CN111925376B - Fluorescent probe for detecting Cu (II) and Hg (II) and preparation method thereof - Google Patents

Fluorescent probe for detecting Cu (II) and Hg (II) and preparation method thereof Download PDF

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CN111925376B
CN111925376B CN202010717648.6A CN202010717648A CN111925376B CN 111925376 B CN111925376 B CN 111925376B CN 202010717648 A CN202010717648 A CN 202010717648A CN 111925376 B CN111925376 B CN 111925376B
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姜慧娥
唐丹妮
李俊炜
韩庆鑫
刘新华
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a fluorescent probe for detecting Cu (II) and Hg (II), and also discloses a preparation method of the fluorescent probe, wherein rhodamine fluorophores and 2-aldehyde-8-hydroxyquinoline are used as raw materials, and the fluorescent probe is prepared through five-step reaction. The fluorescence probe can detect Cu (II) and Hg (II) with high sensitivity and high selectivity by utilizing fluorescence spectrum and ultraviolet-visible absorption spectrum in a solution with the volume ratio of ethanol to water of 1:1. The fluorescent probe is expected to be applied to detecting out-of-standard Cu (II) and Hg (II) in river water, tap water, sewage and the like.

Description

Fluorescent probe for detecting Cu (II) and Hg (II) and preparation method thereof
Technical Field
The invention belongs to the technical field of fluorescent probes for metal ion detection, and particularly relates to a fluorescent probe for detecting Cu (II) and Hg (II), and a preparation method of the fluorescent probe.
Background
Copper plays a key role as a catalytic cofactor for various metalloenzymes, but excessive amounts of Cu (II) can be toxic to humans, causing gastrointestinal dysfunction and neurological diseases such as Wilson's and Alzheimer's syndrome. The U.S. Environmental Protection Agency (EPA) specifies that the maximum Cu (II) content in drinking water is 20. Mu.M. Hg (II) is a physiologically toxic chemical substance which can be converted into highly toxic methylmercury by bacteria in the environment, and the methylmercury is then transferred into the human body through a food chain to accumulate, so that the methylmercury is not easy to be discharged from the body. The accumulation of Hg (ii) in humans can lead to cognitive disorders, dyskinesias and aquatics, causing serious damage to the central nervous system and even the formation of malignant tumors. Therefore, the detection of Cu (II) and Hg (II) is of great significance in a convenient, rapid, high-selectivity and high-sensitivity manner.
Conventional detection methods for Cu (II) and Hg (II) include Atomic Absorption Spectrometry (AAS), atomic Emission Spectrometry (AES), inductively Coupled Plasma (ICP), and the like. However, these detection methods have some disadvantages such as expensive required instruments, slow detection speed, etc. The fluorescent probe is adopted to detect the metal ions, and the fluorescent probe has low cost, simple and quick operation, high selectivity and high sensitivity, and becomes an important analysis method for analyzing the metal ions.
Rhodamine is commonly used to prepare fluorescent probes because of its good photophysical properties. According to the invention, rhodamine is used as a fluorophore, and quinoline derivatives are connected for auxiliary coordination, so that a fluorescent probe for detecting Cu (II) and Hg (II) is prepared.
Disclosure of Invention
The invention aims to provide a fluorescent probe for detecting Cu (II) and Hg (II), which is obtained by combining rhodamine and quinoline derivatives.
Another object of the present invention is to provide a method for preparing a fluorescent probe for detecting Cu (II) and Hg (II).
The technical scheme adopted by the invention is that a fluorescent probe for detecting Cu (II) and Hg (II) has the following structural formula:
the first technical scheme of the invention is also characterized in that the synthetic route of the fluorescent probe is as follows:
wherein, p-toluenesulfonic acid is p-toluenesulfonic acid and HCl acid is hydrochloric acid.
The fluorescent probe can selectively detect Cu (II) and Hg (II) in an aqueous solution of an organic solvent, wherein the organic solvent is any one of methanol, ethanol and acetonitrile.
The second technical scheme adopted by the invention is that a preparation method of a fluorescent probe for detecting Cu (II) and Hg (II) comprises the following specific steps:
step 1, adding a compound 2, ethylene glycol, p-methanesulfonic acid and 60-100 mL of toluene into a round-bottom flask, stirring to dissolve the mixture, and refluxing the mixture for 5-10 hours until the upper liquid of a water knockout drum is clarified; cooling the reaction system to room temperature, decompressing, evaporating toluene, and separating by dichloromethane chromatography to obtain a compound 3; the structural formula of compound 3 is as follows:
step 2, adding 20-50 mL of acetone into a round-bottomed flask, completely dissolving the compound 3 obtained in the step 1, and then adding K 2 CO 3 And 3-bromopropene, stirred and refluxed for 2 to 6 hours. The reaction mixture was cooled to room temperature, the solids were filtered off and the acetone was distilled off using a rotary evaporator. Then 10-30 mL of saturated saline solution is added, 30-60 mL of CH is used 2 Cl 2 Extracting, anhydrous Na 2 SO 4 Drying for 1-5 hr, filtering, evaporating CH by rotary evaporator 2 Cl 2 Finally, separating by column chromatography with dichloromethane as eluent to obtain a compound 4; the structural formula of compound 4 is as follows:
step 3, adding the compound 4 obtained in the step 2 and 5-20 mL of N-methylpyrrolidone into a round bottom flask, heating to 200-250 ℃, stirring and refluxing for 1-4 hours, cooling the reaction system mixture to room temperature, steaming under reduced pressure to remove the N-methylpyrrolidone, and separating by using dichloromethane as an eluent by column chromatography to obtain a compound 5; the structural formula of compound 5 is as follows:
and 4, adding the compound 5 obtained in the step 3 into a round-bottom flask, dropwise adding 1-3 mol/L of dilute hydrochloric acid into the mixture, and stirring and refluxing the mixture at 60-100 ℃ for 0.5-2 hours. Then cooling the reaction to room temperature, pouring the reaction product into 10-30 mL of water, adjusting the reaction product to be neutral by NaOH, extracting the reaction product by using dichloromethane, collecting an organic phase, and finally separating the reaction product by using dichloromethane as an eluent by column chromatography to obtain a compound 6; the structural formula of compound 6 is as follows:
step 5, adding the compound 7 and 10-30 mL of ethanol into a round-bottom flask, stirring to dissolve, then adding the compound 6 obtained in the step 4, stirring for 2-5 hours at 60-100 ℃, then cooling the reaction system to room temperature, evaporating the ethanol by a rotary evaporator, and finally washing by absolute ethanol to obtain the Probe 1, wherein the structural formula of the Probe 1 is shown as follows:
the second technical proposal of the invention is also characterized in that,
in the step 1, the mol ratio of the compound 2, the ethylene glycol and the p-toluenesulfonic acid is 1:1:1-2.
Compound 3, 3-bromopropene and K in step 2 2 CO 3 The molar ratio of (2) is 1.0:1.5:1.0-2.0.
The molar ratio of the compound 6 to the compound 7 in the step 5 is 1.0:1.0-1.2.
The invention discloses a fluorescent probe for detecting Cu (II) and Hg (II), and also discloses a preparation method of the fluorescent probe, wherein rhodamine fluorophores and 2-aldehyde-8-hydroxyquinoline are used as raw materials, and the fluorescent probe is prepared through five-step reaction. The fluorescent probe can detect Cu (II) and Hg (II) with high sensitivity and high selectivity through a fluorescence spectrum and an ultraviolet-visible absorption spectrum in a solution with the volume ratio of ethanol to water of 1:1. The fluorescent probe is expected to be applied to detecting out-of-standard Cu (II) and Hg (II) in river water, tap water, sewage and the like.
Drawings
FIG. 1 is a diagram showing a fluorescent probe for detecting Cu (II) and Hg (II) and a fluorescence spectrum of the probe in the presence of different metal ions according to the present invention;
FIG. 2 is a graph showing the ultraviolet-visible absorption spectra of a fluorescent probe for detecting Cu (II) and Hg (II) and the probe in the presence of different metal ions according to the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention discloses a fluorescent probe for detecting Cu (II) and Hg (II), which has the following structural formula:
the synthetic route of the fluorescent probe is as follows:
wherein, p-toluenesulfonic acid is p-toluenesulfonic acid and HCl acid is hydrochloric acid. The fluorescent probe can be used for Cu in aqueous solution of organic solvent 2+ And Hg of 2+ Selectively identifying and detecting, wherein the organic solvent is any one of methanol, ethanol and acetonitrile.
The invention also provides a preparation method of the fluorescent probe for detecting Cu (II) and Hg (II), which comprises the following specific steps:
step 1, adding a compound 2 (2-aldehyde-8-hydroxyquinoline), glycol, p-methanesulfonic acid and 60-100 mL of toluene into a round bottom flask, stirring to dissolve the mixture, and refluxing the mixture for 5-10 hours until the upper liquid of a water knockout drum is clarified; cooling the reaction system to room temperature, decompressing, evaporating toluene, and separating by dichloromethane chromatography to obtain a compound 3; the structural formula of compound 3 is as follows:
in the step 1, the mol ratio of the compound 2, the ethylene glycol and the p-toluenesulfonic acid is 1:1:1-2.
Step 2, adding 20-50 mL of acetone into a round-bottomed flask, completely dissolving the compound 3 obtained in the step 1, and then adding K 2 CO 3 And 3-bromopropene, stirred and refluxed for 2 to 6 hours. The reaction mixture was cooled to room temperature, the solids were filtered off and the acetone was distilled off using a rotary evaporator. Then 10-30 mL of saturated saline solution is added, 30-60 mL of CH is used 2 Cl 2 Extracting, anhydrous Na 2 SO 4 Drying for 1-5 hr, filtering, evaporating CH by rotary evaporator 2 Cl 2 Finally, separating by column chromatography with dichloromethane as eluent to obtain a compound 4; the structural formula of compound 4 is as follows:
compound 3, 3-bromopropene and K in step 2 2 CO 3 The molar ratio of (2) is 1.0:1.5:1.0-2.0.
Step 3, adding the compound 4 obtained in the step 2 and 5-20 mL of N-methylpyrrolidone into a round bottom flask, heating to 200-250 ℃, stirring and refluxing for 1-4 hours, cooling the reaction system mixture to room temperature, steaming under reduced pressure to remove the N-methylpyrrolidone, and separating by using dichloromethane as an eluent by column chromatography to obtain a compound 5; the structural formula of compound 5 is as follows:
and 4, adding the compound 5 obtained in the step 3 into a round-bottom flask, dropwise adding 1-3 mol/L of dilute hydrochloric acid into the mixture, and stirring and refluxing the mixture at 60-100 ℃ for 0.5-2 hours. Then cooling the reaction to room temperature, pouring the reaction product into 10-30 mL of water, adjusting the reaction product to be neutral by NaOH, extracting the reaction product by using dichloromethane, collecting an organic phase, and finally separating the reaction product by using dichloromethane as an eluent by column chromatography to obtain a compound 6; the structural formula of compound 6 is as follows:
step 5, adding a compound 7 (rhodamine fluorophor) and 10-30 mL of ethanol into a round-bottom flask, stirring to dissolve, then adding the compound 6 obtained in the step 4, stirring for 2-5 hours at 60-100 ℃, cooling the reaction system to room temperature, evaporating the ethanol by a rotary evaporator, and finally washing by absolute ethanol to obtain the Probe 1, wherein the structural formula of the Probe 1 is shown as follows:
the molar ratio of the compound 6 to the compound 7 in the step 5 is 1.0:1.0-1.2.
Example 1: to a 150mL round bottom flask was added 8.9mmol 2, 8.9mmol ethylene glycol, 60mL toluene and 8.9mmol p-toluene sulfonic acid, which were dissolved with stirring and refluxed for 8 hours until the water trap supernatant was clear. The reaction was cooled to room temperature and toluene was distilled off using a rotary evaporator. Column chromatography using dichloromethane as eluent gave 1.73g of compound 3, yield: 90%. The structural formula of compound 3 is as follows:
example 2 to a 50mL round bottom flask was added 30mL of acetone to dissolve 10.0mmol of Compound 3 from step 1 completely, followed by 15.0mmol K 2 CO 3 And 15.0mmol of 3-bromopropene, stirred and refluxed for 4 hours. The reaction mixture was cooled to room temperature, the solids were filtered off and the acetone was distilled off using a rotary evaporator. Then saturated 15mL of saline was added, followed by 50mL of CH 2 Cl 2 Extracting, anhydrous Na 2 SO 4 Drying for 1 hr, filtering, evaporating CH with rotary evaporator 2 Cl 2 Finally, separating by column chromatography with dichloromethane as eluent to obtain compound 4, yield: 90%. The structural formula of compound 4 is as follows:
example 3 to a 25mL round bottom flask were added 7.5mmol of compound 4 from step 2, 10mL of N-methylpyrrolidone, heated to 220 c, stirred and refluxed for 3 hours, the reaction mixture was cooled to room temperature and the N-methylpyrrolidone was distilled off under reduced pressure. Column chromatography using dichloromethane as eluent gave compound 5, yield: 92%. The structural formula of compound 5 is as follows:
example 4 to a 100mL round bottom flask was added 1.75mmol of compound 5 obtained in step 3, 2mol/L of dilute hydrochloric acid was slowly added dropwise thereto, and the mixture was refluxed with stirring at 80 c for 1 hour. Subsequently, the reaction was cooled to room temperature, poured into 20mL of water, neutralized with dilute NaOH, extracted with dichloromethane, and the organic phase was collected. Finally, 387mg of compound 6 was isolated by column chromatography using dichloromethane as eluent. Yield: 95%. The structural formula of compound 6 is as follows:
example 5: to a 50mL round bottom flask was added 286mg of Compound 7 and 20mL of ethanol and dissolved with stirring. Then 133.4mg of Compound 6 from step 4 was added thereto, and the mixture was refluxed with stirring at 80℃for 3 hours. Subsequently, the reaction system was cooled to room temperature, and ethanol was distilled off using a rotary evaporator. Finally, 387mg of Probe 1 is obtained after washing by absolute ethyl alcohol, and the yield is: 95%.
Example 6: probe 1 pair Cu 2+ And Hg of 2+ Is characterized by comprising the following steps:
in a solution with the volume ratio of ethanol to water being 1:1, 50 mu M of metal salt solutions of Na (I), K (I), ca (II), mg (II), ba (II), mn (II), co (II), ni (II), zn (II), cu (II) and Hg (II) are respectively dropwise added into a 10 mu M Probe 1 solution, and the fluorescence spectrum of the system is shown in figure 1: probe 1 has a weak emission peak at 570nm of maximum emission wavelength, and when Cu (II) and Hg (II) are added, the emission peak at 570nm is obviously enhanced, while when other metal ions are added, the emission peak remains basically unchanged. The results show that the probe can recognize Cu (II) and Hg (II) with high sensitivity and high selectivity in a plurality of metal ions.
Example 7: ultraviolet-visible spectrum identification detection of Probe 1 on Cu (II) and Hg (II):
in a solution with the volume ratio of ethanol to water being 1:1, 60 mu M of metal salt solutions of Na (I), K (I), ca (II), mg (II), ba (II), mn (II), co (II), ni (II), zn (II), cu (II) and Hg (II) are respectively dropwise added into a 30 mu M Probe 1 solution, and the ultraviolet-visible absorption spectrum of the system is shown in figure 2: when Cu (II) and Hg (II) are added, the absorption peak at 560nm is obviously enhanced, while when other metal ions are added, the absorption peak is kept basically unchanged. The results show that the probe can recognize Cu (II) and Hg (II) with high sensitivity and high selectivity in a plurality of metal ions.

Claims (2)

1. The preparation method of the fluorescent probe for detecting Cu (II) and Hg (II) is characterized by comprising the following steps: the method specifically comprises the following steps:
step 1, adding a compound 2, ethylene glycol, p-toluenesulfonic acid and 60-100 mL of toluene into a round bottom flask, stirring to dissolve the mixture, and refluxing the mixture for 5-10 hours until the upper liquid of a water knockout drum is clarified; cooling the reaction system to room temperature, decompressing, evaporating toluene, and separating by dichloromethane chromatography to obtain a compound 3; the structural formula of compound 3 is as follows:
in the step 1, the mol ratio of the compound 2 to the glycol to the p-toluenesulfonic acid is 1:1:1-2, and the compound 2 is 2-aldehyde-8-hydroxyquinoline;
step 2, adding 20-50 mL of acetone into a round-bottomed flask, completely dissolving the compound 3 obtained in the step 1, and then adding K 2 CO 3 And 3-bromopropene, stirring and refluxing for 2-6 hrThe reaction mixture was cooled to room temperature, the solid was filtered off, acetone was distilled off by means of a rotary evaporator, 10 to 30mL of saturated brine was then added, and 30 to 60mL of CH was used 2 Cl 2 Extracting, anhydrous Na 2 SO 4 Drying for 0.5-1 hr, filtering, evaporating CH by rotary evaporator 2 Cl 2 Finally, separating by column chromatography with dichloromethane as eluent to obtain a compound 4; the structural formula of compound 4 is as follows:
the compound 3, 3-bromopropene and K in the step 2 2 CO 3 The molar ratio of (2) is 1.0:1.5:1.0-2.0;
step 3, adding the compound 4 obtained in the step 2 and 5-20-mLN-methylpyrrolidone into a round-bottom flask, heating to 200-250 ℃, stirring and refluxing for 1-4 hours, cooling the reaction system mixture to room temperature, decompressing and steaming to remove the N-methylpyrrolidone, and separating by using dichloromethane as an eluent by column chromatography to obtain a compound 5; the structural formula of compound 5 is as follows:
step 4, adding the compound 5 obtained in the step 3 into a round-bottom flask, dropwise adding 1-3 mol/L of dilute hydrochloric acid into the mixture, stirring and refluxing the mixture for 0.5-2 hours at the temperature of 60-100 ℃, then cooling the reaction to room temperature, pouring the reaction product into 10-30 mL of water, adjusting the reaction product to be neutral by NaOH, extracting the reaction product by using dichloromethane, collecting an organic phase, and finally separating the organic phase by using dichloromethane as an eluent by column chromatography to obtain a compound 6; the structural formula of compound 6 is as follows:
step 5, adding the compound 7 and 10-30 mL of ethanol into a round-bottom flask, stirring to dissolve, then adding the compound 6 obtained in the step 4, stirring and refluxing for 2-5 hours at 60-100 ℃, then cooling the reaction system to room temperature, evaporating the ethanol by a rotary evaporator, and finally washing by absolute ethanol to obtain the Probe 1, wherein the structural formula of the Probe 1 is as follows:
the molar ratio of the compound 6 to the compound 7 in the step 5 is 1.0:1.0-1.2; compound 7 is a rhodamine fluorophore.
2. The fluorescent probe prepared by the preparation method of the fluorescent probe for detecting Cu (II) and Hg (II) according to claim 1, wherein the fluorescent probe is characterized in that: the structural formula is as follows:
the synthetic route of the probe is as follows:
wherein, p-toluenesulfonic acid is p-toluenesulfonic acid, and HCl acid is hydrochloric acid;
the fluorescent probe can be used for Cu in aqueous solution of organic solvent 2+ And Hg of 2+ Selectively identifying and detecting, wherein the organic solvent is any one of methanol, ethanol and acetonitrile.
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