Fluorescent probe Tz3 for detecting Ag < + > and ClO <-> based on phenothiazine as well as preparation method and application of fluorescent probe Tz3

Abstract

The invention discloses a fluorescence probe Tz3 for detecting Ag < + > and ClO <-> based on phenothiazine and a preparation method and application thereof, and relates to the technical field of fluorescence probes. Sodium carbonate is added into dichloromethane, then a mixture of 11-ethyl-2-oxo-2, 11-dihydropyrano [2, 3-b] phenothiazine-3-carbonyl bromide and dimethyl pyridylamine is added, the mixture is stirred at the room temperature for a reaction, and the fluorescence probe Tz3 is obtained. According to the fluorescent probe Tz3 and the preparation method thereof, Ag < + > and Hg < 2 + > can be distinguished, and the fluorescent probe Tz3 has good selectivity, anti-interference performance and sensitivity.

Description

Technical Field

[0001] The present invention relates to the technical field of fluorescent probes, and more particularly to a method for detecting Ag based on phenothiazine. + and ClO - Fluorescent probe Tz3 and its preparation method and application. Background Art

[0002] Silver (Ag) has been widely used in all aspects of human life. Due to its physical, chemical and biological advantages, it is widely used in various fields such as photography, agriculture, electronic imaging, medical devices and pharmaceutical industry. However, with the widespread application of nanomaterials, silver may enter the soil, water, air and food, and accumulate in the human body through the food chain. Ag entering the human body can coordinate with thiol, imidazole, amino and carboxyl groups, resulting in protein and enzyme inactivation, causing many serious symptoms and diseases, leading to developmental delay, skin damage, liver and kidney poisoning and central nervous system damage. Therefore, it is more important to develop a silver ion recognition and detection technology.

[0003] At present, the identification and detection methods of silver ions are mostly ion chromatography and electrochemical methods, such as voltammetry, ICP-MS (inductively coupled plasma mass spectrometry), and AAS (atomic absorption spectroscopy). The above methods are expensive and time-consuming. Therefore, the fluorescent probe detection method has attracted people's attention due to its advantages such as simple and fast detection and short response time. However, mercury ions (Hg 2+ ) and silver ions (Ag + ) have similar outer electron configurations. Therefore, when the existing fluorescent probes for detecting silver ions are coordinated with N or O, mercury ions (Hg 2+ ) and silver ions (Ag + ) will respond in the same way; meanwhile, mercury ions (Hg 2+ ) and silver ions (Ag + ) have a high affinity for sulfur. The fluorescent probe designed based on sulfur receptors will also obtain the same reaction products and signal outputs when it reacts with mercury ions and silver ions. Therefore, when detecting silver ions, mercury ions will also respond and interfere with the detection results of silver ions. Summary of the invention

[0004] In order to solve the problem that mercury ions simultaneously respond and interfere with the detection results during the detection of silver ions by fluorescent probes in the prior art, the present invention provides a method for detecting Ag based on phenothiazine. + and ClO - The fluorescent probe Tz3 and its preparation method and application can distinguish Ag + and Hg 2+ , with good selectivity, anti-interference and sensitivity.

[0005] In order to achieve the above-mentioned purpose, the specific scheme adopted by the present invention is: a method for detecting Ag based on phenothiazine + and ClO - The fluorescent probe Tz3 has the structural formula: .

[0006] A method for detecting Ag based on phenothiazine + and ClO - A method for preparing the fluorescent probe Tz3, which is used to prepare the above-mentioned fluorescent probe Tz3, firstly adding sodium carbonate to dichloromethane, and then adding a mixture of 11-ethyl-2-oxo-2,11-dihydropyrano[2,3-b]phenothiazine-3-carbonyl bromide and dimethylpyridinamine, stirring at room temperature, reacting until the reaction is completed by TLC detection, to obtain the fluorescent probe Tz3.

[0007] As a kind of phenothiazine-based Ag detection + and ClO - An optimized scheme for the preparation method of the fluorescent probe Tz3: the molar ratio of 11-ethyl-2-oxo-2,11-dihydropyrano[2,3-b]phenothiazine-3-carbonyl bromide and dimethylpyridinamine in the mixture is 1:1.

[0008] As a kind of phenothiazine-based Ag detection + and ClO - Another optimized scheme for the preparation method of the fluorescent probe Tz3: the ratio of the added amount of the mixture to dichloromethane is 2 mmol:10 ml.

[0009] As a kind of phenothiazine-based Ag detection + and ClO - Another optimized scheme for the preparation method of the fluorescent probe Tz3: the ratio of the added amount of sodium carbonate to dichloromethane is 1 mmol:10 ml.

[0010] A fluorescent probe Tz3 is used to detect Ag + Application in.

[0011] As one of the fluorescent probes mentioned above, Tz3 can detect Ag + An optimization scheme for the application of the method: add the fluorescent probe Tz3 solution and the solution to be detected into the MeOH:PBS solvent, and irradiate with a 360-370nm ultraviolet lamp for 3-5min. If the color of the solution changes from yellow to colorless and transparent, the solution to be detected contains Ag. + If the solution color does not change, the solution to be tested does not contain Ag. + .

[0012] As one of the fluorescent probes mentioned above, Tz3 can detect Ag + Another optimization scheme for application in: the concentration of the fluorescent probe Tz3 solution is 10 μM.

[0013] A fluorescent probe Tz3 is used to detect ClO - Application in.

[0014] As one of the fluorescent probes mentioned above, Tz3 can detect ClO - An optimization scheme for the application of the method: add the fluorescent probe Tz3 solution and the solution to be detected into the MeOH:PBS solvent. If the color of the solution changes from yellow to colorless and transparent, the solution to be detected contains ClO - If the solution color does not change, the solution to be tested does not contain ClO - .

[0015] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention provides a method for detecting Ag based on phenothiazine + and ClO - The fluorescent probe Tz3 has good specificity and can distinguish Ag + and Hg 2+ , has good selectivity, anti-interference and sensitivity, and at the same time, can respond quickly and have a wide pH adaptability range; 2. In the present invention, the fluorescent probe Tz3 can also detect ClO - It can detect with good selectivity and anti-interference. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 is the H NMR spectrum of the fluorescent probe Tz3 ( 1 HNMR) spectrum; Figure 2 The fluorescent probe Tz3 (10 μM) + Ag was prepared in MeOH:PBS (4:6, v:v; 0.1 μM) solvent. + or UV-visible absorption spectra of other ions (100 μM) + UV; Figure 3 The fluorescent probe Tz3 (10 μM) + ClO was added in MeOH:PBS (4:6, v:v; 0.1 μM) solvent. - or UV-visible absorption spectra of other ions (100 μM); Figure 4 The fluorescent probe Tz3 (10 μM) + Ag was prepared in MeOH:PBS (4:6, v:v; 0.1 μM) solvent. + or other ions (100 μM) + UV fluorescence spectra (excitation wavelength: 378 nm; slit width: 2.5 nm); Figure 5 The fluorescent probe Tz3 (10 μM) + ClO was added in MeOH:PBS (4:6, v:v; 0.1 μM) solvent. - or fluorescence spectra of other ions (100 μM) (excitation wavelength: 378 nm; slit width: 2.5 nm); Figure 6 The fluorescent probe Tz3 (10 μM) recognized Ag in the presence of various common metal ion salts in MeOH:H2O=4:6 solvent. + Fluorescence spectra of the competition experiment of (20 μM) (excitation wavelength: 378 nm; slit width: 5 nm), where M is Al 3+ , Ba 2+ , Ca 2+ 、Cd 2+ 、Co 2+ Cr 3+ , Cu 2+ , Fe 2+ , Fe 3+ , Hg 2+ Mg 2+ , Mn 2+ 、Ni 2+ , Pb 2+ , Pd 2+ 、Zn 2+ 、H2O2、S 2- , ClO - One of the following; and the horizontal coordinates 1-20 and Ag + 、Al 3+ , Ba 2+ , Ca 2+ 、Cd 2+ 、Co 2+ Cr 3+ , Cu 2+ , Fe 2+ , Fe 3+ , Hg 2+ Mg 2+ , Mn 2 + 、Ni 2+ , Pb 2+ , Pd 2+ 、Zn 2+ 、H2O2、S 2- , ClO - One to one correspondence; Figure 7 The fluorescent probe Tz3 (10 μM) recognized ClO in the presence of various common metal ion salts in MeOH:H2O=4:6 solvent. -Fluorescence spectrum of the competition experiment of Ag (20 μM) (excitation wavelength: 378 nm; slit width: 5 nm), where M is Ag + 、Al 3+ , Ba 2+ , Ca 2+ 、Cd 2+ 、Co 2+ Cr 3+ , Cu 2+ , Fe 2+ , Fe 3+ , Hg 2+ Mg 2+ , Mn 2+ 、Ni 2+ , Pb 2+ , Pd 2+ 、Zn 2+ 、H2O2、S 2- 、NO2 - 、HSO3 - 、SO3 2- One of them, and the horizontal axis 1-23 is ClO - 、Ag + 、Al 3+ , Ba 2+ , Ca 2+ 、Cd 2+ 、Co 2+ Cr 3+ , Cu 2+ , Fe 2+ , Fe 3+ , Hg 2+ Mg 2+ , Mn 2+ 、Ni 2+ , Pb 2+ , Pd 2+ 、Zn 2+ 、H2O2、S 2- 、NO2 - 、HSO3 - 、SO3 2- One to one correspondence; Figure 8 Ag in MeOH:PBS=4:6 solvent + Linear relationship between the concentration and the fluorescence intensity at 500 nm (excitation wavelength: 378 nm; slit width: 2.5 nm); Fig. 9 The fluorescent probe Tz3 (10 μM) and Ag were reacted in MeOH:PBS=4:6 solvent. + (30 μM) Fluorescence spectrum changing with UV irradiation time; Fig.10It is the fluorescent probe Tz3 (10μM) + ClO - (30 μM) Fluorescence spectrum changing with reaction time (excitation wavelength: 378 nm; slit width: 2.5 nm); Fig.11 Fluorescent probe Tz3 (10 μM), fluorescent probe Tz3 (10 μM) + Ag + (30μM)+UV, fluorescent probe Tz3 (10μM)+ClO - (30 μM) fluorescence intensity with pH changes; Fig.12 ClO in MeOH:PBS=4:6 solvent - Linear relationship between the concentration and the fluorescence intensity at 500 nm (excitation wavelength: 378 nm; slit width: 2.5 nm). DETAILED DESCRIPTION

[0017] The technical scheme of the present invention is further elaborated in detail below in conjunction with specific embodiments. The parts not described and disclosed in detail in the following embodiments of the present invention should be understood as the prior art known or should be known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art; unless otherwise specified, the reagents and materials used in the present invention are commercially available.

[0018] Example 1

[0019] A method for detecting Ag based on phenothiazine + and ClO - The fluorescent probe Tz3 has the structural formula: .

[0020] The H NMR spectrum of the fluorescent probe Tz3 ( 1 HNMR) spectrum is used to confirm the correctness of its structure. Figure 1Shown, H NMR (400MHz, CDCl3) δ in ppm: 8.57-8.56 (m, 1H), 7.75 (s, 1H), 7.68-7.64 (m, 1H), 7.40 (d, J=7.8Hz, 1H), 7.20-7. 15 (m, 2H), 7.14 (s, 1H), 7.11 (dd, J=7.6, 1.4Hz, 1H), 6.99-6.95 (m, 1H), 6.93 (d, J=8.2Hz , 1H), 6.73 (s, 1H), 3.98 (dd, J=14.0, 7.0Hz, 2H), 3.81 (t, J=4.4Hz, 2H), 3.69 (s, 2H), 3. 43 (t, J=4.8Hz, 2H), 2.60 (t, J=5.0Hz, 2H), 2.55 (t, J=4.4Hz, 2H), 1.47 (t, J=6.9Hz, 3H).

[0021] Example 2

[0022] A method for detecting Ag based on phenothiazine + and ClO - The preparation method of the fluorescent probe Tz3 is as follows: first, sodium carbonate is added to dichloromethane, and then a mixture of 11-ethyl-2-oxo-2,11-dihydropyrano[2,3-b]phenothiazine-3-carbonyl bromide and dimethylpyridinamine is added, followed by stirring at room temperature for reaction, and reacting until the reaction is completed by TLC detection, thereby obtaining the fluorescent probe Tz3. The molar ratio of 11-ethyl-2-oxo-2,11-dihydropyrano[2,3-b]phenothiazine-3-carbonyl bromide and dimethylpyridinamine in the mixture is 1:1; the ratio of the amount of the mixture to dichloromethane is 2mmol:10ml; and the ratio of the amount of sodium carbonate to dichloromethane is 1mmol:10ml.

[0023] The reaction equation during the synthesis process is: .

[0024] In this embodiment, 2 mmol of sodium carbonate was first added to 20 ml of dichloromethane, and a mixture consisting of 2 mmol of 11-ethyl-2-oxo-2,11-dihydropyrano[2,3-b]phenothiazine-3-carbonyl bromide and 2 mmol of dimethylpyridinamine was added to the dichloromethane in the presence of sodium carbonate, and stirred at room temperature for 3-4 hours. After the reaction was completed by TLC detection, column chromatography was performed with dichloromethane methanol system as the mobile phase to obtain a light yellow fluorescent probe Tz3.

[0025] In the preparation method of the fluorescent probe Tz3, 11-ethyl-2-oxo-2,11-dihydropyrano[2,3-b]phenothiazine-3-carboxylic acid is reacted with bromine in a chloroform solvent to generate 11-ethyl-2-oxo-2,11-dihydropyrano[2,3-b]phenothiazine-3-carbonyl bromide. It should be noted that 11-ethyl-2-oxo-2,11-dihydropyrano[2,3-b]phenothiazine-3-carboxylic acid is prepared according to the method disclosed in the literature "A novel benzothiazine-fused coumarin derivative for sensing hypochlorite with high performance" (Dyes And Pigments, Vol. 182 (2020) 108675). The preparation method of 11-ethyl-2-oxo-2,11-dihydropyrano[2,3-b]phenothiazine-3-carboxylic acid is briefly described as follows: 2-methoxyphenothiazine is reacted with iodoethane in DMSO solvent to generate an intermediate 10-ethyl-2-methoxy-10H-phenothiazine, which is then reacted with phosphorus oxychloride in DMF solvent to generate an intermediate 10-ethyl-2-methoxy-10H-phenothiazine-3-carboxaldehyde, which is further reacted with trichlorophosphate in dichloromethane to generate an intermediate 10-ethyl-2-methoxy-10H-phenothiazine-3-carboxaldehyde. Aluminum chloride is reacted and hydrolyzed to generate an intermediate 10-ethyl-2-hydroxy-10H-phenothiazine-3-carboxaldehyde, which is then condensed with diethyl malonate in an acetonitrile solvent to generate an intermediate 11-ethyl-2-oxo-2,11-dihydropyrano[2,3-b]phenothiazine-3-carboxylic acid ethyl ester, which is then hydrolyzed in an ethanol solvent under an alkaline environment to generate 11-ethyl-2-oxo-2,11-dihydropyrano[2,3-b]phenothiazine-3-carboxylic acid.

[0026] Example 3

[0027] A fluorescent probe Tz3 is used to detect Ag + The specific detection process is to add a 10μM fluorescent probe Tz3 solution and a solution to be detected in MeOH:PBS (4:6, v:v; 0.1μM) solvent, the volume of the fluorescent probe Tz3 solution and the solution to be detected are both 1μL, and the amount of substance is 1:10; and irradiate with a 360-370nm ultraviolet lamp (UV) for 3-5min. If the color of the solution changes from yellow to colorless and transparent, the solution to be detected contains Ag. + If the solution color does not change, the solution to be tested does not contain Ag. + It should be noted that the MeOH:PBS (4:6, v:v; 0.1 μM) solvent means that the volume ratio of MeOH and PBS in the MeOH:PBS solvent is 4:6, and the concentration of PBS in the solvent is 0.1 μM.

[0028] Example 4

[0029] A fluorescent probe Tz3 is used to detect ClO - The specific detection process is to add a 10 μM fluorescent probe Tz3 solution and a test solution into a MeOH:PBS (4:6, v:v; 0.1 μM) solvent. If the solution changes from yellow to colorless and transparent, the test solution contains ClO. - If the solution color does not change, the solution to be tested does not contain ClO - It should be noted that the MeOH:PBS (4:6, v:v; 0.1 μM) solvent means that the volume ratio of MeOH and PBS in the MeOH:PBS solvent is 4:6, and the concentration of PBS in the solvent is 0.1 μM.

[0030] Comparative Example

[0031] A 10 μM solution of fluorescent probe Tz3 and a 100 μM solution of Hg were added to a MeOH:PBS (4:6, v:v; 0.1 μM) solvent. 2+ solution, add fluorescent probe Tz3 solution and Hg 2+ The volume of the solution is 1 μL, and the amount of substance is 1:10. When irradiated with 360-370 nm ultraviolet light (UV) for 3-5 min, the color of the solution does not change, indicating that the fluorescent probe Tz3 does not react with Hg 2+ Interaction, no response.

[0032] <Optional Test>

[0033] 1. Selectivity means that among many ions, the fluorescent probe Tz3 can eliminate interference and only bind to the target ion. A 10 μM fluorescent probe Tz3 solution and a 100 μM test solution were added to the MeOH:PBS (4:6, v:v; 0.1 μM) solvent. The test solution was Ag. + Solution, Al 3+ Solution, Ba 2+ Solution, Ca 2+ Solution, Cd 2+ Solution, Co 2+ Solution, Cr 3+ Solution, Cu 2+ Solution, Hg 2+ Solution, Mg 2+ Solution, Mn 2+ Solution, Ni 2+ Solution, Pb 2+ Solution, Pd 2+ Solution, Zn 2+ Solution, H2O2 solution, HSO3- Solution, NO2 - Solution, S 2- Solution, SO3 2- Solution, HCO3 - Solution, Fe 2+ Solution, Fe 3+ One of the solutions was irradiated with a 365nm ultraviolet lamp (UV) for 3 minutes to obtain the UV-visible absorption spectra of the solutions with different ions added (e.g. Figure 2 ) and fluorescence spectra (as shown Figure 4 ). Figure 2 It can be seen that only Ag + After interacting with the fluorescent probe Tz3, its UV-visible absorption spectrum blue-shifted, specifically, from 428nm to 378nm, and the intensity increased significantly, and the solution color changed from yellow to colorless and transparent; other ions did not interact with the fluorescent probe Tz3, and the solution color remained unchanged. Figure 4 It can be seen that only Ag + After interacting with the fluorescent probe Tz3, there is a significant fluorescence enhancement, a new peak appears at 500nm, and the fluorescence color changes from rose red to green.

[0034] 2. Add 10 μM fluorescent probe Tz3 solution and 100 μM test solution to MeOH:PBS (4:6, v:v; 0.1 μM) solvent. The test solution is ClO - Solution, Ag + Solution, Al 3+ Solution, Ba 2+ Solution, Ca 2+ Solution, Cd 2+ Solution, Co 2+ Solution, Cr 3+ Solution, Cu 2+ Solution, Hg 2+ Solution, Mg 2+ Solution, Mn 2+ Solution, Ni 2+ Solution, Pb 2+ Solution, Pd 2+ Solution, Zn 2+ Solution, H2O2 solution, HSO3 - Solution, NO2 - Solution, S 2- Solution, SO3 2- Solution, HCO3 - Solution, Fe 2+ Solution, NO3 - Solution, CH3COO - One of the solutions, to obtain the UV-visible absorption spectrum of the solution to be tested with different ions added, such as Figure 3 As shown by Figure 3 It can be seen that only ClO - After interacting with the fluorescent probe Tz3, its UV-visible absorption spectrum blue-shifted, specifically, from 428nm to 378nm, and the intensity increased significantly, and the solution color changed from yellow to colorless and transparent; other ions did not interact with the fluorescent probe Tz3, and the solution color remained unchanged.

[0035] 3. Add 10 μM fluorescent probe Tz3 solution and 100 μM test solution to MeOH:PBS (4:6, v:v; 0.1 μM) solvent. The test solution is ClO - Solution, Ag + Solution, Al 3+ Solution, Ba 2+ Solution, Ca 2+ Solution, Cd 2+ Solution, Co 2+ Solution, Cr 3+ Solution, Cu 2+ Solution, Hg 2+ Solution, Mg 2+ Solution, Mn 2+ Solution, Ni 2+ Solution, Pb 2+ Solution, Pd 2+ Solution, Zn 2+ Solution, H2O2 solution, HSO3 - Solution, NO2 - Solution, S 2- Solution, SO3 2- Solution, HCO3 - Solution, Fe 2+ Solution, NO3 - Solution, CH3COO - One of the solutions, to obtain the fluorescence spectrum of the solution to be tested with different ions added, such as Figure 5 As shown by Figure 5 It can be seen that only ClO - After interacting with the fluorescent probe Tz3, there is a significant fluorescence enhancement, a new peak appears at 500nm, and the fluorescence color changes from rose red to green.

[0036] In summary, the fluorescent probe Tz3 + and ClO - It has good selectivity under UV-visible absorption spectrum, and the solution changes color, so it can be used as a colorimetric probe. Figure 2 It can be seen that Hg 2+ It has no effect on the fluorescent probe Tz3, and the color of the solution does not change; the fluorescent probe Tz3 has no effect on Ag + and ClO- It has good selectivity under the fluorescence spectrum, and the fluorescence color also changes, so it can be used as a fluorescent probe; Figure 4 It can be seen that Hg 2+ It has no effect on the fluorescent probe Tz3, no fluorescence enhancement, and no change in fluorescence color. And Ag is detected under ultraviolet light (UV) + Detect ClO without UV light - .

[0037] <Interference test>

[0038] 1. Add 10μM fluorescent probe Tz3 solution and 20μM Ag solution to MeOH:H2O=4:6 solvent. + The solution was irradiated with 365 nm ultraviolet light (UV) for 3 minutes, and the fluorescent probe Tz3 and Ag + The reaction shows a high intensity fluorescence value ( Figure 6 The area filled with diagonal lines at the horizontal coordinate 1).

[0039] A 10 μM fluorescent probe Tz3 solution and a 50 μM test solution were added to a MeOH:H2O=4:6 solvent and irradiated with a 365 nm ultraviolet lamp (UV) for 3 minutes. The test solution was M+Ag. + Solution, Figure 6 The oblique line filled areas at the horizontal coordinates 2-20 are the fluorescent probes Tz3 and M+Ag respectively. + The fluorescence value of the reaction; where M is Al 3+ , Ba 2+ , Ca 2+ 、Cd 2+ 、Co 2 + Cr 3+ , Cu 2+ , Fe 2+ , Fe 3+ , Hg 2+ Mg 2+ , Mn 2+ 、Ni 2+ , Pb 2+ , Pd 2+ 、Zn 2+ 、H2O2、S 2- , ClO - One of Figure 6 The horizontal coordinate 2-20 and Al 3+ , Ba 2+ , Ca 2+ 、Cd 2+ 、Co 2+ Cr 3+ , Cu2+ , Fe 2+ , Fe 3+ , Hg 2+ Mg 2+ , Mn 2+ 、Ni 2+ , Pb 2+ , Pd 2+ 、Zn 2+ 、H2O2、S 2- , ClO - One to one correspondence. Figure 6 It can be seen that in Ag + In the presence of other ions, the fluorescent probe Tz3 still maintains a high intensity fluorescence value ( Figure 6 The oblique line filling area at the horizontal coordinate 2-20 in the middle), where Figure 6 Ag at 19 in the middle horizontal coordinate + and S 2- Chemical precipitation occurs, resulting in the fluorescence probe Tz3 and S 2- +Ag + The fluorescence value of the reaction is small.

[0040] A 10 μM fluorescent probe Tz3 solution and a 50 μM test solution were added to a MeOH:H2O=4:6 solvent and irradiated with a 365 nm ultraviolet lamp (UV) for 3 minutes. The test solution contained only M, and M was Al. 3+ , Ba 2+ , Ca 2+ 、Cd 2+ 、Co 2 + Cr 3+ , Cu 2+ , Fe 2+ , Fe 3+ , Hg 2+ Mg 2+ , Mn 2+ 、Ni 2+ , Pb 2+ , Pd 2+ 、Zn 2+ 、H2O2、S 2- , ClO - One of Figure 6 The solid filled areas at 2-20 in the middle horizontal axis are the fluorescence values ​​of the fluorescent probe Tz3 when it reacts with M; the fluorescent probe Tz3 has almost no fluorescence value when it reacts with other ions (such as Figure 6 The solid filled area at the horizontal axis 2-20 in the middle shows that the fluorescent probe Tz3 has strong selectivity and anti-interference to silver ions, and under ultraviolet light (UV) irradiation, the fluorescent probe Tz3 has strong selectivity and anti-interference to ClO - No response.

[0041] 2. Add 10 μM fluorescent probe Tz3 and 20 μM ClO to MeOH:H2O=4:6 solvent. - Solution, fluorescent probe Tz3 and ClO - The reaction shows a high intensity fluorescence value ( Figure 7 The area filled with diagonal lines at the horizontal coordinate 1).

[0042] A fluorescent probe Tz3 with a concentration of 10 μM and a solution to be tested with a concentration of 50 μM were added to a solvent of MeOH:H2O=4:6. The solution to be tested was M+ClO - Solution, that is, the solution to be tested contains M and ClO - , Figure 7 The oblique line filled areas at the horizontal coordinates 2-23 are the fluorescent probes Tz3 and M+ClO - The fluorescence value of the reaction, where M is Ag + 、Al 3+ , Ba 2+ , Ca 2+ 、Cd 2+ 、Co 2+ Cr 3+ , Cu 2+ , Fe 2+ , Fe 3+ , Hg 2+ Mg 2+ , Mn 2+ 、Ni 2+ , Pb 2+ , Pd 2+ 、Zn 2+ 、H2O2、S 2- 、NO2 - 、HSO3 - 、SO3 2- One of Figure 7 The horizontal coordinate 2-23 and Ag + 、Al 3+ , Ba 2+ , Ca 2+ 、Cd 2+ 、Co 2+ Cr 3+ , Cu 2+ , Fe 2+ , Fe 3+ , Hg 2+ Mg 2+ , Mn 2 + 、Ni 2+ , Pb 2+ , Pd 2+ 、Zn 2+ 、H2O2、S2- 、NO2 - 、HSO3 - 、SO3 2- One to one correspondence. Figure 7 It can be seen that in ClO - In the presence of other ions, the fluorescent probe Tz3 still maintains a high intensity fluorescence value ( Figure 7 The area filled with diagonal lines at the horizontal coordinate 2-23).

[0043] A fluorescent probe Tz3 with a concentration of 10 μM and a test solution with a concentration of 50 μM were added to a MeOH:H2O=4:6 solvent. The test solution contained only M, and M was Ag. + 、Al 3+ , Ba 2+ , Ca 2+ 、Cd 2+ 、Co 2+ Cr 3+ , Cu 2+ , Fe 2+ , Fe 3+ , Hg 2+ Mg 2+ , Mn 2+ 、Ni 2+ , Pb 2+ , Pd 2+ 、Zn 2+ 、H2O2、S 2- 、NO2 - 、HSO3 - 、SO3 2- One of Figure 7 The solid filled areas at the horizontal coordinates 2-23 are the fluorescence values ​​of the fluorescent probe Tz3 reacting with M. Figure 7 It can be seen that the fluorescent probe Tz3 has almost no fluorescence value when reacting with other ions (such as Figure 7 The solid filled area at the horizontal axis 2-23 in the middle), and in the absence of ultraviolet (UV) irradiation, the fluorescence probe Tz3 + No response, indicating that the fluorescent probe Tz3 is sensitive to ClO - It has strong selectivity and anti-interference ability.

[0044] In summary, the fluorescent probe Tz3 is effective for silver ions and ClO - It has good selectivity and anti-interference under fluorescence spectrum. Figure 6The area filled with diagonal lines at the horizontal axis 1 represents the detection result of the fluorescent probe Tz3 for silver ions, the area filled with diagonal lines at the horizontal axis 11 represents the detection result of the fluorescent probe Tz3 for the mixture of silver ions and mercury ions, and the solid filled column at the horizontal axis 11 represents the detection result of the fluorescent probe Tz3 for mercury ions. The results show that when the fluorescent probe Tz3 detects silver ions, mercury ions do not respond and will not affect the detection results. - The fluorescence probe Tz3 has good selectivity and anti-interference in the fluorescence spectrum. At the same time, under the irradiation of ultraviolet light, the fluorescence probe Tz3 has good selectivity and anti-interference in the fluorescence spectrum. + Responsive to ClO - No response; In the absence of UV light, the fluorescent probe Tz3 responds to ClO - There is a response to Ag + No response; that is, the fluorescent probe Tz3 can well distinguish Ag with or without UV light irradiation. + and ClO - .

[0045] <Detection limit test>

[0046] Preparation of different concentrations of Ag + Solution, add fluorescent probe Tz3 solution and different concentrations of Ag into MeOH:PBS=4:6 solvent + The solution was irradiated with 365nm ultraviolet light (UV) for 3 minutes to obtain different Ag + The linear relationship between the solution and the fluorescence intensity at 500 nm (such as Figure 8 As shown in Figure 2), the linear relationship between the fluorescent probe Tz3 and Ag was obtained. + The fluorescence detection limit concentration was 1.87 nM.

[0047] Preparation of different concentrations of ClO - Solution, add fluorescent probe Tz3 solution and different concentrations of ClO to MeOH:PBS=4:6 solvent - Solution, get different ClO - The linear relationship between the solution and the fluorescence intensity at 500 nm (such as Fig.12 As shown in Figure 2), the linear relationship between the fluorescent probe Tz3 and ClO - The fluorescence detection limit concentration is 0.85 nM.

[0048] In summary, the fluorescent probe Tz3 + and ClO - The detection limit is extremely low, enough to detect trace amounts of Ag + and ClO - .

[0049] <Response time test>

[0050] Add a 10 μM solution of the fluorescent probe Tz3 to a MeOH:PBS = 4:6 solvent and irradiate it with a 360 - 370 nm ultraviolet lamp (UV) for different times to obtain the fluorescence spectra varying with the irradiation time of the ultraviolet lamp (UV) (as Fig. 9 shown); add a 10 μM solution of the fluorescent probe Tz3 and a 30 μM Ag + solution to a MeOH:PBS = 4:6 solvent, and the molar ratios of Ag + to the fluorescent probe Tz3 are 1:1, 3:1, and 5:1 respectively. Then irradiate it with a 360 - 370 nm ultraviolet lamp (UV) for different times to obtain the fluorescence spectra varying with the irradiation time of the ultraviolet lamp (UV) (corresponding to Fig. 9 1eqAg + 、3eqAg + 、5eqAg + ).

[0051] Add a 10 μM solution of the fluorescent probe Tz3 to a MeOH:PBS = 4:6 solvent and react for different times to obtain the fluorescence spectra varying with the reaction time (as Fig.10 shown); add a 10 μM solution of the fluorescent probe Tz3 and a 30 μM ClO - solution to a MeOH:PBS = 4:6 solvent and react for different times. Among them, the mass ratios of ClO - to the fluorescent probe Tz3 are 1:1, 3:1, and 5:1 respectively, to obtain the fluorescence spectra varying with the reaction time (corresponding to Fig.10 1eqClO - 、3eqClO - 、5eqClO - ).

[0052] The reaction time of the fluorescent probe Tz3 with Ag + reaches the maximum fluorescence intensity at 4 min, and the reaction time of the fluorescent probe Tz3 with ClO - reaches the maximum fluorescence intensity at 30 s. The response times of the fluorescent probe Tz3 to both are very short, and the detection can be completed in a short time.

[0053] <pH Influence Test>

[0054] Under different pH conditions, use the fluorescent probe Tz3 to detect Ag + and ClO - and obtain the results (as Fig.11 shown). As shown by Fig.11 , the fluorescent probe Tz3 can maintain a good response at pH = 4 - 10. Therefore, the fluorescent probe Tz3 can achieve the detection of Ag under amphoteric acid-base conditions.+ and ClO - Detection of two ions.

[0055] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for detecting Ag based on phenothiazine + and ClO - The fluorescent probe Tz3 is characterized by: The structural formula of the fluorescent probe Tz3 is: 。 2. A method for detecting Ag based on phenothiazine + and ClO - A method for preparing the fluorescent probe Tz3 according to claim 1, wherein: First, sodium carbonate was added to dichloromethane, and then a mixture of 11-ethyl-2-oxo-2,11-dihydropyrano[2,3-b]phenothiazine-3-carbonyl bromide and dimethylpyridinamine was added, followed by stirring at room temperature for reaction until the reaction was completed as detected by TLC, thereby obtaining the fluorescent probe Tz3.

3. A method for detecting Ag based on phenothiazine as claimed in claim 2 + and ClO - The method for preparing the fluorescent probe Tz3 is characterized by: The molar ratio of 11-ethyl-2-oxo-2,11-dihydropyrano[2,3-b]phenothiazine-3-carbonyl bromide and dimethylpyridinamine in the mixture is 1:

1.

4. A method for detecting Ag based on phenothiazine as claimed in claim 2 + and ClO - The method for preparing the fluorescent probe Tz3 is characterized by: The ratio of the mixture to dichloromethane added was 2mmol:10ml.

5. A method for detecting Ag based on phenothiazine as claimed in claim 2 + and ClO - The method for preparing the fluorescent probe Tz3 is characterized by: The ratio of sodium carbonate to dichloromethane added is 1mmol:10ml.

6. A fluorescent probe Tz3 as claimed in claim 1 for detecting Ag + Application in.

7. The fluorescent probe Tz3 as claimed in claim 6 is used to detect Ag + The application is characterized by: Add fluorescent probe Tz3 solution and the solution to be tested into MeOH:PBS solvent and irradiate with 360-370nm UV lamp for 3-5min. If the solution changes from yellow to colorless and transparent, the solution to be tested contains Ag. + If the color of the solution does not change, the solution to be tested does not contain Ag. + .

8. The fluorescent probe Tz3 as claimed in claim 7 is used to detect Ag + The application is characterized by: The concentration of the fluorescent probe Tz3 solution was 10 μM.

9. A fluorescent probe Tz3 as claimed in claim 1 for detecting ClO - Application in.

10. The fluorescent probe Tz3 as claimed in claim 9 is used to detect ClO - The application is characterized by: Add the fluorescent probe Tz3 solution and the solution to be tested into the MeOH:PBS solvent. If the solution changes from yellow to colorless and transparent, the solution to be tested contains ClO. - If the solution color does not change, the solution to be tested does not contain ClO - .

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