH values were measured using a pH-10C digital pH meter. The absorption spectra were recorded using a Varian UV-Cary 5000 spectrophotometer. The fluorescence spectra were recorded using a Hitachi F-7000 scanning fluorescence spectrophotometer equipped with a xenon flash lamp. The samples used for absorption and fluorescence measurements were included in a 1 cm × 1 cm quartz cuvette (3.5 mL volume).

[0062] 1. Spectral properties of the target probe

[0063] Reference Figure 3 , the absorption and emission spectra of the target probe (5 μM) in the presence or absence of N2H4 in a DMF solution at 25 °C were studied. When N2H4 (100 eq) was added to the probe solution, the target probe detected hydrazine as a quenching-type probe. After adding hydrazine, the fluorescence intensities of the two strong emission peaks at 465 nm and 500 nm both decreased significantly. Similarly, reference Figure 9A and Figure 9B, the color of the target probe observed with the naked eye changed from light yellow to dark yellow before and after recognizing hydrazine; the color of the target probe under fluorescence irradiation changed from dark green to light green before and after recognizing hydrazine. It can be seen that the fluorescence intensity of the target probe decreased significantly after reacting with hydrazine.

[0064] 2. Fluorescence intensity change of the target probe with hydrazine concentration

[0065] Reference Figure 4 , as the concentration of hydrazine increased, the fluorescence intensity of the target probe solution gradually decreased.

[0066] Reference Figure 1 , a good linear relationship y = -2.2743x + 1399.8 (R 2 = 0.9925) was shown between the fluorescence intensity at 465 nm and the concentration of hydrazine, where the concentration of the target probe was 5 10 -6 mol·L -1 , and the concentration of N2H4 was in the range of 40 - 90 eq, based on 3.3σ / k. The detection limit of the target probe was relatively low, being 13.6 10 -6 M.

[0067] 3. Time response of the target probe

[0068] The response speed of a fluorescent probe to an analyte is an important parameter for measuring the performance of the probe. A fluorescent probe with a fast response is expected to be applied in dynamic real-time sensing and monitoring during biomedical research processes.

[0069] The time-dependent fluorescence change of the target probe (5 μM) in a DMF solution at 25 °C in the presence of 150 eq hydrazine was obtained by plotting the fluorescence intensity at 465 nm Figure 2 The fluorescence response curve shown in. Before adding N2H4, the maximum absorption peak of the target probe was at 465 nm; after adding N2H4, the fluorescence intensity of the probe at this wavelength decreased rapidly, almost an instantaneous reaction. The fluorescence change was detected every 10 s, and the results showed that it reached the minimum value at about 25 s, and the system reaction reached equilibrium, with a significant response, thus also reflecting the sensitive reaction characteristic of the target probe.

[0070] 4. Selectivity and competitiveness of the target probe

[0071] High sensitivity, strong anti-interference ability and good selectivity are important references for determining the performance of probe molecules. In actual environmental factors, the presence of common cations, anions and nitrogen-containing small molecule compounds may interfere with the behavior of the probe to recognize hydrazine. Therefore, selectivity and competitive tests of the probe were carried out to ensure the authenticity and reliability of the detection results when the probe actually detects hydrazine. To evaluate the selectivity of the probe, various interfering analyte cations (Na + 、K + 、Ca 2+ 、Mg 2+ 、Cu + 、Cu 2+ 、Co 2+ 、Fe 2+ 、Fe 3+ 、Zn 2+ 、Al 3+ 、NH4 + ); anions (Cl - 、F - 、Br - 、I - 、SO4 2- 、HSO3 - 、HSO4 - 、S 2- 、NO2 - 、NO3 - 、CO3 2- 、HCO3 - 、ClO3 - 、ClO4 - 、BrO3 - 、Cr2O7 2- 、S2O8 2- 、SCN - 、CH3COO - ) were all dissolved in the DMF solution containing the probe (5 μM) at 10 eq. After 2 minutes, the fluorescence intensities of these analytes at 465 nm were measured respectively and compared with the non-interfered blank sample.

[0072] It should be noted that the relative intensity is the ratio of the fluorescence intensity of the probe system after adding ions to the fluorescence intensity of the blank probe system. The closer its value is to 1, the smaller the influence of the ion on the probe, or the lower the selectivity or interference of the probe to the ion.

[0073] As Figure 5A 、 5B 、6A, 6B show, only Fe 2+ 、Fe 3+ and Cr2O7 -The influence on the probe is relatively large, but it is significantly not in the same order of magnitude as that of hydrazine. Therefore, the target probe has low selectivity for various cations and anions, and the influence of various cations and anions on the probe can be almost negligible.

[0074] 5. pH Effect of the Probe Molecule

[0075] Take 1 ml of the standard solution of the target probe with a concentration of 5 μmol / L, and add 1 ml of the mother liquor with pH = 1 - 14 prepared respectively. After measuring with a pH meter, the standard solution with pH = 1 - 14 in the system can be obtained. Perform spectral analysis on the sample with a fluorescence spectrometer, where the excitation wavelength is 535 nm, the emission wavelength scanning range is 480 nm - 600 nm, and the slit width is 5.0 nm / 5.0 nm.

[0076] As Figure 7 shown, the target probe has a good response to strong acids and strong bases, and the fluorescence is relatively stable under alkaline conditions of 7 - 12. In the case of strong acids and strong bases, the fluorescence intensity has a significant increase.

[0077] In summary, the target probe 1,10 - dioxime - bis - anthracene - 9,10 - dione is synthesized by one - step synthesis of 1,10 - dialdehyde - bis - anthracene - 9,10 - dione in the present invention. The synthesis route is simple and the raw materials are cheap and easily available; the oxime group on the conjugate structure of the target probe can be used as an identification site to achieve specific detection of hydrazine; the target probe has a short response time, obvious phenomenon, and high sensitivity to hydrazine, realizing selective and rapid detection of hydrazine, and can be applied to a wide pH range and quantitative detection. Therefore, the present invention effectively overcomes various disadvantages in the prior art and has high industrial utilization value.

[0078] The above embodiments are only illustrative of the principles and effects of the present invention, and are not used to limit the present invention. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes completed by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. A fluorescent probe for detecting hydrazine with a binaphthol parent structure, characterized in that, Its chemical name is: 1,10-dioxime dioxanthene anthracene, and its chemical structural formula is: .

2. A preparation method of a fluorescent probe for hydrazine detection with a binaphthol parent structure, characterized in that, It includes the following steps: S1. Using the racemate of binaphthol as the substrate, anhydrous potassium carbonate as the base, copper chloride as the catalyst and N-methylimidazole as the ring-closing agent, synthesize dioxanthraanthracene; S2. Using the dioxanthraanthracene obtained in step S1 as the substrate, reacting with DMF and POCl3 to introduce aldehyde groups at its 1,10 positions to obtain a probe precursor, namely 1,10-dialdehyde dioxanthraanthracene; S3. Reacting 1,10-dialdehyde dioxanthraanthracene with hydroxylamine to obtain the target probe, namely 1,10-dioxime dioxanthraanthracene; The reaction formula of this preparation process is as follows: 。 3. The preparation method of a fluorescence probe for hydrazine detection with a binaphthol parent structure according to claim 2, characterized in that, The step S1 is completed by the following method: Add the racemate of binaphthol, copper chloride and anhydrous potassium carbonate to the solvent, stir well to dissolve it. After the solution becomes transparent, slowly add N-methylimidazole, heat under reflux at 120 °C for 20 hours, remove the solvent by reduced pressure distillation, then purify by column chromatography, and spin-dry to obtain yellow crystals, namely dioxanthraanthracene.

4. The preparation method of a fluorescent probe for hydrazine detection with a binaphthol parent structure according to claim 3, characterized in that, The solvent is selected from m-xylene or DMF; the eluent of the column chromatography is selected from petroleum ether / dichloromethane with a volume ratio of 19:

1.

5. The preparation method of a fluorescent probe for hydrazine detection with a binaphthol parent structure according to any one of claims 2 to 4, characterized in that, The racemate of binaphthol is prepared by the following method: Add powdered 2-naphthol to the aqueous FeCl3 solution to obtain a suspension, heat the suspension with sufficient stirring, filter after cooling, dissolve the separated solid in CH2Cl2, wash, decolorize, dry, filter the obtained solution, remove the solvent under vacuum, obtain a solid crude product, vacuum-dry the crude product at room temperature, and recrystallize with toluene to obtain the white needle-like racemate of binaphthol.

6. The preparation method of a fluorescent probe for hydrazine detection with a binaphthol parent structure according to claim 2, characterized in that, The step S2 is completed by the following method: Add POCl3 to the DMF solvent, add the dioxanthraanthracene obtained in step S1 during stirring, slowly heat up to 60 ± 2 °C, stop the reaction after a period of reaction; adjust the pH to neutral with saturated sodium carbonate solution to obtain a red flocculent precipitate, filter it by suction, wash, dry, purify by column chromatography, and spin-dry to obtain a red powdery solid, namely 1,10-dialdehyde dioxanthraanthracene.

7. The preparation method of a fluorescence probe for hydrazine detection with a binaphthol parent structure according to claim 6, characterized in that, In step S2, 1 - 2 ml of POCl3 and 300 mg of dioxanthraanthracene are added to every 20 - 30 ml of DMF solvent; the eluent of the column chromatography is selected from petroleum ether / dichloromethane with a volume ratio of 19:

1.

8. The preparation method of a fluorescence probe for hydrazine detection with a binaphthol matrix structure according to claim 2, characterized in that, The step S3 is completed by the following method: Add hydroxylamine hydrochloride and sodium bicarbonate to the DMF solvent, stir well to dissolve it, then add the 1,10-dialdehyde dioxanthraanthracene obtained in step S2, heat up to 60 °C, stop the reaction after heating for 1 h, then add water, after extraction, purification by column chromatography, and spin-drying, obtain a yellowish-brown powdery solid, which is the target probe 1,10-dioxime dioxanthraanthracene.

9. The preparation method of a fluorescence probe for hydrazine detection with a binaphthol parent structure according to claim 8, characterized in that, In step S3, 200 mg of purified 1,10-dialdehyde dioxanthraanthracene, 160 - 180 mg of hydroxylamine hydrochloride and 180 - 220 mg of sodium bicarbonate are added to every 20 - 30 ml of DMF solvent; the eluent of the column chromatography is selected from petroleum ether / ethyl acetate with a volume ratio of 2:

1.

10. Use of a fluorescent probe for detecting hydrazine with a binaphthol parent structure according to claim 1, characterized in that, For the specific detection of hydrazine, and this application does not belong to disease diagnosis.

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