Used for continuous detection of Al with dual excitation wavelengths 3+ and F - Fluorescent probe and preparation method and application thereof

Abstract

The invention discloses a method for continuous detection of Al by dual excitation wavelengths. 3+ and F-fluorescent probe and its preparation method and application, the probe can react with Al in DMSO solvent 3+ Complexation enhances the fluorescence of the probe. Adding F ‑ The probe molecule of the present invention can not only detect Al 3+ The probe is then 3+ After binding, F ‑ Moreover, the probe Pyr is 3+ and F ‑ Dual excitation wavelength detection was established. At low excitation wavelength, the probe Pyr has the characteristics of a ratiometric fluorescent probe; at long excitation wavelength, it has the advantage of a low detection limit. At the same time, the probe is prepared into a film and can also detect Al 3+ and F ‑ Perform qualitative testing.

Description

Technical Field

[0001] The invention belongs to the field of fluorescence detection, and in particular relates to a method for continuous detection of Al by dual excitation wavelengths. 3+ and F - Fluorescent probe and its preparation method and application. Background Art

[0002] Aluminum ranks third in the earth's crust after oxygen and silicon, and is the most abundant metal element in the earth's crust. In nature, aluminum exists mainly in the form of aluminum silicate compounds in the soil. Wheat flour is a variety of foods made from flour as the main raw material through baking, roasting, steaming and frying. It is an indispensable and popular food in people's daily life. However, alum needs to be added when making fried products, and aluminum sulfate is used as baking powder when baking cakes, biscuits and bread. All of these contain aluminum. Studies have shown that aluminum is an element that is harmful to human health. It can accumulate in the human body and produce chronic toxicity. Aluminum can accumulate in brain tissue and cause central nervous system disorders; aluminum directly acts on bone tissue and causes bone pathological changes; aluminum also has embryotoxicity and embryo teratogenicity, etc. Therefore, detecting and controlling the aluminum content in food and water is of great significance to human health.

[0003] Fluoride ions are widely present in the water environment. Fluoride is present in all tissues of the human body, but it is mainly accumulated in teeth and bones. A moderate amount of fluoride is necessary for the human body, but excessive fluoride is harmful to the human body. In severe cases, it can cause people to have fragile bones. At the same time, the detection of fluoride ions is of great significance to production and life and various scientific and technological activities, such as the environment (soil, air, water), nuclear industry, electroplating, metallurgy, and minerals. - There are strict requirements for quantitative and qualitative analysis, and some industries even require up to ppb level. Due to the limitations of various complex test environments and analytical methods, errors are easily introduced, which brings many unstable factors to the control of fluoride ions. Therefore, it is necessary to develop a simpler and faster detection method for the detection of fluoride ions.

[0004] Currently, the detection of Al 3+ There are many analytical techniques, such as spectrophotometry, inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS) and graphite furnace atomic absorption spectrometry. Among them, spectrophotometry and inductively coupled plasma mass spectrometry are the most widely used. For fluoride ion detection, there are ion selective electrode method, colorimetry and ion chromatography. However, most of these methods have limitations such as complex operation and time-consuming. Fluorescence spectroscopy has the advantages of high sensitivity, good specificity and fast response time. Fluorescence spectroscopy is used to detect Al 3+ and F - Therefore, researchers are developing methods to detect these Al3+ and F - Considerable efforts have been made in the development of fluorescent probes for Al 3+ and F - Research on fluorescence detection has made great progress, but many reported probes still have problems such as low selectivity and long response time. Therefore, it is very necessary to develop a simple, highly selective and fast-response fluorescent probe for the detection of Al 3+ and F - . Summary of the invention

[0005] The present invention aims to provide a method for detecting Al2O3 by double excitation continuity in view of the shortcomings of the prior art. 3+ and F - Fluorescent probe and preparation method and application thereof.

[0006] The object of the present invention is to achieve the following technical solution: a method for continuous detection of Al2O3 by dual excitation wavelengths 3+ and F - The fluorescent probe has the following structural formula:

[0007]

[0008] A method for continuous detection of Al by dual excitation wavelengths 3+ and F - The method for preparing a fluorescent probe comprises the following steps:

[0009] (1) Synthesizing 1-methoxypyrene; comprising the following sub-steps:

[0010] (1.1) Dissolve sodium methoxide, 1-bromopyrene and anhydrous DMF in anhydrous methanol under nitrogen protection;

[0011] (1.2) heating to 110° C., adding cuprous iodide, and reacting at 110° C. for 12 hours; the molar ratio of sodium methoxide: 1-bromopyrene: anhydrous DMF: cuprous iodide is 1.5:1.0:145.2:0.1;

[0012] (1.3) After the reaction is completed, the reaction mixture is cooled to room temperature, and the reaction solution is subjected to rotary evaporation to obtain a crude product; the crude product is extracted with dichloromethane and water; after extraction, 1-methoxypyrene is obtained by column chromatography, and the eluent is: V 二氯甲烷 / V 石油醚 =1 / 1;

[0013] (2) Synthesizing 1-methoxy-2-pyrenecarboxaldehyde; comprising the following sub-steps:

[0014] (2.1) Dissolve 1-methoxypyrene and anhydrous DMF in anhydrous n-hexane at 0°C under N2 protection;

[0015] (2.2) Then, butyl lithium and N,N,N',N'-tetraaminoethylenediamine were added, and after stirring at 0°C for 4 hours, the mixture was reacted at room temperature for 12 hours; the molar ratio of 1-methoxypyrene: anhydrous DMF: butyl lithium and N,N,N',N'-tetraaminoethylenediamine was 1.0:0.3:1.3:1.3;

[0016] (2.3) After the reaction is completed, hydrochloric acid is added to quench the reaction, and the reaction solution is subjected to rotary evaporation to obtain a crude product, which is extracted with dichloromethane and water; after extraction, 1-methoxypyrene carboxaldehyde is obtained by column chromatography, and the eluent is: V 二氯甲烷 / V 石油醚 =1 / 1;

[0017] (3) Synthesizing 1-hydroxypyrene carboxaldehyde; comprising the following sub-steps:

[0018] 1-methoxypyrene carboxaldehyde and anhydrous aluminum chloride are dissolved in anhydrous dichloromethane; wherein the molar ratio of 1-methoxypyrene carboxaldehyde to anhydrous aluminum chloride is 1:6; after stirring at room temperature for 4 hours, hydrochloric acid is added to quench the reaction, and the reaction solution is subjected to rotary evaporation to obtain a crude product; the crude product is extracted with dichloromethane and water; after extraction, a yellow product 1-hydroxypyrene carboxaldehyde is obtained by column chromatography, and the eluent is: V 二氯甲烷 / V 石油醚 =9 / 1;

[0019] (4) Synthetic probe Pyr;

[0020] 1-Hydroxypyrenecarboxaldehyde and 1-hydrazinepyridine were dissolved in anhydrous ethanol, reacted at room temperature for 24 hours, and then the reaction solution was subjected to rotary evaporation to obtain a crude product, which was extracted with dichloromethane and water; after extraction, the probe Pyr was obtained by column chromatography, and the eluent was: V 二氯甲烷 / V 石油醚 =10 / 1; wherein the molar ratio of 1-hydroxypyrenecarboxaldehyde:1-hydrazinepyridine is: 1.0:1.1.

[0021] Furthermore, in the step (2), the nitrogen is replaced three times or more before adding butyl lithium to exhaust the air.

[0022] An application of the above fluorescent probe for quantitative detection of Al 3+ and F - .

[0023] Furthermore, the detection of Al 3+ The steps are as follows: dissolving the fluorescent probe Pyr in DMSO solvent, and then adding the substance to be tested; wherein the final concentration of the fluorescent probe Pyr is 1.00×10 -5mol / L probe solution; fluorescence detection is performed after the reaction.

[0024] Furthermore, the detection of F - The steps are as follows: dissolve the fluorescent probe Pyr in DMSO solvent, then add Al 3+ , and then add the substance to be tested; the final concentration of the fluorescent probe Pyr is 1×10 -5 mol / L,Al 3+ The final concentration is 2×10 -5 mol / L; fluorescence detection was performed after the reaction.

[0025] Furthermore, Al 3+ and F - The steps are as follows: dissolving the fluorescent probe Pyr in DMSO and then adding the sample to be tested; wherein the final concentration of the fluorescent probe Pyr is 1.00×10 -5 mol / L; fluorescence detection was performed after the reaction.

[0026] An application of the above fluorescent probe is used to prepare a fluorescent probe for detecting Al 3+ The membrane and the - membrane.

[0027] Further, the method for detecting Al 3+ The preparation process of the membrane is as follows: add polyvinyl alcohol to deionized water and heat it to dissolve; after cooling to room temperature, add probe Pyr to make the final concentration of polyvinyl alcohol solution 41.85g / L and the final concentration of probe Pyr solution 10μmol / L; after stirring and mixing evenly, pour into a culture dish and put it on an oscillator to shake evenly; place the culture dish in an oven at 60°C to dry. 3+ of film formation.

[0028] Furthermore, the method for detecting F - The preparation process of the membrane is as follows: polyvinyl alcohol is added to deionized water and heated until dissolved; after cooling to room temperature, Al 3+ and probe Pyr, making the final concentration of the polyvinyl alcohol solution 41.85 g / L, Al 3 + The final concentration is 4.00×10 -5 mol / L, the final concentration of the probe Pyr solution was 10 μmol / L; after stirring and mixing evenly, the mixture was poured into a culture dish and placed on an oscillator for even shaking; the culture dish was placed in an oven at 60°C for drying. - of film formation.

[0029] The beneficial effects of the present invention are: the fluorescent probe of the present invention can not only qualitatively and quantitatively detect Al 3+The probe is then 3+ After binding, F - The fluorescent probe has dual excitation wavelength detection, fast response, high sensitivity, good selectivity, and strong anti-interference ability, and can accurately identify Al in complex systems. 3+ and F - The fluorescent probe of the present invention has the characteristics of simple operation, mild reaction conditions and low cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 is a mechanism diagram of the probe of the present invention;

[0031] Figure 2 It is a diagram of the probe synthesis process in the present invention;

[0032] Figure 3 It is the hydrogen spectrum of the probe Pyr in deuterated DMSO in the present invention; the abscissa is the chemical shift (ppm), and the ordinate is the intensity;

[0033] Figure 4 Mass spectrum of the probe Pyr in the invention; ionization source: ESI + .

[0034] Figure 5 The probe Pyr(1.00×10 -5 mol / L), in 10% DMSO solution, at room temperature, and compared with control, Na + ,K + ,Ca 2+ Mg 2+ ,Al 3+ ,Cu 2+ ,Fe 3+ ,Ag + ,Mn 2+ ,Zn 2+ ,Ni + ,Pb 2+ ,Cd 2+ ,Cr 2+ ,Ba 2+ ,Hg 2+ and Fe 2+ Fluorescence spectrum of the reaction record; the excitation wavelength is 345nm;

[0035] Figure 6 The probe Pyr(1.00×10 -5 mol / L), in 10% DMSO solution, at room temperature, and compared with control, Na + ,K + ,Ca 2+ Mg 2+ ,Al 3+ ,Cu2+ ,Fe 3+ ,Ag + ,Mn 2+ ,Zn 2+ ,Ni + ,Pb 2+ ,Cd 2+ ,Cr 2+ ,Ba 2+ ,Hg 2+ and Fe 2+ Fluorescence spectrum of the reaction record; the excitation wavelength is 400nm;

[0036] Figure 7 The probe Pyr of the present invention is reacted with different concentrations of Al 3+ Fluorescence intensity and linear relationship diagram after reaction; excitation wavelength is 345nm;

[0037] Figure 8 The probe Pyr of the present invention is reacted with different concentrations of Al 3+ Fluorescence intensity and linear relationship diagram after reaction; excitation wavelength is 400nm;

[0038] Fig. 9 The probe Pyr-Al 3+ (1.00×10 -5 mol / L), in 10% DMSO solution, at room temperature, respectively with control, Cl - ,Br - ,I - ,CO3 2- ,SO4 2- ,NO3 - ,PO4 3- ,HCO3 - ,HSO4 - ,ClO - ,HPO4 2- ,H2PO4 - Fluorescence spectrum of the reaction record; excitation wavelength: 345nm;

[0039] Fig.10 The probe Pyr-Al 3+ (1.00×10 -5 mol / L), in 10% DMSO solution, at room temperature, respectively with control, Cl - ,Br - ,I - ,CO3 2- ,SO4 2- ,NO3 - ,PO4 3- ,HCO3 - ,HSO4 -,ClO - ,HPO4 2- ,H2PO4 - Fluorescence spectrum of the reaction record; excitation wavelength: 400nm;

[0040] Fig.11 Pyr-Al 3+ With different concentrations of F - Fluorescence intensity and linear relationship diagram of the reaction; excitation wavelength: 345nm.

[0041] Fig.12 Pyr-Al 3+ With different concentrations of F - Fluorescence intensity and linear relationship diagram of the reaction; excitation wavelength: 400nm;

[0042] Fig.13 The fluorescence color change diagram of the film prepared by the fluorescent probe of the present invention when different equivalents of Al3+ and F- are added. DETAILED DESCRIPTION

[0043] The present invention is further described below in conjunction with examples and drawings, but the present invention is not limited to the following embodiments.

[0044] Example 1: Synthesis of Pyr fluorescent probe; Figure 2 As shown;

[0045] Step 1: In a 250 mL round-bottom flask under N2 protection, add 1-bromopyrene (5.00 g, 18.00 × 10 -3 mol) and sodium methoxide (1.44 g, 26.68 × 10 -3 mol), heated to 110°C. After the temperature rose to 110°C, CuI (0.34 g, 1.80 × 10 -3 mol). The reaction was carried out at 110°C for 12 hours. After the reaction was completed, the reaction solution was cooled and subjected to rotary evaporation to obtain a crude product. The crude product was extracted with water and dichloromethane three times. The upper organic layer was collected and then dried over anhydrous Na2SO4. After removing the solvent under reduced pressure, column chromatography was performed with CH2Cl2 / petroleum ether (v / v, 1:9) as the eluent to obtain the first step product 1-methoxypyrene solid (3.00 g, yield 60.00%).

[0046] Step 2: In a 250 mL round-bottom flask under N2 protection, 1-methoxypyrene (0.50 g, 2.15 × 10 -3 mol), then n-butyl lithium (1.05 mL, 2.80 × 10 -3mol), N,N,N',N'-tetramethylaminoethylenediamine (0.27mL, 2.80×10 -3 mol) and anhydrous DMF 0.16mL. Stir the reaction at 0℃ for 4 hours and at room temperature for 12 hours. After the reaction is completed, add 3mL of 0.50mol / L dilute hydrochloric acid to quench the reaction. After the reaction is completed, the reaction solution is rotary evaporated to obtain a crude product. The crude product is extracted with water and dichloromethane 3 times. The upper organic layer is collected and then dried over anhydrous Na2SO4. After removing the solvent under reduced pressure, CH2Cl2 / petroleum ether (v / v, 1:1) is used as the eluent and purified by column chromatography to obtain the second step product 1-methoxypyrene formaldehyde solid (0.30g, yield 60.00%).

[0047] Step 3: Under normal temperature, add 0.25 of 1-methoxypyrene carboxaldehyde to 10mL of anhydrous dichloromethane, and then add 1.00g AlCl3. After stirring at room temperature for 4 hours, add 0.50mol / L of dilute hydrochloric acid to quench the reaction. After the reaction is completed, the reaction solution is rotary evaporated to obtain a crude product. The crude product is extracted 3 times with water and dichloromethane. Collect the upper organic layer and then dry it with anhydrous Na2SO4. After removing the solvent under reduced pressure, use CH2Cl2 / petroleum ether (v / v, 1:1) as the eluent, and purify by column chromatography to obtain the third step product 1-hydroxypyrene carboxaldehyde solid (0.50g, yield 60.00%).

[0048] Step 4: At room temperature, 1-hydroxypyrene carboxaldehyde (0.25 g, 1.01 × 10 -3 mol) and 2-hydrazinepyridine (0.11 g, 1.02 × 10 -3 mol), after reacting overnight, the reaction solution was rotary evaporated to obtain a crude product. The crude product was extracted with water and dichloromethane three times. The upper organic layer was collected and then dried over anhydrous Na2SO4. After removing the solvent under reduced pressure, CH2Cl2 / petroleum ether (v / v, 4:1) was used as the eluent for column chromatography purification to obtain the third step product probe Pyr solid (0.20 g, yield 80.00%).

[0049] After synthesis, the probe structure was characterized by hydrogen nuclear magnetic resonance spectrum and mass spectrometry: Figure 3 As shown, 1H NMR(500MHz,Chloroform-d)δ12.30(s,1H),11.34(s,1H),8.66(s,1H),8.44(d,J=9.1Hz,1H),8.33(s,1H),8.25(d,J=3.8Hz,1H),8.18–8.15(m,2H),8 .12(d,J=9.3Hz,1H),8.06(d,J=9.0Hz,1H),8.00(t,J=7.6Hz,1H),7.95(d, J=9.0Hz,1H),7.77–7.73(m,1H),7.06(d,J=8.3Hz,1H),6.89-6.86(m,1H); such as Figure 4 As shown, the maximum mass-to-charge ratio is consistent with the relative molecular mass of the probe.

[0050] The mechanism of the probe of the present invention is as follows Figure 1 As shown, the probe itself exhibits blue fluorescence under a handheld UV lamp, and the fluorescence color of the probe changes from green to blue after the addition of aluminum ions.

[0051] The mechanism of action of the fluorescent probe of the present invention is as follows: in the probe molecule, nitrogen and oxygen are Al 3+ Provides a selective chelator "pocket", resulting in a strong blue fluorescence color (Ex = 340nm detection limit: 3.31×10 -7 mol / L, Ex400 nm detection limit: 1.87×10 -9 mol / L). At the same time, a 1:1 stoichiometric ratio of Pyr-Al 3+ Complex. Complex added F - Later, due to Al 3+ With F - The binding force between them is greater than that between Pyr and Al 3+ The binding force between them makes F - Al 3+ From the originally formed Pyr-Al 3+ The complex was replaced, and then the fluorescence returned to green (Ex = 340nm detection limit: 3.99×10 -7 mol / L, Ex400 nm detection limit: 2.97×10 -9 mol / L). - For Al 3+ The displacement method causes the probe itself to be released, so the detection system shows the detection of Al 3+ With F - High selectivity, obvious color change and dual excitation wavelength detection.

[0052] Example 2: Selectivity of Pyr fluorescent probe for different metal ions

[0053] The fluorescent probe Pyr prepared in Example 1 was prepared with DMSO as solvent at a concentration of 1×10 -4 mol / L probe stock solution. The concentration of the probe stock solution used in the following examples is 1×10 -4 mol / L.

[0054] The following substances NaCl, KCl, CaCl2, MgCl2·6H2O, AlCl3, CuCl2·2H2O, FeCl3·6H2O, AgNO3, MnCl2·4H2O, ZnCl2, NiCl·6H2O, PbCl2, CdCl2·2.5H2O, CrCl3·6H2O, BaCl2·2H2O, FeCl2·4H2O, HgCl2 are arranged into 1×10 -2 mol / L metal ion stock solution.

[0055] Take 18 test tubes, add 150μL of the above different metal ion mother solutions in turn, replace the interfering substances with an equal amount of water, then add 2550μL of ultrapure water, and finally add 300μL of probe mother solution. After each solution is shaken, perform fluorescence detection (Ex = 345nm, Ex = 400nm). Use fluorescence intensity as the ordinate and wavelength as the abscissa Figure 5 and Figure 6 ,Depend on Figure 5 and Figure 6 It can be found that Al 3+ It can significantly change the fluorescence intensity of Pyr, while other metal ions have little interference with its fluorescence intensity.

[0056] Example 3: Different concentrations of Al 3+ The fluorescence intensity of Pyr

[0057] The concentration is 1×10 -3 mol / LAl 3+ The final Al 3+ concentration, forming 0-10 equivalents of Al 3+ Add different volumes of Al 3+ After reacting with the probe, fluorescence detection was performed at two different excitation wavelengths (Ex = 345nm, Ex = 400nm) to detect the fluorescence intensity in each system. 3+ The concentration is plotted as the horizontal axis, and a linear relationship is plotted. Figure 7 and Figure 8 It can be seen that with the Al 3+As the concentration increases, the fluorescence intensity of the probe changes continuously (Ex = 345 nm, detection limit: 3.31 × 10 -7 mol / L, Ex = 400nm Detection limit: 1.89×10 -7 mol / L).

[0058] Example 4: Pyr-Al 3+ Selectivity of the complexes for different anions

[0059] The following substances, F - , Cl - ,Br - ,I - ,CO3 2- ,SO4 2- ,NO3 - ,PO4 3- ,HCO3 - ,HSO4 - ,ClO - ,HPO4 2- ,H2PO4 - Configured as 1×10 -3 mol / L anion stock solution.

[0060] Take 21 test tubes, add 30 μL of different metal ion mother solutions in Example 2 in turn, replace the interfering substances with equal amount of water, add 2640 μL of ultrapure water, and then add 300 μL of probe mother solution respectively. After the reaction, add 30 μL of anion mother solution. After each solution is shaken, perform fluorescence detection (Ex = 345nm, Ex = 400nm). Use fluorescence intensity as the ordinate and wavelength as the abscissa Fig. 9 and Fig.10 .Depend on Fig. 9 and Fig.10 It can be seen that only F - Able to be used with Pyr-Al 3+ The complex undergoes a displacement reaction, allowing the fluorescence of the probe to be restored.

[0061] Example 5: Different concentrations of F - Lower Pyr-Al 3+ Fluorescence intensity of the complex

[0062] The concentration is 1.00×10 -4 mol / L F - Similar to Example 3, the final F - concentration, forming different equivalents of F - Add 300 μL of probe stock solution to the test tube and then add 10 equivalents of Al 3+, so that the probe fluorescence is completely quenched. Then different volumes of F - After the reaction, fluorescence detection (Ex = 345nm, Ex = 400nm) was performed to detect the fluorescence intensity in each system. Fig.11 and Fig.12 As shown in the figure, a curve was drawn with the fluorescence intensity as the ordinate and the concentration of L-Cys as the abscissa, and a linear relationship diagram was drawn (Ex = 345nm detection limit: 3.99×10 - 7 mol / L, Ex = 400nm, detection limit: 2.97×10 -9 mol / L).

[0063] Example 6: Pyr fluorescent probe for Al in different water samples 3+ Detection

[0064] Five water samples were selected for spike recovery experiments (including tap water, food factory wastewater, chemical plant wastewater, sewage treatment plant wastewater and mineral water). Five Al 3+ The concentration is 1.00×10 -3 mol / L solution.

[0065] Add 300 μL of Pyr stock solution to 5 test tubes, dilute to 3 mL with 2700 μL of 5 water samples, and perform fluorescence detection at Ex = 345 nm and Ex = 400 nm. Calculate the recovery rate and relative standard deviation (RSD). 3+ Concentration, recovery rate, and RSD are plotted as the horizontal axis in Tables 1 and 2. As shown in Tables 1 and 2, under the two excitation wavelengths, the probe can obtain good recovery rates (Ex = 340 is 99.49%-100.4%, Ex = 400 is 100.3%-100.8%) and RSD values ​​(Ex = 340 is less than 1.2%, Ex = 400 is less than 0.7%).

[0066] Table 1: Al in actual water samples 3+ Recovery rate dataEx:340nm

[0067]

[0068] Table 2: Al in actual water samples 3+ Recovery rate dataEx:400nm

[0069]

[0070] Example 7: Pyr-Al 3+ Effect of the complex on F in different water samples - Detection

[0071] Five water samples were selected for spike recovery experiments (including tap water, food factory wastewater, chemical plant wastewater, sewage treatment plant wastewater and mineral water). Five F - The concentration is 1.00×10 -3 mol / L solution.

[0072] When testing water samples, take 300 μL of Pyr mother solution and add 10 equivalents of Al 3+ Reaction, add 30μL water sample to dilute to 3mL, and react in the same way. After each solution is shaken, fluorescence detection (Ex=345nm and Ex=400nm) is performed to calculate the recovery rate and RSD. Tables 3 and 4 are plotted with the actual sample as the ordinate and L-Cys concentration, recovery rate, and RSD as the abscissa. As shown in Tables 3 and 4, under two excitation wavelengths, the probe can obtain good recovery rates (Ex=340 is 99.00%-100.2%, Ex=400 is 99.77%-100.5%) and RSD values ​​(Ex=340 is less than 1.6%, Ex=400 is less than 1.6%).

[0073] Table 3: F in actual water samples - Recovery rate dataEx:340nm

[0074]

[0075] Table 4: F in actual water samples - Recovery rate dataEx:400nm

[0076]

[0077] Example 8: Pyr fluorescent probe for Al in different common foods 3+ Detection

[0078] Fluorescence detection of Al in common foods 3+ When the Al contained in the test sample is 3+ When the content is high, take 0.50g of sample and add 50.00mL ultrapure water to the juicer and crush it thoroughly. Let it stand and take the supernatant for centrifugation. After centrifugation, take 30.00μL in a test tube, then add 2670.00μL ultrapure water and mix well. Finally, add 300.00μL probe mother solution, shake well and react for 5 minutes before detection (Ex=345nm and Ex=400nm). Detection of added Al 3+ When the concentration is , add the corresponding Al to the solution after centrifugation of the sample 3+, other steps are similar. Calculate the recovery rate and RSD, and draw Tables 5 and 6. As shown in Tables 5 and 6, under the two excitation wavelengths, the probe can obtain good recovery rates (Ex = 340 is 99.23%-104%, Ex = 400 is 99.56%-103%) and RSD values ​​(Ex = 340 is less than 1.7%, Ex = 400 is less than 1.3%). The P value is a significance test method, which is used to test whether there is a significant difference between the experimental group and the control group in a scientific experiment. Statistically, P>0.05 is defined as no statistical difference, that is, there is no significant difference between the two groups of data. This also proves that the fluorescence method proposed in this application is used to detect Al in samples. 3+ There is no significant difference in the detection results compared with the traditional method, which proves that the fluorescence method can be used to detect Al in actual samples. 3+ .

[0079] Table 5: Al in common foods 3+ Recovery data Ex = 340nm

[0080]

[0081] Table 6: Al in common foods 3+ Recovery data Ex = 400nm

[0082]

[0083]

[0084] Example 9: Pyr fluorescent probe for F in different daily chemicals - Detection

[0085] Fluorescence detection of F in common daily chemicals - When the toothpaste is 1.50g, add 30.00mL ultrapure water to the test tube. Stir thoroughly, centrifuge and take 30.00μL of the supernatant in the test tube, then add 2550.00μL of ultrapure water and mix well. Finally, add 300.00μL of probe mother solution and 120.00μL of Al 3+ The mother solution was shaken and reacted for 5 minutes before detection (Ex = 345nm and Ex = 400nm). When detecting mouthwash, 50.00μL of mouthwash was directly taken, diluted to 20.00mL, and 50.00μL was taken for detection. The recovery rate and RSD were calculated and Tables 7 and 8 were plotted. As shown in Tables 7 and 8, the probe can obtain good RSD values ​​under two excitation wavelengths (Ex = 340 is less than 1.8%, Ex = 400 is less than 2.4%).

[0086] Table 7: F in common daily chemical products - Recovery data Ex = 340nm

[0087]

[0088]

[0089] Table 8: F in common daily chemical products - Recovery data Ex = 400nm

[0090]

[0091] Example 10: Application of Pyr fluorescent probe in membrane detection

[0092] Add 1.13 g of polyvinyl alcohol to 27.00 mL of water and heat until dissolved. Prepare 1.00 × 10 -4 mol / L probe stock solution. After cooling, add 3.00mL probe stock solution and stir evenly. Pour the solution into a petri dish and shake it evenly on a micro-oscillator. Transfer to an oven and dry at 60°C (generally for 3 hours). After drying, tear off the membrane with tweezers, and then drop different concentrations of Al 3+ , observe the fluorescence color change of the membrane under a handheld UV lamp. - , prepare polyvinyl alcohol solution in the same way, and add a certain amount of Al 3+ , so that the final concentration of polyvinyl alcohol solution is 41.85g / L, Al 3+ The final concentration is 4.00×10 -5 mol / L, the final concentration of the probe Pyr solution was 1.00×10 -5 mol / L; prepare the film, add different equivalents of F- and observe the fluorescence color change under a handheld UV lamp. Take photos of all the fluorescence color changes and draw a picture. Fig.13 ;like Fig.13 As shown in the figure, as the concentration of aluminum ions added increases, the fluorescence color of the membrane gradually changes from blue to green. 3+ For the membrane, as the concentration of added fluoride ions increases, the fluorescence color of the membrane gradually recovers from blue to the blue fluorescence of the probe itself.

[0093] The above embodiments are only used to illustrate the design ideas and features of the present invention, and their purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. The protection scope of the present invention is not limited to the above embodiments. Therefore, any equivalent changes or modifications made based on the principles and design ideas disclosed by the present invention are within the protection scope of the present invention.

[0094] Those skilled in the art will readily appreciate other embodiments of the present application after considering the description and practicing the contents disclosed herein. The present application is intended to cover any variations, uses or adaptations of the present application, which follow the general principles of the present application and include common knowledge or customary technical means in the art that are not disclosed in the present application. The description and examples are intended to be exemplary only.

Claims

1. A method for continuous detection of Al with dual excitation wavelengths 3+ and F - A fluorescent probe characterized in that Has the following structural formula:

2. A method for continuous detection of Al by dual excitation wavelengths according to claim 1 3+ and F - A method for preparing a fluorescent probe, characterized in that: The following steps are involved: (1) Synthesis of 1-methoxypyrene; It includes the following sub-steps: (1.1) Dissolve sodium methoxide, 1-bromopyrene and anhydrous DMF in anhydrous methanol under nitrogen protection; (1.2) heating to 110° C., adding cuprous iodide, and reacting at 110° C. for 12 hours; the molar ratio of sodium methoxide: 1-bromopyrene: anhydrous DMF: cuprous iodide is 1.5:1.0:145.2:0.1; (1.3) After the reaction is completed, the reaction mixture is cooled to room temperature, and the reaction solution is subjected to rotary evaporation to obtain a crude product; the crude product is extracted with dichloromethane and water; after extraction, 1-methoxypyrene is obtained by column chromatography, and the eluent is: V 二氯甲烷 / V 石油醚 =1 / 1; (2) Synthesis of 1-methoxy-2-pyrenecarboxaldehyde; It includes the following sub-steps: (2.1) Dissolve 1-methoxypyrene and anhydrous DMF in anhydrous n-hexane at 0°C under N2 protection; (2.2) Then, butyl lithium and N,N,N',N'-tetraaminoethylenediamine were added, and after stirring at 0°C for 4 hours, the mixture was reacted at room temperature for 12 hours; the molar ratio of 1-methoxypyrene: anhydrous DMF: butyl lithium and N,N,N',N'-tetraaminoethylenediamine was 1.0:0.3:1.3:1.3; (2.3) After the reaction is completed, hydrochloric acid is added to quench the reaction, and the reaction solution is subjected to rotary evaporation to obtain a crude product, which is extracted with dichloromethane and water; after extraction, 1-methoxypyrene carboxaldehyde is obtained by column chromatography, and the eluent is: V 二氯甲烷 / V 石油醚 =1 / 1; (3) Synthesis of 1-hydroxypyrene carboxaldehyde; It includes the following sub-steps: 1-methoxypyrene carboxaldehyde and anhydrous aluminum chloride are dissolved in anhydrous dichloromethane; wherein the molar ratio of 1-methoxypyrene carboxaldehyde to anhydrous aluminum chloride is 1:6; after stirring at room temperature for 4 hours, hydrochloric acid is added to quench the reaction, and the reaction solution is subjected to rotary evaporation to obtain a crude product; the crude product is extracted with dichloromethane and water; after extraction, a yellow product 1-hydroxypyrene carboxaldehyde is obtained by column chromatography, and the eluent is: V 二氯甲烷 / V 石油醚 =9 / 1; (4) Synthetic probe Pyr; 1-Hydroxypyrene carboxaldehyde and 1-hydrazine pyridine were dissolved in anhydrous ethanol, reacted at room temperature for 24 hours, and then the reaction solution was subjected to rotary evaporation to obtain a crude product, which was extracted with dichloromethane and water; after extraction, the probe Pyr was obtained by column chromatography, and the eluent was: V 二氯甲烷 / V 石油醚 =10 / 1; wherein the molar ratio of 1-hydroxypyrenecarboxaldehyde:1-hydrazinepyridine is: 1.0:1.

1.

3. A method for continuous detection of Al by dual excitation wavelengths according to claim 2. 3+ and F - A method for preparing a fluorescent probe, characterized in that: In the step (2), nitrogen is replaced three or more times before adding butyl lithium to exhaust air.

4. A use of the fluorescent probe according to claim 1, characterized in that: For quantitative detection of Al 3+ and F - .

5. The use of the fluorescent probe according to claim 4, characterized in that: Detection of Al 3+ The steps are as follows: dissolving the fluorescent probe Pyr in DMSO solvent, and then adding the substance to be tested; wherein the final concentration of the fluorescent probe Pyr is 1.00×10 -5 mol / L probe solution; fluorescence detection is performed after the reaction.

6. The use of the fluorescent probe according to claim 4, characterized in that: Detection F - The steps are as follows: dissolve the fluorescent probe Pyr in DMSO solvent, then add Al 3+ , and then add the substance to be tested; the final concentration of the fluorescent probe Pyr is 1×10 -5 mol / L,Al 3+ The final concentration is 2×10 -5 mol / L; fluorescence detection was performed after the reaction.

7. The use of the fluorescent probe according to claim 4, characterized in that: Simultaneous detection of Al 3+ and F - The steps are as follows: dissolving the fluorescent probe Pyr in DMSO and then adding the sample to be tested; wherein the final concentration of the fluorescent probe Pyr is 1.00×10 - 5 mol / L; fluorescence detection was performed after the reaction.

8. A use of the fluorescent probe according to claim 1, characterized in that: For the preparation of Al 3+ The membrane and the - membrane.

9. The use of the fluorescent probe according to claim 8, characterized in that: The method for detecting Al 3+ The preparation process of the membrane is as follows: add polyvinyl alcohol to deionized water and heat it to dissolve; after cooling to room temperature, add probe Pyr to make the final concentration of polyvinyl alcohol solution 41.85g / L and the final concentration of probe Pyr solution 10μmol / L; after stirring and mixing evenly, pour into a culture dish and put it on an oscillator to shake evenly; place the culture dish in an oven at 60°C to dry. 3+ of film formation.

10. The use of the fluorescent probe according to claim 8, characterized in that: The method for detecting F - The preparation process of the membrane is as follows: polyvinyl alcohol is added to deionized water and heated until dissolved; after cooling to room temperature, Al 3+ and probe Pyr, making the final concentration of the polyvinyl alcohol solution 41.85 g / L, Al 3+ The final concentration is 4.00×10 -5 mol / L, the final concentration of the probe Pyr solution was 10 μmol / L; after stirring and mixing evenly, the mixture was poured into a culture dish and placed on an oscillator for even shaking; the culture dish was placed in an oven at 60°C for drying. - of film formation.

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