Coumarin molecular probe containing porphin group as well as preparation method and application of coumarin molecular probe

Abstract

The invention belongs to the technical field of fluorescent probes, and discloses a coumarin molecular probe containing a porphin group and a preparation method and application of the coumarin molecular probe. The preparation method comprises the following steps: performing chloroacylation modification on two carboxyl groups in dicarboxyphenyl porphin molecules to obtain a chloroacylated porphin compound; and carrying out nucleophilic addition reaction on the chlorine compound subjected to chlorine acylation and coumarin containing hydroxyl to prepare the coumarin molecular probe containing the chlorine group, the preparation process is simple, the requirement for reaction conditions is low, the yield is high, the molecular probe has high selectivity, sensitivity and anti-interference performance on Fe < 3 + >, Fe < 2 + > and Fe < 3 + > can be accurately distinguished, and the molecular probe has good application prospects in the fields of light absorption antennas, organic light emitting diodes, fluorescent probes, anti-tumor drugs and the like.

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, and a preparation method and application thereof. Background Art

[0002] The iron content in the water vapor system of a thermal power plant is an important basis for evaluating the corrosion and scaling of the thermal system of a power generation unit, and it is one of the important monitoring indicators in the daily production of a thermal power plant; at present, the determination methods for total iron in power production feed water, boiler water and drain water mainly include o-phenanthroline spectrophotometry (standard for determination of iron in boiler water and cooling water analysis method, GB / T14427-2008) and graphite furnace atomic absorption method (graphite furnace atomic absorption method for determination of copper and iron in thermal power plant water and steam test method, DL / T955-2005); among them, o-phenanthroline spectrophotometry is a traditional manual analysis method, which is complicated to operate, has low analysis efficiency, narrow linear range, and sample water is easily contaminated, especially for low concentration (<10μg / L) of iron ion detection accuracy is not high, and human error is inevitable; and the instrument used in the graphite furnace atomic absorption method is expensive and requires high operation and maintenance. Therefore, the study 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 measure iron ions. From a structural point of view, it mainly includes rhodamine B type, pyridine, naphthylimide type, coumarin and coumarin compounds with benzo α-pyrone structure. However, the above-mentioned Fe 3+ Fluorescent molecular probes generally have the disadvantages 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 a preparation method and application thereof to solve the existing Fe 3+ Fluorescent molecular probes generally have the disadvantages of low selectivity and sensitivity, and are unable to detect Fe 2+ and Fe 3+ Technical issues for 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 taking dicarboxyphenylporphine as a raw material; performing chlorination modification on two carboxyl groups in the dicarboxyphenylporphine molecule to obtain a chlorinated porphine compound; and 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.

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

[0010] The 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 diformyl chloride phenylporphine;

[0011] Diformylchlorophenylporphine, triethylamine and chloroform are mixed, stirred evenly, and then 6-hydroxy-4-methylcoumarin is added, stirred for reaction, and 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 millimole 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, stirred and then added with 6-hydroxy-4-methylcoumarin, and the millimole ratio of 6-hydroxy-4-methylcoumarin to dichlorophenylporphine is (5-8):(12-17).

[0016] Furthermore, the cooling process is carried out under ethanol-dry ice low-temperature bath conditions; 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 coumarin molecular probe containing a porphine group provided by the present invention, and the preparation method and application thereof, adopt the method of introducing a biologically active and photoactive coumarin derivative into a chlorinated porphine compound through a nucleophilic addition reaction to obtain a coumarin molecular probe containing a porphine group; since the nitrogen atom on the porphine group has a lone pair of electrons, it can form a coordination bond with iron ions to achieve complexation with iron ions; by introducing a coumarin group with fluorescent properties, the electron-withdrawing ester group therein increases the probability of charge transfer within the molecule, thereby enhancing the fluorescent performance, achieving a fluorescent effect under visible light, and thereby effectively enhancing the recognition ability of the molecular probe; secondly, since Fe 3+ Compared with Fe 2+ With a 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 Fe 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 the 6-hydroxy-4-methylcoumarin, and the acyl chloride containing active hydrogen can easily release hydrogen chloride in the reaction, further promoting the reaction, thereby generating a target molecular probe, and the corresponding molecular probe can be prepared through two-step reaction, and the molecular structure and properties of the molecular probe can be accurately controlled; the preparation process of the present invention is simple, the reaction conditions are low and the yield is high, and the molecular probe has high affinity for Fe 3+ It has high selectivity, sensitivity and anti-interference, and can 2+ and Fe 3+ It can be accurately identified 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 drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. 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 paying creative work.

[0020] Figure 1 The synthetic route of the coumarin molecular probe containing porphine group described in 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 at 4 ℃ and 8 ℃;

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

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

[0027] In order to make the technical problems, technical solutions and beneficial effects solved by this application clearer, the technical solutions in the embodiments of this application will be described clearly and completely in combination with the drawings in the embodiments of this application; obviously, the described embodiments are only part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0028] The present invention provides a coumarin molecular probe containing a porphine group, and 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; 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.

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

[0032] Step 1, dicarboxylphenylporphine is mixed with chloroform, and after sufficient stirring, the mixture is cooled to a first preset temperature under ice bath conditions, and then anhydrous thionyl chloride is added; wherein chloroform and dicarboxylphenylporphine are mixed in a millimole ratio of (80-100):(8-10); wherein the 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 mixture is heated to a second preset temperature and stirred for reaction; 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 diformylchlorophenylporphine; 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 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 millimole ratio of (5-8):(12-24):(100-160), and the millimole ratio of 6-hydroxy-4-methylcoumarin to dichlorophenylporphine is (5-8):(12-17); preferably, the third preset temperature is 70°C.

[0034] Step 3: Cool, filter, wash, recrystallize and dry 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 electrophilic substitution reaction with the acylating agent thionyl chloride to generate a chloroacylated product diformylchlorophenylporphine, and the chloroacyl group in the diformylchlorophenylporphine can undergo nucleophilic addition reaction with the hydroxyl group in 6-hydroxy-4-methylcoumarin, and the acyl chloride containing active hydrogen can easily release hydrogen chloride in the reaction, further promoting the reaction, thereby generating a target molecular probe, and the corresponding molecular probe can be prepared through two-step reaction.

[0037] The coumarin molecular probe containing porphine groups 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 about 400nm and the Q band at 450-700nm. Since the coordination number of the iron ion is usually 6, it can form coordination bonds with multiple ligand atoms, such as nitrogen atoms. In the case of the porphine ring, the iron ion forms a four-coordinated structure with the four nitrogen atoms on the porphine ring. The coumarin group itself has fluorescence properties, and due to the introduction of the electron-withdrawing ester group in the molecule, the probability of intramolecular charge transfer is increased, and the fluorescence of the molecule itself is enhanced, so that the fluorescence 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 the effect of synergistically enhancing fluorescence. Therefore, it is applied to trace Fe in ultrapure water. 3+ When detecting trace Fe 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+ Then, adjust the pH value 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. According to the relationship between the detected fluorescence intensity and the concentration of the solution sample, construct the Fe 3+ The relationship curve between the concentration and fluorescence intensity of the Fe in the ultrapure water to be tested is obtained by using the coumarin molecular probe containing the porphine group. 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 between the concentration and fluorescence intensity can be obtained by 3+ Content detection results; wherein, the test conditions are excitation voltage 700V, slit 5nm, 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, adding 3mmol of dried dicarboxylphenylporphine to chloroform, stirring thoroughly and cooling to below 5°C in an ice-salt bath; then passing nitrogen, adding 4mmol of anhydrous thionyl chloride dropwise, and the addition is completed within 0.5h, and the nitrogen is stopped; after the anhydrous thionyl chloride is added dropwise, the temperature is raised to 65°C, and the reaction is stirred for 3h; after the reaction is completed, the vacuum is evacuated to a vacuum degree of 740mmHg, and reduced pressure distillation is performed at 60°C to remove thionyl chloride and chloroform; then, vacuum drying is performed at 70°C to obtain diformyl chloride phenylporphine; wherein the yield of the diformyl chloride phenylporphine is 82%.

[0043] Step 2, dichlorophenyl porphine, triethylamine and chloroform are mixed in a millimole ratio of 5:15:10, and after stirring evenly, 6-hydroxy-4-methyl coumarin is added dropwise, and after stirring at room temperature for reaction, the temperature is raised to 70° C., stirred, heated and refluxed for 2 h to obtain a post-reaction system; wherein the millimole 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 h.

[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 filtration product; then, the filtration 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, vacuum dried at 80°C to obtain a coumarin molecular probe (CDPP) containing a porphine group; wherein the yield of the coumarin molecular probe containing a porphine group 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, adding 3.5mmol of dried dicarboxylphenylporphine to chloroform, stirring thoroughly and cooling to below 5°C in an ice-salt bath; then passing nitrogen, adding 5mmol of anhydrous thionyl chloride dropwise, adding within 0.6h, and stopping passing nitrogen; after the anhydrous thionyl chloride is added dropwise, heating to 65°C, stirring and reacting for 3.5h; after the reaction is completed, evacuating to a vacuum degree of 745mmHg, and performing reduced pressure distillation at 60°C to remove thionyl chloride and chloroform; then, vacuum drying is performed at 70°C to obtain diformyl chloride phenylporphine; wherein the yield of the diformyl chloride phenylporphine is 84%.

[0048] Step 2, dichlorophenyl porphine, triethylamine and chloroform are mixed in a millimole ratio of 6:17:120, and 6-hydroxy-4-methyl coumarin is added dropwise after stirring evenly. After stirring at room temperature for reaction, the temperature is raised to 70° C., stirred, heated and refluxed for 2.5 h to obtain a post-reaction system; wherein the millimole 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 h.

[0049] Step 3, placing the post-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 filtration product; then, the filtration product is washed 3 times with a saturated sodium bicarbonate solution, and then washed 3 times with distilled water to obtain a purple-black solid; then, the purple-black solid is recrystallized with anhydrous ethanol; finally, vacuum dried at 80°C to obtain a coumarin molecular probe (CDPP) containing a porphine group; wherein the yield of the coumarin molecular probe containing a porphine group 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, adding 4mmol of dried dicarboxylphenylporphine to chloroform, stirring thoroughly and cooling to below 5°C in an ice-salt bath; then passing nitrogen, adding 5.5mmol of anhydrous thionyl chloride dropwise, adding within 0.7h, stopping passing nitrogen; after the anhydrous thionyl chloride is added dropwise, heating to 65°C, stirring and reacting for 4h; after the reaction is completed, evacuating to a vacuum degree of 740mmHg, and performing reduced pressure distillation at 60°C to remove thionyl chloride and chloroform; then, vacuum drying is performed at 70°C to obtain diformyl chloride phenylporphine; wherein the yield of the diformyl chloride phenylporphine is 86%.

[0053] Step 2, dichlorophenyl porphine, triethylamine and chloroform are mixed in a millimole ratio of 7:19:140, and 6-hydroxy-4-methyl coumarin is added dropwise after stirring evenly. After stirring at room temperature for reaction, the temperature is raised to 70° C., stirred, heated and refluxed for 3 h to obtain a post-reaction system; wherein the millimole ratio of the 6-hydroxy-4-methyl coumarin to the dichlorophenyl porphine is 7:14, 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 0.7 h.

[0054] Step 3, placing the post-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 filtration product; then, the filtration 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, vacuum dried at 80°C to obtain a porphine group-containing coumarin molecular probe (CDPP); wherein the yield of the porphine group-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, adding 4.5mmol of dried dicarboxylphenylporphine to chloroform, stirring thoroughly and cooling to below 5°C in an ice-salt bath; then passing nitrogen, adding 6.5mmol of anhydrous thionyl chloride dropwise, adding within 0.8h, stopping passing nitrogen; after the anhydrous thionyl chloride is added dropwise, heating to 65°C, stirring and reacting for 4.5h; after the reaction is completed, evacuating to a vacuum degree of 740mmHg, and performing reduced pressure distillation at 60°C to remove thionyl chloride and chloroform; then, vacuum drying is performed at 70°C to obtain diformyl chloride phenylporphine; wherein the yield of the diformyl chloride phenylporphine is 88%.

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

[0059] Step 3, placing the post-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 filtration product; then, the filtration product is washed 3 times with a saturated sodium bicarbonate solution, and then washed 3 times with distilled water to obtain a purple-black solid; then, the purple-black solid is recrystallized with anhydrous ethanol; finally, vacuum dried at 80°C to obtain a coumarin molecular probe (CDPP) containing a porphine group; wherein the yield of the coumarin molecular probe containing a porphine group is 90%.

[0060] Example 5

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

[0062] Step 1, adding 5mmol of dried dicarboxylphenylporphine to chloroform, stirring thoroughly and cooling to below 5°C in an ice-salt bath; then passing nitrogen, adding 8mmol of anhydrous thionyl chloride dropwise, the addition is completed within 1 hour, and the passing of nitrogen is stopped; after the addition of anhydrous thionyl chloride is completed, the temperature is raised to 65°C, and the reaction is stirred for 5 hours; after the reaction is completed, the vacuum is evacuated to a vacuum degree of 750mmHg, and reduced pressure distillation is performed at 60°C to remove thionyl chloride and chloroform; then, vacuum drying is performed at 70°C to obtain diformyl chloride phenylporphine; wherein the yield of the diformyl chloride phenylporphine is 89%.

[0063] Step 2, dichlorophenyl porphine, triethylamine and chloroform are mixed in a millimole ratio of 8:24:160, and after stirring evenly, 6-hydroxy-4-methyl coumarin is added dropwise, and after stirring at room temperature for reaction, the temperature is raised to 70° C., stirred, heated and refluxed for 4 hours to obtain a post-reaction system; wherein the millimole ratio of the 6-hydroxy-4-methyl coumarin to the dichlorophenyl porphine is 8:17, the 6-hydroxy-4-methyl coumarin is dissolved in chloroform and added dropwise, the mass of the chloroform solution of 6-hydroxy-4-methyl coumarin 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 filtration product; then, the filtration product is washed 3 times with a saturated sodium bicarbonate solution, and then washed 3 times with distilled water to obtain a purple-black solid; then, the purple-black solid is recrystallized with anhydrous ethanol; finally, vacuum dried at 80°C to obtain a coumarin molecular probe (CDPP) containing a porphine group; wherein the yield of the coumarin molecular probe containing a porphine group is 92%.

[0065] Performance verification experiment:

[0066] The following is 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 six factors affecting the concentration of coumarin, as follows:

[0067] (1) Common metal ions 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 / LFe 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 had similar fluorescence intensities; when 2.0×10 -5 mol / LFe 3+ After that, fluorescence quenching phenomenon appeared; this shows that the coumarin molecular probe can effectively inhibit the growth of 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 experiment

[0071] Take 5mL (1.0×10 -4mol / L) coumarin molecular probe prepared in Example 1, and pipette 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 for detecting Fe 3+ The relationship between the measurement time and the fluorescence intensity is shown in the figure. 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 detection of Fe by coumarin molecular probe 3+ The impact experiment

[0074] Use a pipette to transfer 1 mL (1.0 × 10 -4 mol / L) coumarin molecular probe prepared in Example 1, and pipette 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 to test CDPP+Fe in the temperature range of 10-70°C. 3+ Fluorescence intensity changes of the system.

[0075] As attached Figure 4 As stated, attached Figure 4 The coumarin molecular probe prepared in Example 1 for detecting 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 the recognition of CDPP was not significant; therefore, the fluorescence test was performed between 20-40°C.

[0076] (4) pH-induced coumarin molecular probe detection of Fe 3+ The impact 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; Figure 5 As shown, attached Figure 5 The coumarin molecular probe prepared in Example 1 for detecting Fe 3+The relationship between pH and fluorescence intensity is shown in the figure. 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, when 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 experiment

[0079] The Job-Plot method was used to determine the molecular probe of coumarin prepared in Example 1 and 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. 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 for detecting Fe 3+ Time 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, 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 perform the above verification experiments, the conclusions obtained were basically the same as the verification experiment results using the coumarin molecular probes 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 two carboxyl groups in the porphine molecule, perform nucleophilic addition reaction on the chlorinated porphine compound and 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 has high sensitivity 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 the 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, characterized in that: Dicarboxylphenylporphine is used as a raw material; two carboxyl groups in the dicarboxylphenylporphine molecule are chlorinated to obtain a chlorinated porphine compound; the chlorinated porphine compound is subjected to a nucleophilic addition reaction with a hydroxyl-containing coumarin to prepare the coumarin molecular probe containing a 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: The 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 diformyl chloride phenylporphine; Diformylchlorophenylporphine, triethylamine and chloroform are mixed, stirred evenly, and then 6-hydroxy-4-methylcoumarin is added, stirred for reaction, and 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: Dichlorophenylporphine, 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 dichlorophenylporphine 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 under ethanol-dry ice low-temperature bath conditions; wherein the cooling temperature is -45°C to -35°C.

9. The use of a coumarin molecular probe containing a porphine group as claimed in claim 1, characterized in that: The coumarin molecular probe is used as a probe to detect Fe 3+ of fluorescent probes.

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

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