CN109928913B - Fluorescent probe for identifying mercury ions and preparation method and identification method thereof - Google Patents
Fluorescent probe for identifying mercury ions and preparation method and identification method thereof Download PDFInfo
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- CN109928913B CN109928913B CN201910330225.6A CN201910330225A CN109928913B CN 109928913 B CN109928913 B CN 109928913B CN 201910330225 A CN201910330225 A CN 201910330225A CN 109928913 B CN109928913 B CN 109928913B
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Abstract
The invention discloses a fluorescent probe for identifying mercury ions and a preparation method and an identification method thereof. The chemical structural formula of the probe is shown in figure 1. The preparation method comprises adding 2, 5-dibromoaniline, 4-vinylpyridine, bis (triphenylphosphine) palladium dichloride and anhydrous potassium carbonate into DMF, mixing, sealing the mixture in N2Reacting for 18-32h at the temperature of 100-120 ℃ in a high-pressure reaction bottle under the atmosphere to obtain a product A; completely dissolving product A in dichloromethane to obtain black suspension to obtain product B; washing the product B with water and saturated saline solution sequentially to obtain product C; and standing the product C for layering, separating a dichloromethane layer at the lowest layer, drying by using anhydrous magnesium sulfate, spin-drying, and finally recrystallizing by using ethanol to obtain the fluorescent probe. The identification method is to identify mercury ions in a DMF system. The invention is a novel mercury ion recognition fluorescent probe, and has the characteristics of low recognition cost, simple recognition process, visible result, high sensitivity and good selectivity.
Description
Technical Field
The invention relates to a reagent for identifying mercury ions, a preparation method and an identification method thereof, in particular to a fluorescent probe for identifying mercury ions, a preparation method and an identification method thereof.
Background
Mercury is one of the most dangerous metal pollutants, is a typical heavy metal ion, has extremely strong toxicity, and can cause permanent damage to biological nervous systems. The mercury in the environment is oxidized into water-soluble divalent mercury ions in the air, and once the mercury ions enter the water environment, the mercury ions are converted into organic methyl mercury by bacteria microorganisms and are rapidly accumulated in organisms such as fish so as to enter the food chain. Methyl mercury destroys the human nervous system, causes brain damage, cognitive and motor disorders, etc., and world-borne water-induced disease is one type of organic mercury poisoning. Therefore, the development of a high-selectivity and high-sensitivity Hg2+ detection method is important for environmental protection and human health.
Many analytical methods have been used to determine mercury ions, such as atomic absorption spectrometry, inductively coupled plasma mass spectrometry, cold atomic fluorescence spectrometry, inductively coupled plasma atomic emission spectrometry, electrochemical methods, and uv-vis spectrophotometry. Although these methods have high sensitivity, they have the disadvantages of high detection cost, complex sample processing, time consuming, and unsuitability for real-time and on-site detection. Since fluorescent probes have absolute advantages in terms of selectivity, detection cost, and the like, designing and using fluorescent probes to detect mercury ions currently draws a great deal of attention from analysts. The design and synthesis of the fluorescent probe with selectivity to mercury ions can realize the visual detection of the mercury ions, so that the high-efficiency and accurate detection method has important significance in the fields of environment, medicine and biology.
Disclosure of Invention
The invention aims to provide a fluorescent probe for identifying mercury ions, and a preparation method and an identification method thereof. The invention is a novel mercury ion recognition fluorescent probe, and has the characteristics of low recognition cost, simple recognition process, visible result, high sensitivity and good selectivity.
The technical scheme of the invention is as follows: a fluorescent probe for identifying mercury ions has a molecular formula as follows: c20H17N3The structural formula is as follows:
the preparation method of the fluorescent probe for identifying mercury ions comprises the following steps:
(1) adding 2, 5-dibromoaniline, 4-vinylpyridine, bis (triphenylphosphine) palladium dichloride and anhydrous potassium carbonate into DMF, mixing, and sealing the mixture in N2Reacting for 18-32h at the temperature of 100-120 ℃ in a high-pressure reaction bottle under the atmosphere to obtain a product A;
(2) completely dissolving product A in dichloromethane to obtain black suspension to obtain product B;
(3) washing the product B with water and saturated saline water sequentially to obtain product C;
(4) and standing and layering the product C, separating a dichloromethane layer at the lowest layer, drying with anhydrous magnesium sulfate, spin-drying, and finally recrystallizing with ethanol to obtain the fluorescent probe.
In the preparation method of the fluorescent probe for identifying mercury ions, the solvent DMF is an anhydrous reagent.
In the preparation method of the fluorescent probe for identifying mercury ions, in the step (1), 0.5 to 1.5g of 2, 5-dibromoaniline, 1 to 1.5g of 4-vinylpyridine, 40 to 60mg of bis (triphenylphosphine) palladium dichloride and 1 to 1.5g of anhydrous potassium carbonate are added into every 5mL of DMF.
The fluorescent probe for identifying mercury ions was prepared by adding 1g of 2, 5-dibromoaniline, 1.2g of 4-vinylpyridine, 50mg of bis (triphenylphosphine) palladium dichloride and 1.2g of anhydrous potassium carbonate to 5mL of DMF.
In the preparation method of the fluorescent probe for identifying mercury ions, in the step (3), the article B is washed with water and saturated saline solution for 3 times.
In the preparation method of the fluorescent probe for identifying mercury ions, in the step (4), anhydrous ethanol is used for recrystallization.
The method for identifying the fluorescent probe for identifying the mercury ions is to identify the mercury ions in a DMF system.
The application of the fluorescent probe for identifying mercury ions comprises the following specific steps: dissolving a probe in DMF to obtain a fluorescent reagent, then dripping a sample to be identified into the reagent to obtain a sample solution, carrying out fluorescence excitation on the sample solution, and testing and analyzing the fluorescence wavelength excited by fluorescence.
The application of the fluorescent probe for identifying mercury ions is that the concentration of the probe in the fluorescent reagent is 10-5And the used fluorescence excitation wavelength is 343nm, and when the sample to be identified is added and mercury ions are identified, the maximum fluorescence emission wavelength of the reagent is red shifted from 528nm to 610 nm.
The invention has the advantages of
As a novel fluorescent probe, the invention can identify mercury ions in a DMF system, and has the advantages of low identification cost, simple operation, visible structure, high sensitivity and good selectivity similar to the effect of other fluorescent probes.
To illustrate the advantageous effects of the present invention, the inventors made the following experiments:
first, qualitative analysis test
1. In the concentration range of 10-6～10-4In mol/L fluorescent probe water solution, when the excitation wavelength is 343nm, the maximum emission wavelength of the fluorescent probe is 528nm, and when Hg is added into the fluorescent probe solution2+The maximum emission wavelength of the fluorescent probe then red shifts from 528nm to 610nm, which appears as an orange-red fluorescence.
Second, quantitative analysis test
1. The preparation method of the fluorescent probe solution comprises the following steps: 3mg of the probe was weighed, dissolved in DMF and prepared to a volume of 10mL and a concentration of 1.0X 10-3mol·L-1Taking 1 100.0mL volumetric flask, taking 1mL of the prepared probe solution in the volumetric flask, diluting the probe solution with DMF to scale mark to obtain a concentration of 1.0X 10-5mol·L-1The probe solution of (1).
2. Weighing superior pure mercury perchlorate to prepare 10mL DMF (or secondary water) solution with concentration of 1.0 × 10- 2mol·L-1And gradually diluted with DMF (or secondary water) as required.
3. Taking fluorescent reagent 1.0X 10-5Adding 3mL of fluorescent reagent into the cuvette according to mol.L-1 standard solution, and respectively dropwise adding 1.0 × 10-3mol·L-1Hg2+ ion solution, and fluorescence spectrum is introduced for measurement, and the excitation wavelength is 343 nm.
4. Respectively with Hg2+The ion concentration is the abscissa, and the fluorescence intensity is the ordinate, to obtain the working curve.
5. And (3) sample determination: two 10.0mL volumetric flasks were taken and added with a fluorescent reagent of 1.0X 10-3mol·L-10.1mL of standard solution, Hg was added to each of the two volumes2+Diluting the ionic solution to scale, standing at room temperature for 5 min, introducing into a quartz cuvette of 3.0cm for fluorescence measurement, and performing fluorescence measurement according to fluorescence intensityThe concentration of the sample was checked on the curve.
Third, anti-interference experiment
At a probe concentration of 1.00X 10-5mol·L-1Hg is added into the reagent2+Red shift of the post-fluorescence, and adding other cations (Zn) into the fluorescent reagent2+,Al3+,Ca2+,Fe2+,Pb2+,Ba2+,Cu2+,Ag+,Fe3+,Cr3+,Li+,Ni2+,K+,Mg2 +,Co2+,Na+,Mn2+) The results are shown in FIG. 5, which shows only Hg2+The maximum emission wavelength of the fluorescent reagent can be blue-shifted from 528nm to 610nm, and the fluorescence intensity is reduced.
Drawings
FIG. 1 is a chemical structural formula of a fluorescent probe molecule;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a fluorescent probe molecule;
FIG. 3 is a fluorescence spectrum of the interaction of fluorescent probe molecules with different metal ions;
FIG. 4 is a graph showing the change of fluorescence of fluorescent probe molecules in DMF with the addition of mercury ions;
FIG. 5 is an anti-interference experimental diagram of fluorescent probe molecules.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Examples of the invention
Example 1: a preparation method of a fluorescent probe for identifying mercury ions comprises the following steps:
(1) 1g of 2, 5-dibromoaniline, 1.2g of 4-vinylpyridine, 50mg of bistriphenylphosphine palladium dichloride and 1.2g of anhydrous potassium carbonate are added to 5ml of anhydrous DMF and mixed, and the mixture is sealed in N2Reacting for 25h at 110 ℃ in a high-pressure reaction bottle in the atmosphere to obtain a product A;
(2) completely dissolving product A in dichloromethane to obtain black suspension to obtain product B;
(3) washing the product B with water and saturated saline solution for 3 times to obtain product C;
(4) and standing and layering the product C, separating a dichloromethane layer at the lowest layer, drying with anhydrous magnesium sulfate, spin-drying, and finally recrystallizing with anhydrous ethanol to obtain the fluorescent probe.
Example 2: a preparation method of a fluorescent probe for identifying mercury ions comprises the following steps:
(1) 0.5g of 2, 5-dibromoaniline, 1g of 4-vinylpyridine, 40mg of bistriphenylphosphine palladium dichloride and 1g of anhydrous potassium carbonate are added to 5ml of anhydrous DMF and mixed, and the mixture is sealed in N2Reacting for 18h at 100 ℃ in a high-pressure reaction bottle in the atmosphere to obtain a product A;
(2) completely dissolving product A in dichloromethane to obtain black suspension to obtain product B;
(3) washing the product B with water and saturated saline solution for 3 times to obtain product C;
(4) and standing and layering the product C, separating a dichloromethane layer at the lowest layer, drying with anhydrous magnesium sulfate, spin-drying, and finally recrystallizing with anhydrous ethanol to obtain the fluorescent probe.
Example 3: a preparation method of a fluorescent probe for identifying mercury ions comprises the following steps:
(1) 1.5g of 2, 5-dibromoaniline, 1.5g of 4-vinylpyridine, 60mg of bistriphenylphosphine palladium dichloride and 1.5g of anhydrous potassium carbonate are added to 5ml of anhydrous DMF and mixed, and the mixture is sealed in N2Reacting for 32 hours at 120 ℃ in a high-pressure reaction bottle in the atmosphere to obtain a product A;
(2) completely dissolving product A in dichloromethane to obtain black suspension to obtain product B;
(3) washing the product B with water and saturated saline solution for 3 times to obtain product C;
(4) and standing and layering the product C, separating a dichloromethane layer at the lowest layer, drying with anhydrous magnesium sulfate, spin-drying, and finally recrystallizing with anhydrous ethanol to obtain the fluorescent probe.
Example 4: the method for identifying the fluorescent probe for identifying the mercury ions comprises the steps of dissolving the probe in DMF to prepare the probe with the concentration of 10-5A mol/L fluorescent reagent, then a sample to be identified is dripped into the reagent to obtain a sample solution, and the sample solution is subjected to fluorescenceFluorescence excitation is carried out at an excitation wavelength of 343nm, the fluorescence wavelength of fluorescence excitation is tested and analyzed, and when a sample to be identified is added and mercury ions are identified, the maximum fluorescence emission wavelength of the reagent is red-shifted from 528nm to 610 nm.
Claims (10)
1. A fluorescent probe for identifying mercury ions is characterized in that the molecular formula of the probe is as follows: c20H17N3The structural formula is as follows:
2. the method for preparing the fluorescent probe for identifying mercury ions according to claim 1, comprising the following steps:
(1) adding 2, 5-dibromoaniline, 4-vinylpyridine, bis (triphenylphosphine) palladium dichloride and anhydrous potassium carbonate into DMF, mixing, and sealing the mixture in N2Reacting for 18-32h at the temperature of 100-120 ℃ in a high-pressure reaction bottle under the atmosphere to obtain a product A;
(2) completely dissolving product A in dichloromethane to obtain black suspension to obtain product B;
(3) washing the product B with water and saturated saline solution sequentially to obtain product C;
(4) and standing and layering the product C, separating a dichloromethane layer at the lowest layer, drying with anhydrous magnesium sulfate, spin-drying, and finally recrystallizing with ethanol to obtain the fluorescent probe.
3. The method for preparing a fluorescent probe for identifying mercury ions according to claim 2, wherein: the DMF is an anhydrous reagent.
4. The method for preparing a fluorescent probe for identifying mercury ions according to claim 2, wherein: in the step (1), 0.5-1.5g of 2, 5-dibromoaniline, 1-1.5g of 4-vinylpyridine, 40-60mg of bis (triphenylphosphine) palladium dichloride and 1-1.5g of anhydrous potassium carbonate are added per 5mL of DMF.
5. The method for preparing a fluorescent probe for identifying mercury ions according to claim 4, wherein: 1g of 2, 5-dibromoaniline, 1.2g of 4-vinylpyridine, 50mg of bistriphenylphosphine palladium dichloride and 1.2g of anhydrous potassium carbonate are added per 5mL of the DMF.
6. The method for preparing a fluorescent probe for identifying mercury ions according to claim 2, wherein: in the step (3), the product B is washed for 3 times by water and saturated salt solution in sequence.
7. The method for preparing a fluorescent probe for identifying mercury ions according to claim 2, wherein: in the step (4), anhydrous ethanol is adopted for recrystallization.
8. The method for identifying a fluorescent probe for identifying mercury ions according to claim 1, wherein: is used for identifying mercury ions in a DMF system.
9. The method for identifying the fluorescent probe for mercury ions according to claim 8, wherein the specific method for identifying the mercury ions is as follows: dissolving a probe in DMF to obtain a fluorescent reagent, then dripping a sample to be identified into the reagent to obtain a sample solution, carrying out fluorescence excitation on the sample solution, and testing and analyzing the fluorescence wavelength excited by fluorescence.
10. The method for identifying a fluorescent probe for mercury ions according to claim 9, wherein: the concentration of the probe in the fluorescent reagent is 10-5And the used fluorescence excitation wavelength is 343nm, and when the sample to be identified is added and mercury ions are identified, the maximum fluorescence emission wavelength of the reagent is red shifted from 528nm to 610 nm.
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| CN103242195A (en) * | 2013-04-28 | 2013-08-14 | 中南大学 | Synthesis and application of fluorescence enhancement detection mercury ion probe |
| CN107056667A (en) * | 2017-03-14 | 2017-08-18 | 华东师范大学 | A kind of mercury ion probe and its preparation method and application |
| WO2017210874A1 (en) * | 2016-06-08 | 2017-12-14 | Xia, Ling | Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation |
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| CN103242195A (en) * | 2013-04-28 | 2013-08-14 | 中南大学 | Synthesis and application of fluorescence enhancement detection mercury ion probe |
| WO2017210874A1 (en) * | 2016-06-08 | 2017-12-14 | Xia, Ling | Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation |
| CN107056667A (en) * | 2017-03-14 | 2017-08-18 | 华东师范大学 | A kind of mercury ion probe and its preparation method and application |
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