WO2019051627A1

WO2019051627A1 - Fluorogenic probe for detecting polyazole heterocyclic compound and preparation method therefor

Info

Publication number: WO2019051627A1
Application number: PCT/CN2017/000748
Authority: WO
Inventors: 董宇平; 张亚会; 许卫权; 佟斌; 石建兵
Original assignee: 北京理工大学; 董宇平; 张亚会; 许卫权; 佟斌; 石建兵
Priority date: 2017-09-13
Filing date: 2017-12-25
Publication date: 2019-03-21
Also published as: CN107721837A; CN107721837B

Abstract

The present invention relates to a fluorogenic probe for detecting a polyazole heterocyclic compound and a preparation method therefor, relating to the technical field of fluorescent chemical sensors. The fluorogenic probe is prepared from HPB-ID, an organic solvent, and water. The fluorogenic probe lights up in response to a polyazole heterocyclic compound having three or more nitrogen atoms and having a 5-membered ring structure, and achieves detection limits to the ng level. Further, the fluorogenic probe has good specific selectivity for polyazole heterocyclic compounds having three or more nitrogen atoms and having 5-membered ring structures, and can exclude interference from other common explosive substances and diazole compounds. The fluorogenic probe of the present invention has the advantages of a simple preparation method, convenient detection operation, strong practicability, and easy promotion.

Description

Light-emitting fluorescent probe for detecting polyazole-based heterocyclic compound and preparation method thereof

Technical field

The invention relates to a fluorescent probe for detecting a high energy density material, in particular to a lighting fluorescent probe for detecting a polyazole heterocyclic compound having high energy density and a preparation method thereof, and belongs to a fluorescent chemical sensor. Technical field.

Background technique

High energy density material (HEDM) consists of high-energy components, which refers to substances with high potential per unit volume/mass, ie energetic materials with high energy density, which can be used to make explosives, propellants or pyrotechnics. Product. Since the polyazole-containing heterocyclic compound has a high nitrogen content, the molecule contains a large number of high-energy chemical bonds such as NN bond and NC bond, and has the advantages of high heat generation, high density, and easy to achieve zero oxygen balance, and decomposition product pollution. The degree is low. Therefore, polyazole-based heterocyclic compounds have become one of the research hotspots of current high energy density energetic materials.

Among the polyazole heterocyclic compounds, 3-nitro-1,2,4-triazol-5-one (NTO) has been affected in recent years. A representative high energy density material of general interest with a density of up to 1.93 g/cm ³ . According to reports, the NTO detonation energy is close to that of black gold (RDX), but the sensitivity is similar to triaminotrinitrobenzene (TATB), which is a low-volume explosive for application. NTO is low in toxicity, easy to prepare raw materials, easy to prepare, and has good compatibility with other materials. Research on its synthesis, properties and applications has received widespread attention at home and abroad and has been widely used. Similarly, other derivatives of triazole are also good candidates for explosives. 1,5-diaminotetrazole (DAT) has higher nitrogen content, higher normal enthalpy of formation and good thermal stability, and is a representative of tetrazolium high energy density energetic materials.

Because of the excellent application of polyazole heterocyclic compounds in the field of explosives, it has certain dangers in daily life. At present, there are explosive detection methods in densely populated places such as airports, subway stations, shopping malls and cinemas, but The detection method is complicated, and the high cost increases the difficulty of security protection, which makes the illegal elements available, which brings certain threats to life safety and public utilities.

Currently commonly used methods for detecting explosives include chromatographic mass spectrometry, colorimetry, fluorescence, fluorescence resonance energy transfer, electrochemical, and surface plasmon resonance. Among them, the fluorescence method is widely used due to its advantages of simple operation, low cost, fast detection speed and high sensitivity. At present, the method of detecting explosives by fluorescence mainly utilizes the nitro group contained in the explosive molecules to act on the chromophore in the luminescent molecule to quench its fluorescence efficiency, thereby achieving the purpose of detection. However, this detection method is suitable for detecting derivatives of trinitrobenzene, such as trinitrophenol (PA) and trinitrotoluene (TNT), since the nitrogen content of the trinitrobenzene derivative is low, With the development of science and technology, PA and TNT have gradually been replaced by other high-energy high-energy density materials. In addition, the detection method based on fluorescence quenching mechanism is easily interfered by the application environment and conditions, and the detection results are not suitable for observation. It is even prone to false detection signals, which limits further applications (Dongdong Li, Jianzhao Liu, Ryan TKKwok, Zhiqiang Liang, Ben Zhong Tang and Jihong Yu, Supersensitive detection of explosives by recyclable AIE luminogen-functionalized mesoporous materials. Chem.Commun. ,2012,48,7167-7169;Yingxin Ma,Hao Li,Shan Peng,and Leyu Wang,Highly Selective and Sensitive Fluorescent Paper Sensor for Nitroaromatic Explosive Detection.Anal.Chem.2012,84,8415-8421;Jianzhao Liu,Yongchun Zhong,Ping Lu,Yuning Hong,Jacky WY Lam,Mahtab Faisal,Yon g Yu, Kam Sing Wong and Ben Zhong Tang, A superamplification effect in the detection of explosives by a fluorescent hyperbranched poly(silylenephenylene) with aggregation-enhanced emission characteristics. Polym. Chem., 2010, 1, 426-429; Shu-Ran Zhang,Dong-Ying Du,Jun-Sheng Qin,Shao-Juan Bao,Shun-Li Li,WenWen He,Ya-Qian Lan,Ping Shen,and Zhong-Min Su,A Fluorescent Sensor for Highly Selective Detection of Nitroaromatic Explosives Based On a 2D, Extremely Stable, Metal-Organic Framework. Chem. Eur. J. 2014, 20, 3589-3594). Due to the limitations of these two defects, the detection of explosives by fluorescence, especially high-energy-density materials, has received widespread attention in recent years, but has not been properly solved and broken.

The fluorescing method of illuminating the detection of explosives can largely overcome the above disadvantages because of its higher detection sensitivity and greater specificity. Professor Wang Bo from the School of Chemistry, Beijing Institute of Technology, etc., synthesized a Metal Organic Framework (MOF) material in 2014, which has achieved the detection of NTO illumination, which is currently available for the detection of explosives. Almost the only "turn-on" type fluorescent compound (Yuexin Guo, Xiao Feng, Tianyu Han, Shah Wang, Zhengguo Lin, Yuping Dong, and Bo Wang, Tuning the Luminescence of Metal-Organic Frameworks for Detection of Energetic Heterocyclic Compounds. J. Am. Chem. Soc. 2014, 136, 15485-15488). However, the MOF material can only achieve illumination type detection for NTO, that is, it has strong specificity, and detection of polyazoles cannot be realized, which is not suitable for practical use. Therefore, the detection of rapid and sensitive "lighting" type fluorescence of explosives has become a popular research of researchers at this stage.

Summary of the invention

Since most of the current detection of explosives requires large equipment, complicated procedures, and the use of more fluorescent methods are almost annihilated, these problems greatly increase the difficulty of detecting explosives. In view of the above problems, an object of the present invention is to provide a light-emitting fluorescent probe for detecting a polyazole-based heterocyclic compound, which has a light-emitting response and a good specificity for a polyazole-based heterocyclic compound. Selectivity, and the detection limit reaches ng level; the preparation method of the fluorescent probe is simple, convenient to operate, strong in practicability, and easy to popularize.

The object of the invention is achieved by the following technical solutions:

A light-emitting fluorescent probe for detecting a polyazole-based heterocyclic compound, which is prepared from HPB-ID, an organic solvent and water;

Wherein, the organic solvent is tetrahydrofuran, dimethyl sulfoxide, acetonitrile or N,N-dimethylformamide, preferably tetrahydrofuran; the volume ratio of organic solvent to water is 1:9, and the mixture of HPB-ID in organic solvent and water The concentration in the solvent is 1×10 ^-3 mol/L to 1×10 ^-5 mol/L, HPB-ID, 2,2'-((1E,3E)-1,2,3,4-tetraphenyl -1,3-butadiene-1,4-substituted)di-1.3 anthrone, the structural formula of which is as follows:

The polyazole-containing heterocyclic compound contains not less than 3 nitrogen atoms and has a five-membered ring structure such as substituted triazole or tetrazolium.

A method for preparing a light-emitting fluorescent probe for detecting a polyazole-based heterocyclic compound according to the present invention, the specific steps of the method are as follows:

(1) Catalyst I, good solvent I, 4-formylbenzeneboronic acid and diphenylacetylene are added to the reactor, and a protective gas is introduced, and the reaction is stirred at 90 ° C to 120 ° C for 40 min to 80 min, and then filtered to collect. The filtrate is spun dry to obtain the crude product I; the crude product I is dissolved in a good solvent II, separated and purified, and dried to obtain the product I;

Wherein, the catalyst I is a mixture of silver carbonate and palladium acetate, and the ratio of the amount of the substance of the silver carbonate to the palladium acetate is preferably 1: (0.025 to 0.035);

The good solvent I is preferably a mixed solvent of n-propanol and water, or acetonitrile; wherein the volume ratio of n-propanol to water is preferably 9:1;

The molar ratio of 4-formylbenzeneboronic acid, diphenylacetylene and silver carbonate is preferably 1: (1 to 1.2):1;

The good solvent II is preferably dichloromethane, chloroform, tetrahydrofuran or ethyl acetate;

The separation and purification is preferably carried out by column chromatography, using petroleum ether and dichloromethane as an eluent; wherein the mass ratio of petroleum ether to dichloromethane is preferably 1:2.5;

The shielding gas is preferably N ₂ or Ar;

(2) The product I, the anthraquinone and the solvent III are added to the reaction vessel, and reacted at 70 ° C to 90 ° C for 3 h to 5 h, then suction filtered, separated and purified, and dried to obtain HPB-ID;

Alternatively, the product I, the anthracenedione, the solvent III and the catalyst II are added to the reaction vessel, and reacted at 50 ° C to 70 ° C for 1 h to 3 h, followed by suction filtration, separation and purification, and drying to obtain HPB-ID;

Wherein, the molar ratio of the product I to the anthracenedion is 1: (2 to 3), preferably 1: 2.4; the catalyst II is a weak base catalyst such as morpholine or triethylamine, and the molar ratio of the product I to the product I is 1-5. 100; Solvent III is an organic solvent such as ethanol or methanol which can dissolve the product I but does not dissolve the product HPB-ID, and the solvent III is added in such a manner that the product I and the anthrone are sufficiently dissolved;

(3) The HPB-ID is dissolved in a mixed solvent of an organic solvent and water, and uniformly mixed to obtain the fluorescent probe.

Beneficial effects:

(1) The fluorescent probe of the present invention has aggregation-inducing luminescent properties, and has a light-emitting response to a high energy density polyazole heterocyclic compound (such as NTO, DTA, etc.), and the detection limit reaches ng level;

(2) The fluorescent probe of the present invention has good specific selectivity and can exclude interference of other high-density energetic materials such as TNT, HMX, RDX, etc.;

(3) The preparation method of the fluorescent probe of the present invention is simple and convenient to operate.

DRAWINGS

Figure 1 is a fluorescence intensity spectrum of HPB-ID in different mixing ratios of THF/H ₂ O;

2 is a fluorescence spectrum showing an increase in the fluorescence intensity of the HPB-ID fluorescent probe as the content of NTO (3-nitro-1,2,4-triazol-5one) increases;

Figure 3 is a line graph showing the relationship between the fluorescence intensity (II ₀ )/I ₀ of the HPB-ID fluorescent probe and the content of NTO;

Figure 4 is a fluorescence spectrum of the fluorescence intensity of the HPB-ID fluorescent probe increased with time after adding 2 × 10 ^-7 mol (2.6 ng) of NTO;

Figure 5 is a fluorescence spectrum of the fluorescence intensity of the HPB-ID fluorescent probe increased with time after adding 2 × 10 ^-7 mol (2.0 ng) of DAT (1,5-diaminotetrazole);

Figure 6 shows the fluorescence intensity of HPB-ID fluorescent probes increasing with time after adding 2 × 10 ^-7 mol (2.3 ng) NT (3-nitro-1,2,4-triazole) Spectral map

Figure 7 shows the increase in fluorescence intensity of HPB-ID fluorescent probes over time after addition of 2 × 10 ^-7 mol (2.7 ng) CTO (3-chloroethyl-1,2,4-triazol-5one) And an increased fluorescence spectrum;

Figure 8 is a fluorescence spectrum of the fluorescence intensity of the HPB-ID fluorescent probe decreased with time after adding 2 × 10 ^-7 mol (4.6 ng) of PA (trinitrophenol);

Figure 9 is a fluorescence spectrum showing the decrease of the fluorescence intensity of the HPB-ID fluorescent probe with the addition of 2 × 10 ^-7 mol (4.5 ng) of TNT (trinitrotoluene);

Figure 10 is a graph showing the fluorescence intensity of the HPB-ID fluorescent probe with almost no change over time after adding 2 × 10 ^-7 mol (5.9 ng) of HMX (cyclotetramethylenetetranitramine);

Figure 11 is a fluorescence spectrum of the fluorescence intensity of the HPB-ID fluorescent probe increased with time after adding 2 × 10 ^-7 mol (4.4 ng) of RDX (cyclotrimethylene trinitramine);

Figure 12 shows the fluorescence intensity of the HPB-ID fluorescent probe with almost constant fluorescence after adding 2×10 ^-7 mol (3.1 ng) CL-20 (hexanitrohexaazaisowurtzitane). Spectral map

Figure 13 is a fluorescence spectrum in which the fluorescence intensity of the HPB-ID fluorescent probe is almost constant with the addition of 2 × 10 ^-7 mol (1.6 ng) of N-IM (N-methylimidazole);

Figure 14 is a fluorescence spectrum of the fluorescence intensity of the HPB-ID fluorescent probe increased with time after adding 2 × 10 ^-7 mol (3.2 ng) of 2N-IM (carbonyldiimidazole);

Figure 15 is a fluorescence spectrum in which the fluorescence intensity of the HPB-ID fluorescent probe is almost constant with the addition of 2 × 10 ^-7 mol (1.3 ng) IM (imidazole);

Fig. 16 is a summary of fluorescence changes of the HPB-ID fluorescent probe after 270 s after the addition of the above substances.

Figure 17 shows the anti-interference detection of NTO in the presence of other explosives.

Detailed ways

The present invention will be described in detail below with reference to specific examples, wherein the method is a conventional method unless otherwise specified, and the raw materials can be obtained from an open commercial route unless otherwise specified.

The main reagent information mentioned in the following examples is shown in Table 1. The main instrument and equipment information is shown in Table 2.

Table 1

Table 2

Example 1

A preparation step of a light-emitting fluorescent probe for detecting a polyazole-based heterocyclic compound is as follows:

(1) 2.00 mmol of 4-formylbenzeneboronic acid, 2.00 mmol of diphenylacetylene, 0.05 mmol of palladium acetate, 2.00 mmol of silver carbonate, 4.5 mL of n-propanol, and 0.5 mL of water were added to a 25 mL three-necked flask, and nitrogen gas was introduced thereto. After stirring at 120 ° C for 60 min, the mixture was suction filtered and the filtrate was evaporated to dryness to give the crude product I. The crude product I was dissolved in 5 mL of dichloromethane, eluting with petroleum ether and dichloromethane (m _petroleum _ether : m _{dichloromethane} = 1:2.5), purified by column chromatography to give a yellow product I;

(2) 0.1 mmol of product I and 0.24 mmol of anthracenedione were added to a 25 mL three-necked flask, and then 10 mL of absolute ethanol was added thereto, and the mixture was refluxed at 80 ° C for 5 hours while stirring, suction-filtered, and the collected solid matter was washed with absolute ethanol. , obtaining a red solid HPB-ID;

(3) Dissolving HPB-ID in THF (tetrahydrofuran) to obtain a THF solution containing 2 × 10 ^-4 mol/L HPB-ID; mixing 300 μL of the above THF solution with 2700 μL of deionized water to obtain 2 × 10 ^- A mixed solution of ⁵ mol/L HPB-ID, which is the fluorescent probe.

Example 2

(2) 0.1 mmol of product I and 0.24 mmol of oxadione were added to a 25 mL three-necked flask, and then 10 mL of absolute ethanol and 0.05 mL of triethylamine were added, and the reaction was refluxed at 70 ° C for 2 h with stirring, suction filtration, and anhydrous The collected solid matter was washed with ethanol to obtain a red solid HPB-ID;

Performance characterization

(1) NMR and mass spectrometry

It was found by NMR spectrometer and mass spectrometer that the red solids prepared in the step (2) of Example 1 and Example 2 were both HPB-ID, and the nuclear magnetic resonance spectrum and mass spectrometry data were as follows:

^{1 H-NMR (400MHz, DMSO} ) δ (ppm): 8.61 (s, 1H), 8.59 (s, 1H), 8.23 (s, 4H), 8.21 (s, 4H), 8.05-7.96 (m, 4H) , 7.84-7.77 (m, 4H), 7.20-6.94 (m, 10H);

MS (MALDI-TOF): Calcd for C ₄₈ H ₃₀ N ₄ , 422.28;

(2) Characterization of Aggregation-induced emission (AIE)

The HPB-ID was separately dissolved in 10 parts of a mixed solvent of tetrahydrofuran and deionized water, and uniformly mixed. The concentration of HPB-ID in the obtained 10 parts of the mixed solution was uniformly 2×10 ^-5 , and the deionized in the above 10 parts of the mixed solution. The volume ratio of water to tetrahydrofuran is 0:100, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10; Fluorescence photometers were used to test the fluorescence intensity of the above 10 mixed solutions, and the test results are shown in Fig. 1. The results show that when the water content is less than 70%, the mixed solution has almost no fluorescence, and when the water content is higher than 70%, the fluorescence intensity rises remarkably. This indicates that HPB-ID is a typical AIE substance in THF and water systems.

(3) Relationship between fluorescence intensity and content of substance to be detected

Take 3 mL of the fluorescent probe prepared in Example 1 (90% water content), and measure its initial fluorescence intensity I ₀ with a fluorophotometer; add NTO tetrahydrofuran solution to the probe 10 times, and add NTO each time. The volume of the tetrahydrofuran solution is 10 μL, and each time the NTO in tetrahydrofuran solution contains 1×10 ^-7 mol (1.3 ng) of NTO; after each addition of NTO in tetrahydrofuran solution, the fluorescence intensity of the mixed solution is measured by a fluorometer. I _i (i is the volume of the tetrahydrofuran solution of the added NTO). According to the detection results, the fluorescence spectra of the fluorescent probe prepared in Example 1 in the presence of different NTO contents were plotted, as shown in Figures 2 and 3.

It can be seen from Fig. 2 that as the NTO content increases, the fluorescence intensity increases; when the number of moles of NTO reaches 1 × 10 ^-6 mol, the fluorescence intensity I ₁₀₀ is 4967, (I ₁₀₀ -I ₀ )/ I ₀ is 2.5, indicating that the fluorescent probe has a light-emitting response to NTO. It can be seen from Fig. 3 that when the number of moles of NTO is 0-6×10 ^-7 mol, the molar ratio of NTO has a good linear relationship with the ratio of fluorescence intensity, which can be used as a response curve and calculated based on the fluorescence intensity. The amount of NTO in response.

(4) Relationship between fluorescence intensity and detection time

Take 3 mL of the fluorescent probe prepared in Example 1 (90% water content), and measure its initial fluorescence intensity I ₀ with a fluorophotometer; then, add 2.6 ng of NTO to the fluorescent probe, and immediately test the addition of NTO. After the fluorescence intensity I _NTO , the fluorescence intensity I _i after adding NTO was again tested every 30 s (i is the time after the addition of NTO). Fluorescence spectra of the fluorescent probes at different times were plotted according to the detection results, as shown in FIG. After 270s, (I ₂₇₀ -I ₀ )/I ₀ is 2.4, indicating that the probe responds to NTO in a time-dependent manner, not an immediate response.

Based on the above test methods, 2.6 ng of NTO was replaced with other polyazoles: 2.0 ng DAT, 2.3 ng NT, 2.7 ng CTO, other common explosives: 4.6 ng PA, 4.5 ng TNT, 5.9 ng HMX, 4.4 ng RDX, 3.1 ng CL-20, and azole compound containing 2 nitrogen: 1.6 ng N-IM, 3.2 ng 2N-IM, 1.3 ng IM, other operating procedures and test conditions are unchanged, according to test results Fluorescence spectra of the compounds at different times were plotted against fluorescent probes, as shown in Figures 5-15. According to the test results, the fluorescence intensity increases with the increase of the detection time when DAT, NT, and CTO are detected. After 270s, DTA (I ₂₇₀ -I ₀ )/I ₀ is 1.1, NT (I ₂₇₀₎ -I ₀ )/I ₀ is 1.93, and the (I ₂₇₀ -I ₀ )/I ₀ of the CTO is 1.63, indicating that the probe has a light-emitting response to other azoles containing more than three nitrogens; for other explosives When PA, TNT, HMX, RDX and CL-20 were detected, the fluorescence intensity of PA and TNT decreased sharply. The fluorescence intensity of HMX, RDX and CL-20 did not change much, indicating that the fluorescent probe contains more than three. Nitrogen azole explosives have a specific response and are not responsive to other explosives. They can be used as probes for distinguishing explosives; detection of azoles containing 2 nitrogen, N-IM, 2N-IM, IM At the time, the fluorescence intensity hardly changed, indicating that the probe did not respond to diazole.

The fluorescence of the fluorescent probe after 270 s of the above-mentioned various substances was collected into a histogram, as shown in FIG. It can be seen that the fluorescent probe of the present invention has a light-emitting type test for a polyazole-based heterocyclic compound, and does not respond to other common explosives and diazole compounds.

(5) Research on anti-interference of other substances

60 μL of solution I containing NTO (1.3 ng), PA (2.3 ng), TNT (2.3 ng), HMX (2.9 ng), RDX (2.2 ng) and CL-20 (1.5 ng) was prepared with THF; 40 μL was prepared with THF Solution II containing NTO (1.3 ng), N-IM (0.8 ng), 2N-IM (1.6 ng) and IM (0.7 ng); 50 μL containing NTO (1.3 ng), N-IM (0.8 ng) in THF 2N-IM (1.6 ng), HMX (2.9 ng) and RDX (2.2 ng) solution III; 10 μL of NTO (1.3 ng) solution was prepared as THF as a comparative solution; 4 parts of 3 mL was prepared in Example 1. a fluorescent probe (90% water content), and its initial fluorescence intensity I ₀ is detected by a fluorophotometer; a fluorescent probe is mixed with one of the above solutions, and after mixing for 270 s, the fluorescence intensity of the 4 mixed solutions is detected, and the result is detected. See Figure 17 for details. In the figure, 0, 1, 2, and 3 correspond to the fluorescence intensity of the contrast solution, solution I, solution II, and solution III. It can be seen from the test results that the fluorescence intensity of the fluorescent probe detected by the solution I, the solution II, the solution III and the comparative solution is almost the same, indicating that the fluorescent probe has strong anti-interference.

The present invention includes, but is not limited to, the above embodiments, and any equivalent or partial modifications made under the principles of the spirit of the invention are considered to be within the scope of the invention.

Claims

A light-emitting fluorescent probe for detecting a polyazole-based heterocyclic compound, characterized in that the fluorescent probe is prepared from HPB-ID, an organic solvent and water;

Wherein the organic solvent is tetrahydrofuran, dimethyl sulfoxide, acetonitrile or N,N-dimethylformamide; the HPB-ID is 2,2'-((1E,3E)-1,2,3 , 4-tetraphenyl-1,3-butadiene-1,4-substituted)di-1.3 anthrone, which has the following structural formula,
A light-emitting fluorescent probe for detecting a polyazole-containing heterocyclic compound according to claim 1, wherein the volume ratio of the organic solvent to water is 1:9.
A light-emitting fluorescent probe for detecting a polyazole-containing heterocyclic compound according to claim 1, wherein the concentration of HPB-ID in a mixed solvent of an organic solvent and water is 1 × 10 -3 mol /L~1×10 -5 mol/L.
The illuminating fluorescent probe for detecting a polyazole-based heterocyclic compound according to claim 1, wherein the fluorescent probe has a nitrogen atom number of not less than 3 and a five-membered ring structure The azole-based heterocyclic compound has a light-emitting response.
A method for preparing a light-emitting fluorescent probe for detecting a polyazole-based heterocyclic compound according to any one of claims 1 to 4, wherein the specific steps of the method are as follows.

(1) Catalyst I, good solvent I, 4-formylbenzeneboronic acid and diphenylacetylene are added to the reactor, and a protective gas is introduced, and the reaction is stirred at 90 ° C to 120 ° C for 40 min to 80 min, and then filtered to collect. The filtrate is spun dry to obtain the crude product I; the crude product I is dissolved in a good solvent II, separated and purified, and dried to obtain the product I;

(2) The product I, the anthraquinone and the solvent III are added to the reaction vessel, and reacted at 70 ° C to 90 ° C for 3 h to 5 h, then suction filtered, separated and purified, and dried to obtain HPB-ID;

Alternatively, the product I, the anthracenedione, the solvent III and the catalyst II are added to the reaction vessel, and reacted at 50 ° C to 70 ° C for 1 h to 3 h, followed by suction filtration, separation and purification, and drying to obtain HPB-ID;

(3) dissolving HPB-ID in a mixed solvent of an organic solvent and water, and uniformly mixing to obtain the fluorescent probe;

Wherein, the catalyst I is a mixture of silver carbonate and palladium acetate; the molar ratio of 4-formylbenzeneboronic acid, diphenylacetylene to silver carbonate is 1: (1 to 1.2):1; the shielding gas is nitrogen or argon; The molar ratio to the oxadione is 1: (2 ~ 3); the catalyst II is morpholine or triethylamine, the molar ratio of the catalyst II to the product I is 1-5: 100; the solvent III is capable of dissolving the product I, but Does not dissolve the organic solvent of HPB-ID.
The method for preparing a light-emitting fluorescent probe for detecting a polyazole-based heterocyclic compound according to claim 5, wherein the good solvent I is a mixed solvent of n-propanol and water, or acetonitrile; The volume ratio of propanol to water was 9:1.
The method for producing a light-emitting fluorescent probe for detecting a polyazole-based heterocyclic compound according to claim 5, wherein the good solvent II is dichloromethane, chloroform, tetrahydrofuran or ethyl acetate.
The method for preparing a light-emitting fluorescent probe for detecting a polyazole-based heterocyclic compound according to claim 5, wherein in the catalyst 1, the ratio of the amount of the substance of the silver carbonate to the palladium acetate is 1: (0.025) ~0.035).
The method for preparing a luminescent fluorescent probe for detecting a polyazole-based heterocyclic compound according to claim 5, wherein the separation and purification are carried out by column chromatography, and petroleum ether and dichloromethane are used as an eluent; Among them, the mass ratio of petroleum ether to dichloromethane was 1:2.5.
The method for producing a light-emitting fluorescent probe for detecting a polyazole-based heterocyclic compound according to claim 5, wherein the solvent III is methanol or ethanol.