A coumarin molecular probe containing a porphine group, and its preparation method and application

Abstract

The present invention belongs to the technical field of fluorescent probes and discloses a coumarin molecular probe containing a porphine group, a preparation method and an application thereof, comprising: using dicarboxyphenylporphine as a raw material; performing chlorination modification on two carboxyl groups in the dicarboxyphenylporphine molecule to obtain a chlorinated porphine compound; performing a nucleophilic addition reaction on the chlorinated porphine compound and a hydroxyl-containing coumarin to prepare the coumarin molecular probe containing a porphine group; the preparation process of the present invention is simple, the reaction conditions are low and the yield is high, and the molecular probe is sensitive to Fe 3+ It has high selectivity, sensitivity and anti-interference, and can 2+ and Fe 3+ It can be used for precise identification and has good application prospects in the fields of light absorption antennas, organic light-emitting diodes, fluorescent probes and anti-tumor drugs.

Description

Technical Field

[0001] The invention belongs to the technical field of fluorescent probes, and particularly relates to a coumarin molecular probe containing a porphine group, a preparation method and an application thereof. Background Art

[0002] The iron content in the water-steam system of a thermal power plant is an important basis for evaluating the corrosion and scaling status of the thermal system of a power generation unit. It is one of the key monitoring indicators in the daily operation of a thermal power plant. Currently, the main methods for determining total iron in power production feed water, boiler water, and drain water include o-phenanthroline spectrophotometry (Boiler Water and Cooling Water Analysis Method - Determination of Iron Standard, GB / T14427-2008) and graphite furnace atomic absorption spectrometry (Graphite Furnace Atomic Absorption Spectrometry (Graphite Furnace Atomic Absorption Spectrometry, DL / T955-2005)). Among them, o-phenanthroline spectrophotometry is a traditional manual analysis method with complex operation, low analysis efficiency, narrow linear range, and easy contamination of sample water. In particular, the detection accuracy of low concentrations of iron ions (<10 μg / L) is low, and human error is inevitable. The instrumentation used in the graphite furnace atomic absorption spectrometry is expensive and requires high operation and maintenance. Therefore, the development of fluorescent molecular probes that can be used for iron ion detection is of great significance for iron measurement in power plants.

[0003] At present, there are also reports on the use of Fe 3+ Fluorescent molecular probe technology can be used to determine iron ions. From a structural point of view, it mainly includes rhodamine B type, pyridine type, naphthalimide type, coumarin type and coumarin compounds with benzo α-pyrone structure. However, the above-mentioned Fe 3+ Fluorescent molecular probes generally have the defects of low selectivity and sensitivity, and are unable to detect Fe 2+ and Fe 3+ Make accurate identification. Summary of the Invention

[0004] In view of the technical problems existing in the prior art, the present invention provides a coumarin molecular probe containing a porphine group and its preparation method and application to solve the existing Fe 3+ Fluorescent molecular probes generally have the defects of low selectivity and sensitivity, and are unable to detect Fe 2+ and Fe 3+ Technical issues in making accurate identification.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] The present invention provides a coumarin molecular probe containing a porphine group, wherein the coumarin molecular probe has the following structure:

[0007]

[0008] The present invention also provides a method for preparing a coumarin molecular probe containing a porphine group, which comprises using dicarboxyphenylporphine as a raw material; performing chlorination modification on the two carboxyl groups in the dicarboxyphenylporphine molecule to obtain a chlorinated porphine compound; and subjecting the chlorinated porphine compound to a nucleophilic addition reaction with a hydroxyl-containing coumarin to prepare the coumarin molecular probe containing a porphine group.

[0009] Furthermore, the preparation method of the coumarin molecular probe containing a porphine group comprises the following steps:

[0010] Dicarboxyphenylporphine is mixed with chloroform, stirred thoroughly, and then cooled to a first preset temperature in an ice bath, and then anhydrous thionyl chloride is added; after the anhydrous thionyl chloride is added dropwise, the temperature is raised to a second preset temperature, and stirred for reaction; after the reaction is completed, reduced pressure distillation is performed under vacuum conditions to remove anhydrous thionyl chloride and chloroform, and vacuum drying is performed to obtain diformylchlorophenylporphine;

[0011] Diformylchlorophenylporphine, triethylamine and chloroform are mixed and stirred evenly, and then 6-hydroxy-4-methylcoumarin is added and stirred for reaction. After the reaction, the mixture is cooled, filtered, washed, recrystallized and dried to prepare a coumarin molecular probe containing a porphine group.

[0012] Furthermore, in the process of mixing dicarboxyphenylporphine with chloroform, chloroform and dicarboxyphenylporphine are mixed in a millimolar ratio of (80-100):(8-10); wherein, the chloroform is fully dehydrated with anhydrous sodium sulfate before use.

[0013] Furthermore, during the reduced pressure distillation under vacuum conditions, the vacuum degree is 740-750 mmHg.

[0014] Furthermore, in the process of mixing dichlorophenylporphine, triethylamine and chloroform, dichlorophenylporphine, triethylamine and chloroform are mixed in a millimole ratio of (5-8):(12-24):(100-160).

[0015] Furthermore, dichlorophenylporphine, triethylamine and chloroform are mixed and stirred uniformly before adding 6-hydroxy-4-methylcoumarin. The millimole ratio of 6-hydroxy-4-methylcoumarin to dichlorophenylporphine is (5-8):(12-17).

[0016] Furthermore, the cooling process is carried out in an ethanol-dry ice low-temperature bath; wherein the cooling temperature is -45°C to -35°C.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] The present invention provides a coumarin molecular probe containing a porphine group, a preparation method thereof, and an application thereof. The coumarin molecular probe containing a porphine group is obtained by introducing a biologically active and photoactive coumarin derivative into a chlorinated porphine compound through a nucleophilic addition reaction. Since the nitrogen atom on the porphine group has a lone pair of electrons, it can form a coordination bond with the iron ion to achieve complexation of the iron ion. By introducing a coumarin group with fluorescent properties, the electron-withdrawing ester group increases the probability of charge transfer within the molecule, thereby enhancing the fluorescence performance, achieving a fluorescent effect under visible light, and thereby effectively enhancing the recognition ability of the molecular probe. Secondly, due to the Fe 3+ Compared with Fe 2+ With higher positive charge density and smaller ionic radius, the porphin ligand in the porphin group can more easily react with Fe 3+ Forming a stable complex effectively improves the 3+ The complexing ability of the dicarboxyphenylporphine is enhanced, thereby enhancing the selectivity of the molecular probe; in addition, through chloroacylation modification and nucleophilic addition reaction, the carboxyl group in the dicarboxyphenylporphine can undergo an electrophilic substitution reaction with the acylating agent thionyl chloride to generate a chloroacylated product, diformylchlorophenylporphine, and the chloroacyl group in the diformylchlorophenylporphine can undergo a nucleophilic addition reaction with the hydroxyl group in 6-hydroxy-4-methylcoumarin. The acyl chloride containing active hydrogen easily releases hydrogen chloride in the reaction, further promoting the reaction, thereby generating a target molecular probe. The corresponding molecular probe can be prepared through a two-step reaction, and the molecular structure and properties of the molecular probe can be precisely controlled. The preparation process of the present invention is simple, the reaction conditions are low, and the yield is high. The molecular probe has high selectivity to Fe 3+ It has high selectivity, sensitivity and anti-interference, and can 2+ and Fe 3+ It can be used for precise identification and has good application prospects in the fields of light absorption antennas, organic light-emitting diodes, fluorescent probes and anti-tumor drugs. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0020] Figure 1 The synthetic route of the coumarin molecular probe containing porphine group of the present invention;

[0021] Figure 2 The coumarin molecular probe prepared in Example 1 detects Fe for different metal ions. 3+ Impact result diagram;

[0022] Figure 3 The coumarin molecular probe prepared in Example 1 detects Fe 3+ The relationship between the measurement time and the fluorescence intensity is shown in the graph;

[0023] Figure 4 The coumarin molecular probe prepared in Example 1 detects Fe 3+ The relationship between temperature and fluorescence intensity is shown in the graph;

[0024] Figure 5 The coumarin molecular probe prepared in Example 1 detects Fe 3+ The relationship between pH and fluorescence intensity;

[0025] Figure 6 The coumarin molecular probe prepared in Example 1 and Fe 3+ The relationship between the complexation ratio and fluorescence intensity;

[0026] Figure 7 The coumarin molecular probe prepared in Example 1 detects Fe 3+ Time Fe 3+ The relationship between the concentration and fluorescence intensity is shown in the graph. DETAILED DESCRIPTION

[0027] In order to make the technical problems, technical solutions, and beneficial effects solved by this application more clearly understood, the technical solutions in the embodiments of this application will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of this application; it is obvious that the described embodiments are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of this application.

[0028] The present invention provides a coumarin molecular probe containing a porphine group. The structure of the coumarin molecular probe containing a porphine group is as follows:

[0029]

[0030] As attached Figure 1 As shown, the preparation route of the coumarin molecular probe containing a porphine group is as follows: using dicarboxyphenylporphine as a raw material; chlorination modification of the two carboxyl groups in the dicarboxyphenylporphine molecule to obtain a chlorinated porphine compound; and nucleophilic addition reaction of the chlorinated porphine compound with a hydroxyl-containing coumarin to prepare the coumarin molecular probe containing a porphine group.

[0031] Specifically, the method for preparing the coumarin molecular probe containing a porphine group comprises the following steps:

[0032] Step 1, dicarboxyphenylporphine and chloroform are mixed, stirred thoroughly, and then cooled to a first preset temperature under ice bath conditions, and then anhydrous thionyl chloride is added; chloroform and dicarboxyphenylporphine are mixed in a millimolar ratio of (80-100): (8-10); wherein, chloroform is fully dehydrated with anhydrous sodium sulfate before use; preferably, the first preset temperature is below 5°C; after the anhydrous thionyl chloride is added dropwise, the temperature is raised to a second preset temperature, and the reaction is stirred; preferably, the second preset temperature is 65°C; after the stirring reaction is completed, vacuum distillation is performed under a vacuum condition of 740-750 mmHg to remove anhydrous thionyl chloride and chloroform, and vacuum drying is performed to obtain diformyl chloride phenylporphine; it should be noted that when the vacuum distillation is performed under a vacuum condition of 740-750 mmHg, the amount of hydrogen chloride generated can be ensured to be reduced.

[0033] Step 2: Mix dichlorophenylporphine, triethylamine and chloroform, stir evenly, add 6-hydroxy-4-methylcoumarin, stir for reaction, heat to a third preset temperature, stir, heat and reflux for 2-4 hours to obtain a reaction system; wherein, dichlorophenylporphine, triethylamine and chloroform are mixed in a millimolar ratio of (5-8): (12-24): (100-160), and the millimolar ratio of 6-hydroxy-4-methylcoumarin to dichlorophenylporphine is (5-8): (12-17); preferably, the third preset temperature is 70°C.

[0034] Step 3: Cooling, filtering, washing, recrystallizing and drying the reaction system to prepare a coumarin molecular probe containing a porphine group; the cooling process is carried out in an ethanol-dry ice low-temperature bath at a cooling temperature of -45°C to -35°C.

[0035] Preparation principle:

[0036] The preparation method of the coumarin molecular probe containing a porphine group of the present invention comprises the following steps: through chloroacylation modification and nucleophilic addition reaction, the carboxyl group in dicarboxyphenylporphine can undergo an electrophilic substitution reaction with the acylating agent thionyl chloride to generate a chloroacylated product, diformylchlorophenylporphine; and the chloroacyl group in the diformylchlorophenylporphine can undergo a nucleophilic addition reaction with the hydroxyl group in 6-hydroxy-4-methylcoumarin. The acyl chloride containing active hydrogen easily releases hydrogen chloride during the reaction, further promoting the reaction, thereby generating a target molecular probe. The corresponding molecular probe can be prepared through a two-step reaction.

[0037] The porphine group-containing coumarin molecular probe prepared in the present invention contains both a porphine ring and a coumarin group. The porphine ring itself has a characteristic absorption spectrum in the ultraviolet-visible light region, wherein the maximum absorption peak usually appears in the Soret band at around 400 nm and the Q band at 450-700 nm. Since the coordination number of the iron ion is usually 6, it can form a coordination bond with multiple ligand atoms, such as nitrogen atoms. In the case of the porphine ring, the iron ion forms a four-coordinate structure with the four nitrogen atoms on the porphine ring. The coumarin group itself has fluorescent properties, and due to the introduction of the electron-withdrawing ester group in the molecule, the intramolecular charge transfer probability is increased, and the fluorescence itself is enhanced, so that a fluorescent effect under visible light is obtained. Combined with the maximum characteristic absorption wavelength of the porphine ring, which basically belongs to the visible light region, the introduction of the coumarin group has a synergistic effect of enhancing fluorescence. Therefore, it is applied to trace amounts of Fe in ultrapure water. 3+ When detecting trace Fe, the fluorescence quenching phenomenon is used to detect 3+ Accurate detection of 3+ After 1 min, the fluorescence was almost completely quenched, which shows that Fe 3+ The recognition of coumarin molecular probes is relatively rapid.

[0038] Detection of trace Fe in ultrapure water using the coumarin molecular probe containing porphine groups described in the present invention 3+ The process is as follows:

[0039] 1 mL 1×10 -4 mol / L of porphine-containing coumarin molecular probe was added to several 10 mL volumetric flasks in sequence; then, 1 mL of 0-5×10 -5 mol / L of 10 groups of Fe 3+ Aqueous solution sample; then, adjust the pH of the mixed solution to 4-9 with 0.01 mol / L potassium dihydrogen phosphate-sodium hydroxide, dilute to 10 mL with deionized water, shake well, and let stand for 10 min; then, use a fluorescence spectrophotometer to detect the fluorescence intensity in the corresponding volumetric flask; based on the relationship between the detected fluorescence intensity and the concentration of the solution sample, construct the Fe 3+ The relationship between the concentration and fluorescence intensity of the coumarin molecular probe containing the porphyrin group is used to detect Fe in ultrapure water. 3+ The content is detected to obtain the fluorescence intensity corresponding to the ultrapure water to be tested, and then the Fe 3+ The relationship curve between the concentration and fluorescence intensity can be obtained to obtain the Fe 3+ Content detection results; the test conditions are excitation voltage 700V, slit 5nm, and excitation wavelength 420nm.

[0040] Example 1

[0041] This embodiment 1 provides a method for preparing a coumarin molecular probe containing a porphine group, comprising the following steps:

[0042] Step 1. Add 3 mmol of dried dicarboxyphenylporphine to chloroform, stir thoroughly, and cool to below 5°C in an ice-salt bath; then, add 4 mmol of anhydrous thionyl chloride dropwise under nitrogen gas flow, complete the addition within 0.5 h, and stop the nitrogen flow; after the addition of anhydrous thionyl chloride, raise the temperature to 65°C and stir for 3 h; after the reaction, evacuate to a vacuum degree of 740 mmHg, and perform reduced pressure distillation at 60°C to remove thionyl chloride and chloroform; then, perform vacuum drying at 70°C to obtain diformylchlorophenylporphine; wherein the yield of the diformylchlorophenylporphine is 82%.

[0043] Step 2, dichlorophenyl porphine, triethylamine and chloroform are mixed in a millimolar ratio of 5:15:10, stirred evenly and then added dropwise 6-hydroxy-4-methyl coumarin, stirred at room temperature for reaction, and then heated to 70°C with stirring and reflux for 2 hours to obtain a reaction system; wherein the millimolar ratio of the 6-hydroxy-4-methyl coumarin to the dichlorophenyl porphine is 5:12, the 6-hydroxy-4-methyl coumarin is dissolved in chloroform and added dropwise, the mass of the chloroform solution of the 6-hydroxy-4-methyl coumarin is 10%, and the addition is completed within 0.5 hours.

[0044] Step 3, placing the reaction system in a dry ice low-temperature bath to cool and obtain a precipitated solid; wherein the dry ice low-temperature bath is an ethanol-dry ice low-temperature bath at -35°C; the precipitated solid is filtered to obtain a filtered product; then, the filtered product is washed twice with a saturated sodium bicarbonate solution and then washed twice with distilled water to obtain a purple-black solid; then, the purple-black solid is recrystallized with anhydrous ethanol; finally, the product is vacuum-dried at 80°C to obtain a porphine-containing coumarin molecular probe (CDPP); wherein the yield of the porphine-containing coumarin molecular probe is 87%.

[0045] Example 2

[0046] This embodiment 2 provides a method for preparing a coumarin molecular probe containing a porphine group, comprising the following steps:

[0047] Step 1. Add 3.5 mmol of dried dicarboxyphenylporphine to chloroform, stir thoroughly, and cool to below 5°C in an ice-salt bath; then, purge with nitrogen and add 5 mmol of anhydrous thionyl chloride dropwise over 0.6 h, then stop purging with nitrogen; after the addition of anhydrous thionyl chloride is complete, heat to 65°C, stir and react for 3.5 h; after the reaction is completed, evacuate to a vacuum degree of 745 mmHg, and perform reduced pressure distillation at 60°C to remove thionyl chloride and chloroform; then, perform vacuum drying at 70°C to obtain diformylchlorophenylporphine; wherein the yield of the diformylchlorophenylporphine is 84%.

[0048] Step 2, dichlorophenyl porphine, triethylamine and chloroform are mixed in a millimolar ratio of 6:17:120, stirred evenly and then added dropwise 6-hydroxy-4-methyl coumarin, stirred at room temperature for reaction, and then heated to 70°C with stirring and reflux for 2.5 hours to obtain a reaction system; wherein the millimolar ratio of the 6-hydroxy-4-methyl coumarin to the dichlorophenyl porphine is 6:13, the 6-hydroxy-4-methyl coumarin is dissolved in chloroform and added dropwise, the mass of the chloroform solution of the 6-hydroxy-4-methyl coumarin is 10%, and the addition is completed within 0.6 hours.

[0049] Step 3, placing the reaction system in a dry ice low-temperature bath to cool and obtain a precipitated solid; wherein the dry ice low-temperature bath is an ethanol-dry ice low-temperature bath at -38°C; the precipitated solid is filtered to obtain a filtered product; then, the filtered product is washed three times with a saturated sodium bicarbonate solution and then washed three times with distilled water to obtain a purple-black solid; then, the purple-black solid is recrystallized with anhydrous ethanol; finally, the product is vacuum-dried at 80°C to obtain a porphine-containing coumarin molecular probe (CDPP); wherein the yield of the porphine-containing coumarin molecular probe is 88%.

[0050] Example 3

[0051] This embodiment 3 provides a method for preparing a coumarin molecular probe containing a porphine group, comprising the following steps:

[0052] Step 1. Add 4 mmol of dried dicarboxyphenylporphine to chloroform, stir thoroughly, and cool to below 5°C in an ice-salt bath; then, add 5.5 mmol of anhydrous thionyl chloride dropwise under nitrogen gas flow for 0.7 h, and stop flowing nitrogen gas; after the addition of anhydrous thionyl chloride is completed, heat to 65°C, stir and react for 4 h; after the reaction is completed, evacuate to a vacuum degree of 740 mmHg, and perform reduced pressure distillation at 60°C to remove thionyl chloride and chloroform; then, vacuum dry at 70°C to obtain diformylchlorophenylporphine; wherein the yield of the diformylchlorophenylporphine is 86%.

[0053] Step 2, dichlorophenyl porphine, triethylamine and chloroform are mixed in a millimolar ratio of 7:19:140, stirred evenly and then added dropwise 6-hydroxy-4-methylcoumarin, stirred at room temperature for reaction, and then heated to 70°C with stirring and reflux for 3 hours to obtain a reaction system; wherein the millimolar ratio of the 6-hydroxy-4-methylcoumarin to the dichlorophenyl porphine is 7:14, the 6-hydroxy-4-methylcoumarin is dissolved in chloroform and added dropwise, the mass of the chloroform solution of the 6-hydroxy-4-methylcoumarin is 10%, and the addition is completed within 0.7 hours.

[0054] Step 3, placing the reaction system in a dry ice low-temperature bath to cool and obtain a precipitated solid; wherein the dry ice low-temperature bath is an ethanol-dry ice low-temperature bath at -40°C; the precipitated solid is filtered to obtain a filtered product; then, the filtered product is washed twice with a saturated sodium bicarbonate solution and then washed twice with distilled water to obtain a purple-black solid; then, the purple-black solid is recrystallized with anhydrous ethanol; finally, the product is vacuum-dried at 80°C to obtain a porphine-containing coumarin molecular probe (CDPP); wherein the yield of the porphine-containing coumarin molecular probe is 89%.

[0055] Example 4

[0056] This embodiment 4 provides a method for preparing a coumarin molecular probe containing a porphine group, comprising the following steps:

[0057] Step 1. Add 4.5 mmol of dried dicarboxyphenylporphine to chloroform, stir thoroughly, and cool to below 5°C in an ice-salt bath; then, add 6.5 mmol of anhydrous thionyl chloride dropwise under nitrogen gas flow for 0.8 h, and stop flowing nitrogen gas; after the addition of anhydrous thionyl chloride is completed, heat to 65°C, stir and react for 4.5 h; after the reaction is completed, evacuate to a vacuum degree of 740 mmHg, and perform reduced pressure distillation at 60°C to remove thionyl chloride and chloroform; then, vacuum dry at 70°C to obtain diformylchlorophenylporphine; wherein the yield of the diformylchlorophenylporphine is 88%.

[0058] Step 2, dichlorophenyl porphine, triethylamine and chloroform are mixed in a millimolar ratio of 6.8:22:150, stirred evenly and then added dropwise 6-hydroxy-4-methyl coumarin, stirred at room temperature for reaction, and then heated to 70°C with stirring and reflux for 4 hours to obtain a reaction system; wherein the millimolar ratio of the 6-hydroxy-4-methyl coumarin to the dichlorophenyl porphine is 7.5:16, the 6-hydroxy-4-methyl coumarin is dissolved in chloroform and added dropwise, the mass of the chloroform solution of the 6-hydroxy-4-methyl coumarin is 10%, and the addition is completed within 0.9 hours.

[0059] Step 3, placing the reaction system in a dry ice low-temperature bath to cool and obtain a precipitated solid; wherein the dry ice low-temperature bath is an ethanol-dry ice low-temperature bath at -42°C; the precipitated solid is filtered to obtain a filtered product; then, the filtered product is washed three times with a saturated sodium bicarbonate solution and then washed three times with distilled water to obtain a purple-black solid; then, the purple-black solid is recrystallized with anhydrous ethanol; finally, the product is vacuum-dried at 80°C to obtain a porphine-containing coumarin molecular probe (CDPP); wherein the yield of the porphine-containing coumarin molecular probe is 90%.

[0060] Example 5

[0061] This Example 5 provides a method for preparing a coumarin molecular probe containing a porphine group, comprising the following steps:

[0062] Step 1. Add 5 mmol of dried dicarboxyphenylporphine to chloroform, stir thoroughly, and cool to below 5°C in an ice-salt bath; then, flow nitrogen and add 8 mmol of anhydrous thionyl chloride dropwise. The addition is completed within 1 hour, and the flow of nitrogen is stopped; after the addition of anhydrous thionyl chloride is completed, the temperature is raised to 65°C and stirred for reaction for 5 hours; after the reaction is completed, evacuate to a vacuum degree of 750 mmHg, and perform reduced pressure distillation at 60°C to remove thionyl chloride and chloroform; then, vacuum dry at 70°C to obtain diformylchlorophenylporphine; wherein the yield of the diformylchlorophenylporphine is 89%.

[0063] Step 2, dichlorophenyl porphine, triethylamine and chloroform are mixed in a millimolar ratio of 8:24:160, stirred evenly and then added dropwise 6-hydroxy-4-methylcoumarin, stirred at room temperature for reaction, and then heated to 70°C with stirring and reflux for 4 hours to obtain a reaction system; wherein the millimolar ratio of the 6-hydroxy-4-methylcoumarin to the dichlorophenyl porphine is 8:17, the 6-hydroxy-4-methylcoumarin is dissolved in chloroform and added dropwise, the mass of the chloroform solution of the 6-hydroxy-4-methylcoumarin is 10%, and the addition is completed within 1 hour.

[0064] Step 3, placing the reaction system in a dry ice low-temperature bath to cool and obtain a precipitated solid; wherein the dry ice low-temperature bath is an ethanol-dry ice low-temperature bath at -45°C; the precipitated solid is filtered to obtain a filtered product; then, the filtered product is washed three times with a saturated sodium bicarbonate solution and then washed three times with distilled water to obtain a purple-black solid; then, the purple-black solid is recrystallized with anhydrous ethanol; finally, the product is vacuum-dried at 80°C to obtain a porphine-containing coumarin molecular probe (CDPP); wherein the yield of the porphine-containing coumarin molecular probe is 92%.

[0065] Performance verification experiment:

[0066] The following is from the interference of different metal ions, measurement time, measurement temperature, pH, complexation ratio and Fe 3+ The performance of the coumarin molecular probe prepared in Example 1 was verified by experiments in terms of the six factors affecting the concentration of coumarin, as follows:

[0067] (1) Common metal ion pairs for coumarin molecular probe detection of Fe 3+ Interference experiment

[0068] Several groups of coumarin molecular probe samples prepared in Example 1 were obtained, and other metal ions were added to the several groups of coumarin molecular probe samples respectively; then, 2.0×10 -5 mol / L of Fe 3+ , and set up a blank group to observe the fluorescence linearity of the sample; among them, other metal ions include Ca 2+ , Pb 2+ 、Cu 2+ 、Ba 2+ 、Cd 2+ 、Zn 2+ 、Ni 2+ 、Co 2+ 、Fe 2+ 、Mn 2+ 、Hg 2+ 、Li + 、Ag + Mg 2+ , K + 、Na + Cr 3+ and Al 3+ .

[0069] As attached Figure 2 As shown, attached Figure 2 The results of different metal ions on the coumarin molecular probe prepared in Example 1 to detect Fe 3+ The impact result diagram of Figure 2 It can be seen that without adding Fe 3+ Previously, the coumarin molecular probe solutions of various metal ions all had similar fluorescence intensities; when 2.0×10 -5 mol / L of Fe 3+ After that, fluorescence quenching phenomenon occurred; this shows that the coumarin molecular probe is sensitive to Fe 3+ The recognition has good selectivity and anti-interference ability.

[0070] (2) Effect of time on detection of Fe by coumarin molecular probe 3+ The impact of the experiment

[0071] Pipette 5mL (1.0×10 -4mol / L) coumarin molecular probe prepared in Example 1, and 0.2 mL of 0.05 mol / L Fe 3+ Add to a 10 mL volumetric flask; then dilute with deionized water, shake well, and quickly perform a fluorescence test. Test CDPP+Fe within 25 minutes. 3+ Fluorescence intensity changes of the system.

[0072] As attached Figure 3 As shown, attached Figure 3 The coumarin molecular probe prepared in Example 1 is given to detect Fe 3+ The relationship between the measurement time and the fluorescence intensity is shown in the figure below. Figure 3 It can be seen that after adding Fe 3+ After 1 min, the fluorescence was almost completely quenched; thus, Fe 3+ The recognition of coumarin molecular probe is relatively rapid; therefore, in order to fully ensure the effect, fluorescence testing was performed after 3 minutes.

[0073] (3) Effect of reaction temperature on Fe detection by coumarin molecular probe 3+ The impact of the experiment

[0074] Use a pipette to transfer 1 mL (1.0 × 10 -4 mol / L) coumarin molecular probe prepared in Example 1, and 0.2 mL of 0.05 mol / L Fe 3+ Add to a 10mL volumetric flask, then dilute with deionized water, shake well, and quickly perform a fluorescence test to test CDPP+Fe in the temperature range of 10-70℃. 3+ Fluorescence intensity changes of the system.

[0075] As attached Figure 4 As mentioned above, Figure 4 The coumarin molecular probe prepared in Example 1 is given to detect Fe 3+ The relationship between temperature and fluorescence intensity is shown in the figure below. Figure 4 It can be seen that temperature has a great influence on Fe 3+ The effect on CDPP recognition was not significant; therefore, the fluorescence test was performed between 20 and 40°C.

[0076] (4) pH-coumarin molecular probe for Fe detection 3+ The impact of the experiment

[0077] The coumarin molecular probe prepared in Example 1 was investigated for its effect on Fe in the range of pH 3-9. 3+ The test results; as attached Figure 5 As shown, attached Figure 5 The coumarin molecular probe prepared in Example 1 is given to detect Fe 3+The relationship curve between pH and fluorescence intensity; Figure 5 It can be seen that within pH=3-9, the fluorescence intensity of the CDPP system remains almost unchanged, while the addition of Fe 3+ The fluorescence intensity of the system was significantly weakened after the addition of Fe 3+ Post-CDPP and Fe 3+ The fluorescence of the complex is quenched, and the fluorescence intensity is stable at pH = 3-9. Therefore, at pH = 3-9, CDPP is suitable for Fe 3+ Fluorescence detection.

[0078] (5)With Fe 3+ Complexation comparison of coumarin molecular probe for detection of Fe 3+ The impact of the experiment

[0079] The Job-Plot method was used to determine the affinity of the coumarin molecular probe prepared in Example 1 with Fe 3+ The complexation ratio of Figure 6 As shown, attached Figure 6 The coumarin molecular probe prepared in Example 1 and Fe 3+ The relationship between the complexation ratio and fluorescence intensity is shown in the figure below. Figure 6 It can be seen that the intersection of the two straight lines is around 0.5, indicating that CDPP and Fe 3+ The complexation ratio is 1:1.

[0080] (6)Fe 3+ The relationship between the concentration and fluorescence intensity

[0081] At room temperature, different low concentrations of Fe 3+ , using the coumarin molecular probe prepared in Example 1 to measure the Fe 3+ The standard working curve was drawn by fluorescence spectrometer. Figure 7 As shown, attached Figure 7 The coumarin molecular probe prepared in Example 1 is given to detect Fe 3+ Time Fe 3+ The relationship between the concentration and fluorescence intensity of Figure 7 It can be seen that the fluorescence intensity of the solution is between 0-7×10 -6 mol / L range, and the relationship is linear. 3+ The detection limit was 1.25×10 -6 mol / L(R 2 =0.9993).

[0082] It should be noted that when the coumarin molecular probes prepared in Examples 2-5 were used to conduct the above verification experiments, the conclusions obtained were basically the same as the verification experiment results using the coumarin molecular probe prepared in Example 1, and will not be repeated here.

[0083] The coumarin molecular probe containing a porphine group and the preparation method thereof of the present invention use dicarboxyphenylporphine as a raw material, perform chlorination modification on the two carboxyl groups in the porphine molecule, and perform a nucleophilic addition reaction between the chlorinated porphine compound and a hydroxyl-containing coumarin to prepare the coumarin molecular probe containing a porphine group. The preparation process is simple, the reaction conditions are easy to control, and the prepared fluorescent probe has excellent optical properties and chemical stability, and is responsive to Fe in the pH range of 4 to 9. 3+ It has good recognition performance and strong anti-interference ability, and can be used for the analysis and detection of trace iron in the water vapor system of thermal power plants.

[0084] The above embodiment is only one of the implementation methods that can realize the technical solution of the present invention. The scope of protection claimed by the present invention is not limited only to this embodiment, but also includes changes, replacements and other implementation methods that can be easily thought of by any technician familiar with this technical field within the technical scope disclosed by the present invention.

Claims

1. A coumarin molecular probe containing a porphine group, characterized in that: The coumarin molecular probe has the following structure: 。 2. The method for preparing a coumarin molecular probe containing a porphine group according to claim 1, wherein: Dicarboxyphenylporphine is used as a raw material; two carboxyl groups in the dicarboxyphenylporphine molecule are chlorinated to obtain a chlorinated porphine compound; the chlorinated porphine compound is subjected to a nucleophilic addition reaction with 6-hydroxy-4-methylcoumarin to prepare the coumarin molecular probe containing the porphine group.

3. The method for preparing a coumarin molecular probe containing a porphine group according to claim 2, characterized in that: The following steps are involved: Dicarboxyphenylporphine is mixed with chloroform, stirred thoroughly, and then cooled to a first preset temperature in an ice bath, and then anhydrous thionyl chloride is added; after the anhydrous thionyl chloride is added dropwise, the temperature is raised to a second preset temperature, and stirred for reaction; after the reaction is completed, reduced pressure distillation is performed under vacuum conditions to remove anhydrous thionyl chloride and chloroform, and vacuum drying is performed to obtain diformylchlorophenylporphine; Diformylchlorophenylporphine, triethylamine and chloroform are mixed and stirred evenly, and then 6-hydroxy-4-methylcoumarin is added and stirred for reaction. After the reaction, the mixture is cooled, filtered, washed, recrystallized and dried to prepare a coumarin molecular probe containing a porphine group.

4. The method for preparing a coumarin molecular probe containing a porphine group according to claim 3, characterized in that: In the process of mixing dicarboxyphenylporphine with chloroform, chloroform and dicarboxyphenylporphine are mixed in a millimole ratio of (80-100): (8-10); wherein, the chloroform is fully dehydrated with anhydrous sodium sulfate before use.

5. The method for preparing a coumarin molecular probe containing a porphine group according to claim 3, characterized in that: During the reduced pressure distillation under vacuum conditions, the vacuum degree is 740-750 mmHg.

6. The method for preparing a coumarin molecular probe containing a porphine group according to claim 3, characterized in that: In the process of mixing dichlorophenylporphine, triethylamine and chloroform, dichlorophenylporphine, triethylamine and chloroform are mixed in a millimole ratio of (5-8): (12-24): (100-160).

7. The method for preparing a coumarin molecular probe containing a porphine group according to claim 3, characterized in that: Dichlorophenyl porphine, triethylamine and chloroform are mixed and stirred evenly, and then 6-hydroxy-4-methylcoumarin is added, and the millimole ratio of 6-hydroxy-4-methylcoumarin to dichlorophenyl porphine is (5-8):(12-17).

8. The method for preparing a coumarin molecular probe containing a porphine group according to claim 3, characterized in that: The cooling process is carried out in an ethanol-dry ice low-temperature bath; wherein the cooling temperature is -45°C to -35°C.

9. The use of a coumarin molecular probe containing a porphine group according to claim 1, characterized in that: The coumarin molecular probe is used to detect trace Fe in ultrapure water 3+ .

Images