CN109928912B - Fluorescent probe for identifying mercury ions and preparation and identification methods thereof - Google Patents
Fluorescent probe for identifying mercury ions and preparation and identification methods thereof Download PDFInfo
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- CN109928912B CN109928912B CN201910084553.2A CN201910084553A CN109928912B CN 109928912 B CN109928912 B CN 109928912B CN 201910084553 A CN201910084553 A CN 201910084553A CN 109928912 B CN109928912 B CN 109928912B
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Abstract
The invention discloses a fluorescent probe for identifying mercury ionsThe preparation method comprises dissolving 4-bromobenzaldehyde in ethanol to obtain A; dissolving 2-acetylpyridine, potassium hydroxide and ammonia water in ethanol to obtain B; mixing the A substance and the B substance, precipitating and filtering after reaction, and recrystallizing in acetic acid to obtain C; adding the C substance, 4-pyridine ethylene, palladium acetate and triphenylphosphine into triethylamine for mixing, and sealing the mixture in N2Reacting in a high-pressure reaction bottle in the atmosphere, dissolving the product in chloroform, then spin-drying, and recrystallizing with ethanol to obtain D; and adding the D substance into N, N-dimethylformamide for dissolving, then adding 6-bromohexanoic acid for reaction, adding diethyl ether into the reaction solution until the reaction solution is completely precipitated, performing suction filtration, washing twice with diethyl ether, and drying to obtain the fluorescent probe for identifying mercury ions. The method can realize qualitative and quantitative analysis of mercury ions, and has the characteristics of low identification cost, simplicity in operation, visual result, high sensitivity, good selectivity and the like.
Description
Technical Field
The invention relates to a fluorescent probe and a preparation method and an identification method thereof, in particular to a fluorescent probe for identifying mercury ions and 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, development of highly selective and highly sensitive Hg2+The 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 method can realize qualitative and quantitative analysis of mercury ions, and has the characteristics of low identification cost, simple operation, visual result, high sensitivity, good selectivity and the like.
The technical scheme of the invention is that the fluorescent probe for identifying mercury ions has a molecular formula as follows: c34H31BrN4O2The structural formula is shown in figure 1.
The preparation method of the fluorescent probe for identifying mercury ions according to claim 1, comprising the following steps:
(1) dissolving 4-bromobenzaldehyde in ethanol to obtain a substance A;
(2) dissolving 2-acetylpyridine, potassium hydroxide and ammonia water in ethanol to obtain a substance B;
(3) mixing the substance A and the substance B, stirring for 1-3 h at 0-5 ℃, refluxing for 10-30h at 70-90 ℃, cooling to room temperature, stirring for 30-60 min, filtering the precipitate, and recrystallizing in acetic acid to obtain a substance C;
(4) adding the C substance, 4-pyridine ethylene, palladium acetate and triphenylphosphine into triethylamine for mixing, and sealing the mixture in N2Reacting for 65-75 h at 100-120 ℃ in a high-pressure reaction bottle in the atmosphere, dissolving the product in chloroform, then spin-drying, and recrystallizing with ethanol to obtain a substance D;
(5) and (3) adding the D substance into N, N-dimethylformamide for dissolving, then adding 6-bromohexanoic acid, heating to 75-85 ℃, reacting for 30-40h, adding diethyl ether into the reaction solution until the diethyl ether is completely precipitated, performing suction filtration, washing twice with diethyl ether, and drying to obtain the fluorescent probe for identifying mercury ions.
In the preparation method of the fluorescent probe for identifying mercury ions, the concentration of ethanol is greater than 95%.
In the preparation method of the fluorescent probe for identifying mercury ions, in the step (1), 0.5 to 1.5g of 4-bromobenzaldehyde is added to each 15mL of ethanol; in the step (2), 1 to 1.5g of 2-acetylpyridine, 0.5 to 1.5g of potassium hydroxide and 10 to 20mL of ammonia water are added into each 20mL of ethanol.
In the step (4), in each 1000mg of substance C, 250-350mg of 4-pyridylethylene, 50-70mg of palladium acetate, 150-250mg of triphenylphosphine and 15-25cm are mixed3Triethylamine; before spin-drying, the organic phase is washed with distilled water for 2-4 times, then washed with saturated saline for 2-4 times, and dried over anhydrous magnesium sulfate for 0.5-2 h.
In the preparation method of the fluorescent probe for identifying mercury ions, in the step (5), the ratio of the amount of the substance D to the amount of the substance 6-bromohexanoic acid is 1: 1.
The method for identifying the fluorescent probe for identifying the mercury ions comprises the steps of dissolving the probe in DMSO, diluting with secondary water to obtain a fluorescent reagent, 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.
In the method for identifying the fluorescent probe for identifying mercury ions, the concentration of the probe in the fluorescent reagent is 10- 5mol.L-1。
In the method for identifying the fluorescent probe for identifying mercury ions, the wavelength of fluorescence excitation is 365nm, and when the sample to be identified is added and mercury ions are identified, the maximum fluorescence emission wavelength of the reagent is blue-shifted from 520nm to 473 nm.
The invention has the advantages of
(1) The invention can be used for treating Hg in aqueous solution2+Performing qualitative and quantitative analysis;
(2) the invention is a fluorescent probe, can realize the identification and detection of mercury ions by adopting a chemical method, does not need expensive detection equipment, has low detection cost, does not need to carry out special treatment on a sample, and has simple operation;
(3) the mercury ions are detected through fluorescence change, and the result is observed through fluorescence change, so that the mercury ion fluorescence detection method has the advantage of visual result;
(4) other common coexisting metal cations do not interfere with the measurement, and have strong interference resistance, high sensitivity and good selectivity.
To further illustrate the beneficial effects of the present invention, the inventors made the following experiments:
first, qualitative analysis test
In the concentration range of 10-6～10-4In mol/L fluorescent probe water solution, when the excitation wavelength is 365nm, the maximum emission wavelength of the fluorescent probe is 520nm, and when Hg is added into the fluorescent probe water solution2+Thereafter, the maximum emission wavelength of the fluorescent probe was blue-shifted from 520nm to 473nm, showing blue fluorescence.
Second, quantitative analysis test
1. The preparation method of the fluorescent probe solution comprises the following steps: 6.08mg of the probe was weighed, dissolved in DMSO, 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 with secondary water to the scale mark to obtain a solution with a concentration of 1.0X 10-5mol·L-1The probe solution of (1).
2. Weighing superior pure mercuric perchlorate and cadmium perchlorate to prepare 10mL of aqueous solution with the concentrations of 1.0 multiplied by 10- 2mol·L-1And diluting with secondary water step by step according to the requirement.
3. Taking fluorescent reagent 1.0 × 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+And introducing a fluorescence spectrum into the ionic solution for measurement, wherein the excitation wavelength is 365 nm.
4. Respectively in 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 containers are takenMeasuring bottles, respectively adding fluorescent reagent 1.0 × 10-3mol·L-10.1mL of standard solution, Hg was added to each of the two volumes2+Diluting the ionic solution to a scale, standing at room temperature for 5 minutes, introducing a quartz cuvette of 3.0cm for fluorescence measurement, and finding out the concentration of the sample on a working curve according to the fluorescence intensity. The lowest concentration value of detection identification is 1.0 multiplied by 10-7mol·L-1。
Third, anti-interference test
At a probe concentration of 1.00X 10-5mol·L-1Hg is added into the reagent2+After the fluorescence is blue-shifted, other cations (Zn) are added into the fluorescent reagent respectively2+,Al3+,Ca2+,Fe2+,Pb2+,Ba2+,Cu2+,Ag+,Fe3+,Cr3+,Li+,Ni2+,K+,Mg2 +,Co2+,Na+,Mn2+) The results are shown in FIG. 3, which shows only Hg2+The maximum emission wavelength of the fluorescent reagent can be blue-shifted from 520nm to 473nm, and the fluorescence intensity is obviously enhanced.
Drawings
FIG. 1 is a chemical structural formula of a fluorescent probe;
FIG. 2 is a nuclear magnetic hydrogen spectrum of a fluorescent probe;
FIG. 3 is a graph of fluorescence spectra of fluorescent probes with different metal ions;
FIG. 4 is a graph showing the change in fluorescence of a fluorescent probe in water with the addition of mercury ions;
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 fluorescent probe for identifying mercury ions has a molecular formula as follows: c34H31BrN4O2The structural formula of the probe is shown in figure 1; the NMR spectrum is shown in figure 2.
Example 2: a method for preparing the probe of embodiment 1, comprising the steps of:
(1) adding 1g of 4-bromobenzaldehyde into 15mL of ethanol to obtain a substance A;
(2) adding 1.21g of 2-acetylpyridine, 0.9g of potassium hydroxide and 15mL of ammonia water into 20mL of ethanol to obtain a substance B;
(3) mixing the A substance and the B substance, stirring at 2 deg.C for 1h, refluxing at 80 deg.C for 20h, cooling to room temperature, stirring for 45min, filtering the precipitate, and recrystallizing in acetic acid to obtain C substance;
(4) 1000mg of substance C were mixed with 300mg of 4-pyridylethylene, 60mg of palladium acetate, 200mg of triphenylphosphine and 20cm of3Triethylamine, sealing the mixture in N2Reacting at 110 ℃ for 70h in a high-pressure reaction bottle in the atmosphere, dissolving the product in chloroform, washing the organic phase with distilled water for 3 times, washing the organic phase with saturated saline water for 3 times, drying the organic phase with anhydrous magnesium sulfate for 1h, then spin-drying the organic phase, and recrystallizing the organic phase with ethanol to obtain a D substance;
(5) and adding the D substance into N, N-dimethylformamide for dissolving, then adding 6-bromohexanoic acid, controlling the mass ratio of the D substance to the 6-bromohexanoic acid to be 1:1, heating to 80 ℃, reacting for 35 hours, adding diethyl ether into the reaction solution until the D substance and the 6-bromohexanoic acid are completely precipitated, performing suction filtration, washing twice with diethyl ether, and drying to obtain the fluorescent probe for identifying mercury ions.
Example 3: a method for preparing the probe of embodiment 1, comprising the steps of:
(1) adding 0.5g of 4-bromobenzaldehyde into 15mL of ethanol to obtain a substance A;
(2) adding 1g of 2-acetylpyridine, 0.5g of potassium hydroxide and 10mL of ammonia water into 20mL of ethanol to obtain a substance B;
(3) mixing the A substance and the B substance, stirring at 0 deg.C for 3h, refluxing at 70 deg.C for 30h, cooling to room temperature, stirring for 30min, filtering the precipitate, and recrystallizing in acetic acid to obtain C substance;
(4) to 1000mg of substance C were mixed 250mg of 4-pyridylethylene, 50mg of palladium acetate, 150mg of triphenylphosphine and 15cm3Triethylamine, sealing the mixture in N2Reacting at 100 deg.C for 65 hr in high pressure reaction flask under atmosphere, dissolving the product in chloroform, washing the organic phase with distilled water for 2 times, and washing the organic phase with saturated saline solution for 2 times withoutDrying with magnesium sulfate, spin drying, and recrystallizing with ethanol to obtain D;
(5) and adding the D substance into N, N-dimethylformamide for dissolving, then adding 6-bromohexanoic acid, controlling the mass ratio of the D substance to the 6-bromohexanoic acid to be 1:1, heating to 75 ℃, reacting for 40 hours, adding diethyl ether into the reaction solution until the D substance and the 6-bromohexanoic acid are completely precipitated, performing suction filtration, washing twice with diethyl ether, and drying to obtain the fluorescent probe for identifying mercury ions.
Example 4: a method for preparing the probe of embodiment 1, comprising the steps of:
(1) adding 1.5g of 4-bromobenzaldehyde into 15mL of ethanol to obtain a substance A;
(2) adding 1.5g of 2-acetylpyridine, 1.5g of potassium hydroxide and 20mL of ammonia water into 20mL of ethanol to obtain a substance B;
(3) mixing the A substance and the B substance, stirring at 5 deg.C for 1h, refluxing at 90 deg.C for 10h, cooling to room temperature, stirring for 60min, filtering the precipitate, and recrystallizing in acetic acid to obtain C substance;
(4) to 1000mg of substance C were mixed 350mg of 4-pyridylethylene, 70mg of palladium acetate, 250mg of triphenylphosphine and 25cm3Triethylamine, sealing the mixture in N2Reacting at 120 ℃ for 65 hours in a high-pressure reaction bottle under the atmosphere, dissolving the product in chloroform, washing the organic phase with distilled water for 4 times, washing the organic phase with saturated saline water for 4 times, drying the organic phase with anhydrous magnesium sulfate for 2 hours, then spin-drying the organic phase, and recrystallizing the organic phase with ethanol to obtain a D substance;
(5) and adding the D substance into N, N-dimethylformamide for dissolving, then adding 6-bromohexanoic acid, controlling the mass ratio of the D substance to the 6-bromohexanoic acid to be 1:1, heating to 85 ℃, reacting for 30 hours, adding diethyl ether into the reaction solution until the D substance and the 6-bromohexanoic acid are completely precipitated, performing suction filtration, washing twice with diethyl ether, and drying to obtain the fluorescent probe for identifying mercury ions.
Example 5: a fluorescent probe for recognizing mercury ions is prepared through dissolving probe in DMSO, diluting with secondary water to obtain the fluorescent probe with concentration of 1.00X 10-5mol·L-1Then dropping the sample to be identified into the reagent, using 365nm as the excitation wavelength, when the sample to be identified is added and Hg is identified2+Fluorescence of the reagentThe maximum emission wavelength was blue-shifted from 520nm to 473nm, demonstrating a discriminating effect.
Claims (9)
1. A fluorescent probe for identifying mercury ions is characterized in that the molecular formula is as follows: c34H31BrN4O2The 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) dissolving 4-bromobenzaldehyde in ethanol to obtain a substance A;
(2) dissolving 2-acetylpyridine, potassium hydroxide and ammonia water in ethanol to obtain a substance B;
(3) mixing the substance A and the substance B, stirring for 1-3 h at 0-5 ℃, refluxing for 10-30h at 70-90 ℃, cooling to room temperature, stirring for 30-60 min, filtering the precipitate, and recrystallizing in acetic acid to obtain a substance C;
(4) adding the C substance, 4-pyridine ethylene, palladium acetate and triphenylphosphine into triethylamine for mixing, and sealing the mixture in N2Reacting for 65-75 h at 100-120 ℃ in a high-pressure reaction bottle in the atmosphere, dissolving the product in chloroform, then spin-drying, and recrystallizing with ethanol to obtain a substance D;
(5) and adding the D into N, N-dimethylformamide for dissolving, then adding 6-bromohexanoic acid, heating to 75-85 ℃, reacting for 30-40h, adding diethyl ether into the reaction solution until the reaction solution is completely precipitated, performing suction filtration, washing twice with diethyl ether, and drying to obtain the fluorescent probe for identifying mercury ions.
3. The method for preparing a fluorescent probe for identifying mercury ions according to claim 2, wherein: the method of claim 2, wherein the concentration of ethanol in the steps (1), (2) and (4) is more than 95%.
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 4-bromobenzaldehyde is added into each 15mL of ethanol; in the step (2), 1 to 1.5g of 2-acetylpyridine, 0.5 to 1.5g of potassium hydroxide and 10 to 20mL of ammonia water are added into each 20mL of ethanol.
5. The method for preparing a fluorescent probe for identifying mercury ions according to claim 2, wherein: in the step (4), every 1000mg of the substance C is mixed with 250-350mg of 4-pyridine ethylene, 50-70mg of palladium acetate, 150-250mg of triphenylphosphine and 15-25cm3Triethylamine; before spin-drying, the organic phase is washed with distilled water for 2-4 times, then washed with saturated saline for 2-4 times, and dried over anhydrous magnesium sulfate for 0.5-2 h.
6. The method for preparing a fluorescent probe for identifying mercury ions according to claim 2, wherein: in the step (5), the quantity ratio of the D substance to the 6-bromohexanoic acid substance is 1: 1.
7. The method for identifying a fluorescent probe for identifying mercury ions according to claim 1, wherein: dissolving a probe in DMSO, diluting with secondary water to obtain a fluorescent reagent, 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.
8. The method for identifying a fluorescent probe for mercury ions according to claim 7, wherein: the concentration of the probe in the fluorescent reagent is 10-5mol.L-1。
9. The method for identifying a fluorescent probe for mercury ions according to claim 7, wherein: the wavelength of the fluorescence excitation is 365nm, and when a sample to be identified is added and mercury ions are identified, the maximum fluorescence emission wavelength of the reagent is blue-shifted from 520nm to 473 nm.
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