A water-soluble phenazine derivative, its synthesis, and application in UV / fluorescence dual-channel identification of hypochlorite ions

Abstract

The present invention provides a method for detecting ClO by fluorescence and ultraviolet. ‑ When the anion ClO is added to the pure aqueous solution of PY, ‑ , AcO ‑ ,H2AsO4 ‑ ,Br ‑ ,F ‑ ,Cl ‑ ,ClO4 ‑ ,CN ‑ ,H2PO4 ‑ ,HSO4 ‑ ,N3 ‑ ,NO3 ‑ ,NO2 ‑ ,OH ‑ ,SCN ‑ ,P2O7 2‑ When ClO ‑ It will cause significant quenching of the fluorescence emission spectrum and red shift of the UV absorption spectrum. However, the addition of other anions has no effect on the fluorescence and UV absorption of the phenazine derivative PY solution. It also shows good selectivity and anti-interference ability. At the same time, through fluorescence and UV titration experiments, it was found that ClO ‑ There is a good linear relationship between the concentration and fluorescence intensity, and the minimum fluorescence detection limit is calculated to be 5.59×10 ‑8 The minimum detection limit of M and UV is 5.84×10 ‑7 M. Finally, we made it into a test strip for semi-quantitative detection of ClO ‑ This recognition and detection performance has important application value in the field of ion recognition.

Description

Technical Field

[0001] The present invention relates to a phenazine derivative and a synthesis method thereof, and also relates to a phenazine derivative in fluorescence and ultraviolet recognition of ClO - The application belongs to the field of chemical synthesis and anion detection technology. Background Art

[0002] Hypochlorite ion (ClO - ) is a chemical with strong oxidizing properties. It has important applications in various fields such as water treatment, disinfection, bleaching, and wastewater treatment. However, although the toxicity of hypochlorite is very low, high concentrations of hypochlorite ions can be harmful to the human body. Long-term exposure to high-concentration hypochlorite ion solutions may cause irritation to the eyes and skin, disrupt normal cell function, and damage vital organs such as the liver and kidneys. Large amounts of hypochlorite discharged into the soil can affect soil microorganisms and plants, thereby destroying the soil ecosystem and posing a potential threat to the environment.

[0003] To date, many fluorescent sensors have been developed for the detection and imaging of ClO with various reaction sites. - However, current sensors still have some problems. For example, they often have poor water solubility and require large amounts of organic solvents to dissolve. This not only increases the complexity of operation but also may have negative impacts on the environment. Secondly, these sensors are generally low in sensitivity and are only effective in solutions with high hypochlorite ion concentrations, resulting in poor low-concentration detection performance. Therefore, in further sensor research, these problems need to be addressed in order to accurately and sensitively detect the presence and concentration of hypochlorite ions.

[0004] Phenazine is an organic natural product, mainly used in dyes, medicines, organic synthesis intermediates and biochemical research. It has an electron-deficient π system, a pair of electron-containing nitrogen atoms and three fused aromatic rings. It has the characteristics of structural tunability, excellent optical properties and high quantum yield, and can be used as an ionic ligand and hydrogen bond acceptor. It also facilitates the mutual overlap of π-π electrons, so this compound has considerable application prospects in supramolecular chemistry and is widely used in various sensors. In view of this, based on our previous research work, a water-soluble phenazine derivative was designed and synthesized as a new ClO - Fluorescence sensor (PY). Sensor PY exhibits excellent ClO - Sensing performance, including excellent sensitivity, high specificity, instantaneous response and good biocompatibility. It can recognize ClO with high selectivity and dual channels. - It has the advantages of specific selectivity, low detection limit and little pollution to the environment. Summary of the Invention

[0005] The purpose of the present invention is to provide a water-soluble phenazine derivative and a synthesis method thereof;

[0006] Another object of the present invention is to provide a method for detecting ClO by using phenazine derivatives. - Application in.

[0007] 1. Phenazine derivative PY and its synthesis

[0008] Phenazine derivative PY, whose molecular formula is C 28 H 32 N5OBr, the structural formula is:

[0009]

[0010] The synthesis method of the phenazine derivative sensing molecule PY comprises the following steps:

[0011] (1) Synthesis of intermediate compound 1: 1,6-dibromohexane and KI were dissolved in acetonitrile and stirred at room temperature for 25-35 min. Finally, p-hydroxybenzaldehyde and K2CO3 were added and the mixture was refluxed at 80-90°C for 20-25 h. After cooling to room temperature, the mixture was filtered and the filtrate was concentrated to obtain a crude product, which was purified by column chromatography to obtain a white solid. The molar ratio of 1,6-dibromobutane to KI was 1:2-1:3; the molar ratio of 1,6-dibromohexane to p-hydroxybenzaldehyde was 2:1; and the molar ratio of p-hydroxybenzaldehyde to K2CO3 was 1:3-1:5.

[0012] (2) Synthesis of intermediate compound 2: Intermediate compound 1 and 2,3-diaminophenazine were dissolved in DMF, followed by addition of glacial acetic acid as a catalyst. The solution was stirred and refluxed at 80-90°C for 20-25 hours. After the reaction was completed, the solution was cooled to room temperature and filtered. The filtrate was concentrated to obtain a crude product, which was purified by column chromatography to obtain a yellow powder. The molar ratio of intermediate 1 to 2,3-diaminophenazine was 1:2-1:3.

[0013] (3) Synthesis of Compound PY: The intermediate compound 2 and trimethylamine were dissolved in an ethanol solution and refluxed continuously at 80-90°C for 7-9 hours. After the reaction, the solution was cooled to room temperature, filtered, and dried to obtain the target product, a dark brown water-soluble phenazine derivative PY. The molar ratio of intermediate 2 to trimethylamine was 1:1-1:2.

[0014] The synthetic route is as follows:

[0015]

[0016] 2. Detection of ClO by Phenazine Derivatives -

[0017] 1. ClO -Fluorescent UV recognition performance

[0018] The concentration was 2.0×10 -5 mol / L phenazine derivative pure water solution was added with 10 times the equivalent of ClO - , H2AsO4 - ,Br - , F - , Cl - , ClO4 - , CN - , H2PO4 - , HSO4 - , N3 - , NO3 - , NO2 - , OH - , SCN - , P2O7 2- Aqueous solution (0.1 M). Study on phenazine derivatives (CH3CN, [c] = 2.0 × 10 -5 M) fluorescence signal was detected (e.g. Figure 1 ), when in a solution of compound PY (2.0×10 -5 M) added ClO - When the fluorescence emission signal is quenched, and when irradiated with a 365 nm ultraviolet lamp, the fluorescence color of PY can be clearly observed to change from orange to colorless. The addition of other anions has no significant effect on the fluorescence spectrum of the PY solution. The UV spectrum experiment was carried out under the same experimental conditions (such as Figure 2 ), the absorption peak of PY red-shifts, and the color changes from light yellow to light orange, which can be clearly observed by the naked eye. The addition of other anions has no significant effect on the UV spectrum of the PY solution. Experiments show that PY can highly sensitively single selective fluorescence and UV recognition of ClO - .

[0019] 2. Phenazine derivatives PY and ClO - Fluorescence UV titration experiment

[0020] Pipette 2.0 mL of pure PY solution (2.0×10 -5 mol·L -1 ) in a quartz cell and gradually add ClO using the cumulative addition method. - The fluorescence emission spectrum of the aqueous solution was measured at 25℃ ( Figure 3 ). Titration experiments show that the fluorescence intensity of PY is affected by ClO - The effect of ClO concentration - At the same time, the fluorescence intensity of PY at 558 nm is similar to that of ClO -There is a good linear relationship between the concentrations (R 2 = 0.994), and the titration results of PY on ClO - The detection limit of the fluorescence spectrum was 5.59×10 −8 M( Figure 4 ). UV titration experiment was carried out under the same experimental conditions. - With the increase of concentration, the color of the solution changes from light yellow to light orange ( Figure 5 ), the absorption peak of PY at 400 nm is similar to that of ClO - The concentration showed a good linear relationship (R 2 = 0.992). In addition, the PY to ClO ratio calculated by the 3σ / S method is - The detection limits (LOD) were 5.59×10 -8 M (fluorescence) and 5.84×10 -7 M (UV) ( Figure 4 and Figure 6 This suggests that PY can be used as a method for detecting ClO - A highly sensitive tool.

[0021] 3. Phenazine derivatives PY and ClO - Anion anti-interference performance test

[0022] In order to determine the effect of PY on ClO - To improve the detection effect, we conducted the following test: two sets of 10 mL colorimetric tubes were added with 2 mL of pure PY solution, and then 2 μL of various anion solutions (0.1 mol·L −1 ). In the other group, 2 μL ClO - , add H2AsO4 to each colorimetric tube - , Br - , F - , Cl - , ClO4 - , CN - ,H2PO4 - , HSO4 - , N3 - , NO3 - , NO2 - , OH - , SCN - , P2O7 2- Aqueous solution (0.1 mol·L -1 ) 2µL. Mix the above solutions thoroughly and observe.

[0023] After the above solution was allowed to stand, its fluorescence emission spectrum and UV absorption spectrum were measured at 25°C. - When ClO was added, the fluorescence intensity was almost unaffected. - Compared with the experimental results of the other competitive analytes, the absorbance of the other competitive analytes is almost the same. Therefore, based on the experimental data, it can be concluded that PY as a probe is effective for ClO - It has high selectivity and excellent resistance to interference from other possible interfering substances (see Figure 7 and Figure 8 ).

[0024] 4. PY test paper

[0025] In order to study the effect of PY on ClO - To investigate the application performance of the filter paper, we conducted the following experiment: First, the filter paper was immersed in a PY concentration of 2×10 -5 The test paper was immersed in a pure aqueous solution of M for 4 hours to allow PY to fully penetrate the filter paper. The soaked filter paper was then dried to make a simple test paper. The test paper loaded with PY was irradiated with a 365 nm ultraviolet lamp. Under irradiation, the test paper showed obvious yellow fluorescence. This color change was observed with the increase of ClO - The color gradually deepened with the increase of concentration, and obvious color levels were observed ( Figure 9 This indicates that the PY-based test paper has sensitive detection capabilities and can detect ClO conveniently and quickly. - existence.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] 1. The phenazine derivatives provided by the present invention can achieve ClO - The fluorescence and UV detection showed good selectivity and anti-interference ability, and strong sensitivity. The minimum fluorescence detection limit was 5.59×10 -8 The minimum detection limit of M and UV is 5.84×10 -7 M.

[0028] 2. The portable test strip prepared by the present invention can realize the detection of ClO - Semi-quantitative detection, simple and convenient. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 Add ClO to the phenazine derivative PY in pure aqueous solution - The fluorescence spectrum after

[0030] Figure 2 Add ClO to the phenazine derivative PY in pure aqueous solution -The UV spectrum after

[0031] Figure 3 ClO of phenazine derivative PY - Fluorescence titration graph;

[0032] Figure 4 ClO of phenazine derivative PY - Fluorescence linear fitting plot;

[0033] Figure 5 ClO of phenazine derivative PY - UV titration diagram;

[0034] Figure 6 ClO of phenazine derivative PY - UV-fitting diagram;

[0035] Figure 7 Add ClO to the pure aqueous solution of phenazine derivative PY - , on this basis, different anion fluorescence anti-interference maps were added;

[0036] Figure 8 Add ClO to the pure aqueous solution of phenazine derivative PY - , on this basis, different anion UV anti-interference maps were added;

[0037] Figure 9 Detection of ClO by a test strip prepared for the phenazine derivative PY - ;

[0038] Figure 10 is the hydrogen spectrum of the phenazine derivative PY;

[0039] Figure 11 This is the mass spectrum of the phenazine derivative PY. Specific implementation methods

[0040] Example 1 Preparation of Phenazine Derivative Sensing Molecule PY

[0041] (1) Synthesis of intermediate compound 1: 1,6-Dibromohexane (15.57 g, 64.40 mmol) and KI (10.69 g, 64.40 mmol) were dissolved in acetonitrile and stirred at room temperature for 30 min. Finally, p-hydroxybenzaldehyde (4 g, 32.2 mmol) and K2CO3 (5.89 g, 44.5 mmol) were added. The mixture was refluxed at 85°C for 24 h. After cooling to room temperature, the filtrate was filtered and concentrated to obtain the crude product, which was purified by column chromatography to obtain a white solid.

[0042] (2) Synthesis of intermediate compound 2: Intermediate 1 (5.7 g, 20 mmol) and 2,3-diaminophenazine (4.6 g, 22 mmol) were dissolved in DMF, followed by the addition of 3–4 drops of glacial acetic acid as a catalyst. The solution was refluxed at 85°C for 24 h with stirring. After the reaction was complete, the solution was cooled to room temperature. The filtrate was filtered and concentrated to obtain the crude product, which was then purified by column chromatography to obtain a yellow powder.

[0043] (3) Synthesis of compound PY: Intermediate 2 (2.6 g, 11 mmol) and trimethylamine (0.71 g, 12 mmol) were added to a 100 ml round-bottom flask and dissolved in ethanol solution. The reaction was continued under reflux at 85 °C for 8 h. After the reaction was completed, the solution was cooled to room temperature, filtered and dried to obtain the dark brown target product PY. The hydrogen spectrum and mass spectrum of PY are shown in Figure 2. Figure 10 and 11 shown.

[0044] The synthetic route is as follows:

[0045]

[0046] Example 2 Fluorescence recognition of ClO by the sensing molecule PY -

[0047] At a concentration of 2.0×10 -5 mol / L pure water solution of compound PY was added with 10 times the equivalent of ClO - ,AcO - , H2AsO4 - , Br - , F - , Cl - , ClO4 - , CN - , H2PO4 - , HSO4 - , N3 - , NO3 - , NO2 - , OH - , SCN - ,P2O7 2- If the fluorescence of the pure aqueous solution of PY is quenched and its fluorescence color changes from orange to colorless under 365nm ultraviolet light, then ClO is added. - If the fluorescence emission signal and fluorescence color of the pure aqueous solution of the phenazine derivative do not change significantly, it means that other ions have been added.

[0048] Example 3: Sensing molecule PY UV recognition of ClO -

[0049] At a concentration of 2.0×10 -5 mol / L pure water solution of compound PY was added with 10 times the equivalent of ClO - ,AcO - , H2AsO4 - , Br - , F - , Cl - , ClO4 - , CN - , H2PO4 - , HSO4 - , N3 - , NO3 - , NO2 - , OH - , SCN - ,P2O7 2- If the absorption peak of the ultraviolet spectrum of the pure aqueous solution of PY is red-shifted, the color of the solution will change from light yellow to light orange, indicating that ClO - ; If the color of the pure water solution of PY does not change, it means that other ions have been added.

[0050] Example 4 Preparation of Simple Test Strips

[0051] First, the filter paper was soaked in a PY solution with a concentration of 2×10 -5 M pure water solution for 4 hours to allow PY to fully penetrate into the filter paper. Then, the soaked filter paper was dried to make a simple test paper. Next, we used a 365 nm ultraviolet lamp to irradiate the test paper loaded with PY. Under irradiation, these test papers showed obvious yellow fluorescence. Then, we added different concentrations of ClO - solution, it was found that with the increase of ClO - As the concentration increases, the test paper shows different fluorescent color changes. This color change increases with the increase of ClO - The color gradually deepened with the increase of concentration, and obvious color levels were observed. - The lowest response concentration was 1×10 -6 M.

Claims

1. A water-soluble phenazine derivative having the structural formula: 。 2. The method for synthesizing the water-soluble phenazine derivative according to claim 1, comprising the following steps: (1) Synthesis of intermediate compound 1: 1,6-dibromohexane and KI were dissolved in acetonitrile and stirred at room temperature for 25-35 min. Finally, p-hydroxybenzaldehyde and K2CO3 were added and refluxed at 80-90°C for 20-25 h. After cooling to room temperature, the mixture was filtered and the filtrate was concentrated to obtain a crude product, which was purified by column chromatography to obtain a white solid. The structural formula of intermediate compound 1 is: (2) Synthesis of intermediate compound 2: Intermediate compound 1 and 2,3-diaminophenazine were dissolved in DMF, and then glacial acetic acid was added as a catalyst. The solution was refluxed at 80-90°C for 20-25h under stirring conditions. After the reaction was completed, the solution was cooled to room temperature and filtered. The filtrate was concentrated to obtain a crude product, which was purified by column chromatography to obtain a yellow powder. The structural formula of intermediate compound 2 is: ; (3) Synthesis of water-soluble phenazine derivatives: The intermediate compound 2 and trimethylamine were dissolved in an ethanol solution and refluxed continuously at 80-90°C for 7-9 hours. After the reaction, the solution was cooled to room temperature, filtered and dried to obtain a water-soluble phenazine derivative.

3. The method for synthesizing a water-soluble phenazine derivative according to claim 2, wherein: In step (1), the molar ratio of 1,6-dibromohexane to KI is 1:2-1:3; the molar ratio of 1,6-dibromohexane to p-hydroxybenzaldehyde is 2:1; and the molar ratio of p-hydroxybenzaldehyde to K2CO3 is 1:3-1:

5.

4. The method for synthesizing a water-soluble phenazine derivative according to claim 2, wherein: In step (2), the molar ratio of the intermediate compound 1 to 2,3-diaminophenazine is 1:2 to 1:

3.

5. The method for synthesizing a water-soluble phenazine derivative according to claim 2, wherein: In step (3), the molar ratio of the intermediate compound 2 to trimethylamine is 1:1 to 1:

2.

6. The water-soluble phenazine derivative according to claim 1 is used for detecting ClO - Application in.

7. The water-soluble phenazine derivative according to claim 6 is capable of recognizing ClO - The application is characterized by: Fluorescence detection of ClO by phenazine derivatives - :ClO was added to the pure aqueous solution of phenazine derivatives - , AcO - , H2AsO4 - , Br - , F - ,Cl - , ClO4 - , CN - , H2PO4 - , HSO4 - , N3 - , NO3 - , NO2 - , OH - , SCN - , P2O7 2- , only ClO - The fluorescence emission signal of the pure aqueous solution of the phenazine derivative is quenched. Under the irradiation of a 365nm ultraviolet lamp, the fluorescence color of the pure aqueous solution of the phenazine derivative changes from orange to colorless, while the addition of other ions will not cause a significant change in the fluorescence emission signal and fluorescence color of the pure aqueous solution of the phenazine derivative.

8. The phenazine derivative according to claim 6 is used to detect ClO - The application is characterized by: UV detection of ClO by phenazine derivatives - :ClO was added to the pure aqueous solution of phenazine derivatives - , AcO - , H2AsO4 - , Br - , F - , Cl - , ClO4 - ,CN - , H2PO4 - , HSO4 - , N3 - , NO3 - , NO2 - , OH - , SCN - , P2O7 2- , only ClO - The addition of ions reduces the ultraviolet absorption peak of the pure aqueous solution of phenazine derivatives, and the color is clearly observed to change from light yellow to light orange. However, no obvious color change can be observed with the naked eye when other ions are added.

9. The phenazine derivative according to claim 1 in the preparation of ClO - Application in test strips.

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