CN115057875B - Near-infrared two-region methyl mercury ion detection probe and preparation method and application thereof - Google Patents
Near-infrared two-region methyl mercury ion detection probe and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a near-infrared two-region methyl mercury ion detection probe and preparation and application thereof. Dissolving the near infrared two-region fluorescent dye in dichloromethane, dropwise adding an acyl chloride reagent, carrying out reflux reaction, and cooling to obtain an acyl chloride intermediate; dissolving an acyl chloride intermediate in tetrahydrofuran, adding a sodium sulfide aqueous solution, stirring for reaction, regulating the reaction solution to be neutral, carrying out suction filtration, completely dissolving filter residues in dichloromethane, and drying; and (3) performing silica gel column chromatography on the obtained solid to obtain the near infrared two-zone methyl mercury ion detection probe. The detection probe is used for detecting methyl mercury ions. The detection probe belongs to an activated probe, and the emission wavelength is in a near infrared two-region, so that the interference of complex water sample detection can be greatly reduced, and the detection precision is improved; the detection limit of the methyl mercury ions can reach the nanomole level.
Description
Technical Field
The invention belongs to the technical field of chemical analysis and detection, and relates to an activatable near infrared two-zone methyl mercury ion detection probe and a preparation method and application thereof.
Background
Mercury, one of the most toxic heavy metals in the environment, is converted in nature into more toxic organic mercury. Methylmercury (MeHg) + ) Is a common form of organic mercury and exhibits higher biotoxicity than inorganic mercury. Methyl mercury exists in the ecological environment, is transmitted through an aquatic food chain, is enriched in a human body, and is mainly accumulated in kidney and nerve tissues after entering the human body. "hydrolosis" demonstrates the fatal risk of methylmercury to human health. The rich organics in the water body can accelerate the methylation process of mercury. Therefore, the development of the probe for detecting the methyl mercury has great significance in the aspects of environmental management, social health and the like.
Currently, the detection of methylmercury is mainly performed by chromatographic systems (such as gas chromatography, high performance liquid chromatography and capillary electrophoresis) in combination with different element-specific detectors (such as inductively coupled plasma mass spectrometry, cold vapor atomic absorption spectrometry and atomic emission spectrometry). These methods are limited in application due to the expensive instrumentation, complex analysis procedures, and the need for specialized personnel. Compared with the detection method, the fluorescence detection method is simple and convenient, and has outstanding advantages in the aspects of sensitivity, selectivity, response time, field measurement and the like. Groundwater is a complex environment and contains various organic matters and biological samples, and near infrared two-region fluorescence can effectively avoid interference of fluorescence emission of the organic matters in a complex water sample, so that detection accuracy is greatly improved. Therefore, the development of a novel high-efficiency methyl mercury ion detection probe, in particular to near infrared two-region fluorescence emission, has important significance.
Disclosure of Invention
The invention aims to provide an activatable and efficient near infrared two-zone methyl mercury ion detection probe.
The second object of the present invention is to provide a method for preparing the above detection probe.
The third object of the invention is to provide an application of the detection probe in methyl mercury ion detection.
In order to achieve the above purpose, the invention adopts the following technical scheme: a near infrared two-region (NIR-II) methyl mercury ion detection probe has the following structural formula:
the second technical scheme adopted by the invention is as follows: the preparation method of the detection probe comprises the following steps:
1) Taking near infrared two-region fluorescent dye (compound 1) and acyl chloridizing reagent according to the molar ratio of 1:3-6, and taking dichloromethane according to the proportion that 10-20L dichloromethane is needed for 1mol near infrared two-region fluorescent dye; adding the near infrared two-region fluorescent dye into dichloromethane, and stirring until the near infrared two-region fluorescent dye is completely dissolved to obtain a mixed solution; stirring the mixed solution at the temperature of 0-5 ℃, dropwise adding an acyl chloride reagent, heating to the temperature of 20-40 ℃ after the dropwise adding is completed, carrying out reflux reaction for 2-8 h, changing the color of the solution from green to blue, naturally cooling to room temperature, and removing the solvent under reduced pressure to obtain an acyl chloride intermediate (compound 2);
the acyl chloride reagent adopts thionyl chloride, oxalyl chloride or phosphorus oxychloride.
2) Taking the acyl chloride intermediate, tetrahydrofuran and sodium sulfide aqueous solution respectively according to the proportion that 10-20L of tetrahydrofuran and 2.5-5L of sodium sulfide aqueous solution with the molar concentration of 2M are needed for 1mol of the acyl chloride intermediate;
completely dissolving an acyl chloride intermediate in tetrahydrofuran, adding a sodium sulfide aqueous solution, stirring at a temperature of 20-40 ℃ for reaction for 4-12 h, changing the color of the reaction solution from blue to brown, regulating the reaction solution to be neutral by using a saturated sodium bicarbonate solution to obtain a suspension, filtering the suspension, collecting filter residues, completely dissolving the filter residues in dichloromethane, drying the filter residues by using anhydrous sodium sulfate, and removing the solvent under reduced pressure; separating and purifying the obtained solid by silica gel column chromatography (200-300 meshes), wherein the eluent is petroleum ether and ethyl acetate (volume ratio V) Petroleum ether ︰V Acetic acid ethyl ester =20:1) to prepare a near infrared two-zone methyl mercury ion detection probe (compound 3).
The synthetic route of the preparation method is as follows:
the preparation method of the invention is based on a near infrared two-region cyanine dye skeleton, and utilizes the strong combination between methyl mercury and sulfur atoms to prepare an activatable NIR-II methyl mercury ion detection probe (compound 3). The detection probe contains a monothiospirolactone group in a rhodamine structure, and after being combined with methyl mercury, the probe undergoes a unique transformation from a non-fluorescent thiolactone form compound 3 to a near infrared two-region fluorescent ring-opening form compound 1. Thus, methyl mercury ions can be identified and quantitatively detected from the change in the fluorescence intensity of compound 3.
The detection principle of the detection probe of the invention is as follows:
the third technical scheme adopted by the invention is as follows: the application of the detection probe in the detection of methyl mercury ions comprises the following steps:
1) The following solutions were first prepared:
preparing a buffer solution: weighing 2.9789 g, dissolving 4-hydroxyethyl piperazine ethane sulfonic acid (HEPES) in 200 mL secondary water, adjusting the pH value to 7.4 by using sodium hydroxide solution with the molar concentration of 0.5M, transferring into a 250 mL volumetric flask, and fixing the volume to obtain HEPES buffer solution with the molar concentration of 50 mM (pH=7.4);
dissolving the compound 3 in dimethyl sulfoxide to prepare a first mother solution with the molar concentration of 2.0 mM;
dissolving MeHgCl in secondary water to prepare a second mother solution with the molar concentration of 2.5 and mM;
will NaCl, KCl, caCl 2 、CuCl 2 ·H 2 O、SnCl 2 ·2H 2 O、CrCl 3 ·6H 2 O、PbCl 2 、MgCl 2 、ZnCl 2 、CdCl 2 ·2.5H 2 O、NiCl 2 ·6H 2 O、FeCl 3 ·6H 2 O、MnCl 2 ·4H 2 O is respectively dissolved in secondary water to prepare different metal ion mother solutions, and the molar concentration of all the metal ion mother solutions is 2.5 and mM.
2) Preparing a HEPES buffer solution with a molar concentration of 50 mM and absolute ethyl alcohol into a diluent according to a volume ratio of 1:1; then, diluting the first mother solution and all the metal ion mother solutions to the required concentration by using a diluent;
3) The following tests were performed:
and i) detecting the diluted first mother liquor, and measuring the ultraviolet absorption and fluorescence spectrum of the compound 3.
Ii) adding the second mother liquor into the diluted first mother liquor, and measuring the ultraviolet absorption and fluorescence spectrum of the compound 3 after the reaction with the methyl mercury ions.
Iii) adding the second mother liquor into the diluted first mother liquor, and respectively measuring the ultraviolet absorption spectrum of the solution after the reaction of the compound 3 and the methylmercury ion at different moments.
Iv) respectively taking second mother liquor with different volumes in HEPES buffer solution and ethanol (volume ratio is 1:1) system (diluent), adding the second mother liquor with different volumes into first mother liquor (2 mL) with concentration of 2 mu M after dilution, measuring fluorescence spectrum of solution after reaction of compound 3 and methyl mercury ions with different concentrations, and preparing a working curve according to the relation between the intensity of fluorescence emission peak and the concentration of the methyl mercury ions.
V) taking different metal ion mother solutions with the same volume, then adding the diluted first mother solution with the same volume into each metal ion mother solution, and measuring the fluorescence spectra of the compound 3 and different metal ions.
Vi) taking different metal ion mother solutions with the same volume, then adding the diluted first mother solution with the same volume and the second mother solution with the same volume into each metal ion mother solution, and respectively measuring fluorescence spectra of the compound 3 after reaction with methyl mercury ions and coexisting different metal ions.
The detection probe has the beneficial effects that:
1) In the preparation process of the detection probe, the response group can be modified according to a specific target, and the preparation method is strong in expansibility.
2) The detection probe belongs to an activated probe, and the emission wavelength is in a near infrared two-region, so that the interference of complex water sample detection can be greatly reduced, and the detection precision is improved.
3) The detection limit of the methyl mercury ions is low, and the nanomolar level can be achieved.
4) The recognition sensitivity to methyl mercury ions is high, the specificity is strong, and the anti-interference performance is good.
Drawings
FIG. 1 is a UV spectrum and a fluorescence spectrum of the detection probe prepared in example 1 in the presence of methylmercury ion.
FIG. 2 is a graph showing the change in the absorption intensity at 856 and nm of the detection probe prepared in example 1 with time in the presence of methylmercury ion.
FIG. 3 is a graph showing fluorescence spectra of the detection probes prepared in example 1 in response to different concentrations of methylmercury ions (0-200 nM).
FIG. 4 is a linear plot of fluorescence intensity at 950. 950 nm versus methyl mercury ion concentration for the detection probes prepared in example 1 in response to different concentrations of methyl mercury ions (0-200. 200 nM).
FIG. 5 is a fluorescence spectrum showing the selectivity and anti-interference performance of the detection probe prepared in example 1 to methyl mercury ions.
Detailed Description
The invention is described in further detail below with reference to the drawings and the detailed description.
Example 1
An NIR-II methylmercury ion detection probe (compound 3) was synthesized, and the synthetic route of the NIR-II methylmercury ion detection probe was as follows:
the preparation method comprises the following steps:
adding 0.5mmol (435.9 mg) of the near infrared two-region fluorescent dye (compound 1) into 10 mL anhydrous dichloromethane, and stirring until the near infrared two-region fluorescent dye is completely dissolved to obtain a mixed solution; the mixture was stirred at 0℃and 2.5 mmol (0.23. 0.23 mL) of phosphorus oxychloride was added dropwise, after the completion of the addition, the temperature was raised to 35℃and the mixture was refluxed for 4 hours, the color of the solution was changed from green to blue, and the mixture was naturally cooled to room temperature and the solvent was removed under reduced pressure to give an acid chloride intermediate (compound 2). Without further treatment, 0.5mmol of the acid chloride intermediate was dissolved directly in 10 mL tetrahydrofuran and 2.5 mL molar sodium sulphide in water was added; stirring at 20deg.C for 12 h, regulating the color of the reaction solution from blue to brown, regulating the reaction solution to neutral with saturated sodium bicarbonate solution, precipitating to obtain suspension, vacuum filtering, dissolving the residue in dichloromethane, and collecting the filtrateDried over sodium sulfate and the solvent was removed under reduced pressure. Separating and purifying the obtained solid by silica gel column chromatography (200-300 meshes), wherein the eluent is petroleum ether and ethyl acetate (volume ratio V) Petroleum ether ︰V Acetic acid ethyl ester =20:1) to produce 165.3 mg of reddish-brown near-infrared two-zone methyl mercury ion detection probe (compound 3) in 42% yield.
Example 1 the nuclear magnetism and mass spectrum of the resulting compound 3 were characterized as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 7.81-7.69 (m, 3H), 7.49-7.39 (m, 2H), 7.36-7.30 (m, 3H), 7.28 (d, J = 6.8 Hz, 1H), 7.21 (d, J = 7.9 Hz, 1H), 6.95 (s, 1H), 6.69 (s, 1H), 6.50 (d, J = 8.9 Hz, 1H), 6.34-6.25 (m, 2H), 6.25-6.16 (m, 2H), 3.50-3.33 (m, 2H), 3.32-3.08 (m, 8H), 2.70-2.45 (m, 2H), 2.14-2.03 (m, 1H), 1.85-1.70 (m, 2H), 1.65-1.55 (m, 2H),1.37-1.23 (m, 3H), 1.23-0.93 (m, 15H), 0.83-0.71 (m, 1H). 13 C NMR (101 MHz, CDCl 3 ) δ 197.88, 156.31, 152.09, 150.05, 148.55, 146.87, 145.97, 137.98, 136.59, 134.53, 134.10, 132.91, 129.72, 129.61, 128.83, 128.56, 128.33, 126.75, 124.95, 123.66, 122.81, 120.04, 110.79, 108.60, 107.93, 106.83, 104.62, 102.71, 102.65, 100.53, 98.49, 97.69, 66.85, 55.93, 54.65, 44.55, 42.34, 42.19, 29.81, 27.88, 27.31, 27.23, 26.13, 24.81, 22.73, 22.54, 22.37, 12.79, 11.88, 11.33. MS (ESI): calcd for [C 51 H 53 N 3 O 3 S] + 787.38, found 787.27.
example 1 uv and fluorescence spectrometry of compound 3 in the presence of methylmercury:
the compound 3 prepared in example 1 was dissolved in dimethyl sulfoxide to obtain a probe mother liquor having a molar concentration of 2.0. 2.0mM, and the probe mother liquor was diluted with a diluent to obtain a probe solution in which the molar concentration of the compound 3 was 5. Mu.M, and the ultraviolet spectrum and the fluorescence spectrum of the probe solution were measured, respectively. Taking 2mL of the probe solution, adding 4 mu L of a second mother solution to obtain a diluted solution, wherein the molar concentration of methyl mercury ions in the diluted solution is 5 mu M, and respectively measuring the ultraviolet spectrum and the fluorescence spectrum of the diluted solution to obtain the detection probe shown in figure 1 and the ultraviolet spectrum and the fluorescence spectrum of the detection probe in the presence of the methyl mercury ions. Since compound 3 is a thiolactone type, the probe does not have significant absorption in the near infrared region. After adding methyl mercury ions, the probe is converted from the thiolactone form of the compound 3 to the ring-opened form of the compound 1 under the strong bonding action between the methyl mercury and sulfur atoms, so that the absorption of the diluted liquid in the wavelength range of 700-900 nm is greatly enhanced. With 808 and nm as excitation wavelengths, compound 3 has a maximum emission wavelength of 950 nm in the presence of methylmercury. The probe hardly emits fluorescence under the excitation of 808 and nm wavelength laser, which indicates that the detection probe belongs to an activated probe.
Detection of methylmercury ion by Compound 3 prepared in example 1:
the absorption spectra of the 2mL probe solution were measured at different times by adding 4. Mu.L of the second mother liquor and immediately starting the timing, as shown in FIG. 2. As the reaction time increases, the absorption intensity at 856, 856 nm increases gradually, and at about 200, 200 s the absorption intensity no longer increases and reaches equilibrium, indicating that the detection probes of the present invention have sufficient response sensitivity.
The compound 3 produced in example 1 was dissolved in dimethyl sulfoxide to obtain a probe mother liquor having a molar concentration of 2.0. 2.0mM, and the probe mother liquor was diluted with a diluent to obtain a probe liquor having a molar concentration of 2. Mu.M of the compound 3. Eight parts of MeHgCl were taken and dissolved in secondary water to give eight parts of methylmercury ion solutions with molar concentrations of 0nM, 25nM, 50nM, 75nM, 100nM, 125nM, 150nM and 200nM, respectively. Eight parts of the probe liquid are taken, each part of the probe liquid is 2mL, one part of the probe liquid is added with one part of methyl mercury ion solution, the mixture is uniformly shaken, and after three minutes of standing, the fluorescence spectrum of the system in the wavelength range of 900-1200 nm is recorded on a fluorescence spectrometer (excited by using 808 nm laser), so as to obtain the fluorescence spectrum diagram shown in figure 3. It can be observed that as the methyl mercury ion concentration increases, the fluorescence of the system gradually increases. The fluorescence intensity at 950, 950 nm was plotted on the ordinate and the methyl mercury ion concentration on the abscissa, and a working curve of the detection probe of the present invention shown in fig. 4 was fitted, and the actual detection limit of the detection probe for methyl mercury ions was 25nM (5.4 ppb). As can be seen in FIG. 4, the system fluoresces at 950 nmThe light intensity and the concentration of methyl mercury ion (0-200 nM) have good linear relation (R) 2 = 0.9963). From the slope of the fitted line, the detection limit of compound 3 on methyl mercury ions can be calculated to be about 14 nM (3.0 ppb) by the formula 3σ/k (σ: standard deviation of detection values of 11 blank samples, k: slope of fitted line). The experimental result shows that the detection probe has enough detection sensitivity and can meet the requirement of detecting methyl mercury ions in groundwater.
Example 1 test probe selectivity and anti-interference experiment for different metal ions:
thirteen parts of probe solution were taken, each 2mL by volume. The mother solutions of different metal ions (Na) were taken at molar concentrations of 2.5 and mM, respectively + 、K + 、Ca 2+ 、Cu 2+ 、Sn 2+ 、Cr 3+ 、Pb 2+ 、Mg 2+ 、Zn 2+ 、Cd 2+ 、Ni 2+ 、Fe 3+ 、Mn 2+ ) 4. Mu.L each. One part of the probe solution was added with a metal ion mother solution, shaken well, left for three minutes, and then a signal of fluorescence intensity at 950 and nm was recorded on a fluorescence spectrometer. Subsequently, 4. Mu.L of MeHgCl mother liquor having a molar concentration of 2.5. 2.5 mM was added to the system containing the different metal ions, and after shaking and standing for three minutes, a signal of fluorescence intensity at 950. 950 nm was recorded on a fluorescence spectrometer. The molar equivalent ratio of the compound 3, the methylmercury ion and the different metal ions is 1:1:1. The fluorescence intensity at 950 nm for each experimental group is shown in FIG. 5 (M in the figure + Representing different metal ions), the experimental results obtained demonstrate that compound 3 can specifically recognize and detect MeHg + The interference of other ions is negligible, which indicates that the detection probe has good selectivity and anti-interference performance on methyl mercury ions.
Example 2
Adding 0.5mmol (435.9 mg) of the near infrared two-region fluorescent dye (compound 1) into 10 mL anhydrous dichloromethane, and stirring until the near infrared two-region fluorescent dye is completely dissolved to obtain a mixed solution; 0. stirring the mixture at a temperature of below DEG C, and dripping 2.5 mmol (0.23. 0.23 mL) of phosphorus oxychloride, and lifting after the dripping is completedReflux is carried out for 4 hours at the temperature of 35 ℃, the color of the solution is changed from green to blue, the solution is naturally cooled to room temperature, and the solvent is removed under reduced pressure, thus obtaining the acyl chloride intermediate (compound 2). Directly dissolving an acyl chloride intermediate in 10 mL tetrahydrofuran without further treatment, and adding 2.5 mL concentration of 2M sodium sulfide aqueous solution; the mixture was stirred at 20℃for 6h, the reaction mixture changed from blue to brown. After the reaction, the reaction solution is adjusted to be neutral by saturated sodium bicarbonate solution, and precipitates are separated out to obtain suspension, the suspension is subjected to suction filtration, filter residues are dissolved in dichloromethane, and the solution is dried by anhydrous sodium sulfate and finally the solvent is removed under reduced pressure. The obtained solid is separated and purified by silica gel column chromatography (200-300 meshes) to prepare the reddish brown near infrared two-zone methyl mercury ion detection probe (compound 3) 149.5 mg with the yield of 38 percent. The eluent is petroleum ether and ethyl acetate (volume ratio V) Petroleum ether ︰V Acetic acid ethyl ester =20:1).
Example 2 the nuclear magnetism and mass spectrum of the resulting compound 3 were characterized as follows: 1 H NMR (400 MHz, CDCl 3 ) δ 7.81-7.69 (m, 3H), 7.49-7.39 (m, 2H), 7.36-7.30 (m, 3H), 7.28 (d, J = 6.8 Hz, 1H), 7.21 (d, J = 7.9 Hz, 1H), 6.95 (s, 1H), 6.69 (s, 1H), 6.50 (d, J = 8.9 Hz, 1H), 6.34-6.25 (m, 2H), 6.25-6.16 (m, 2H), 3.50-3.33 (m, 2H), 3.32-3.08 (m, 8H), 2.70-2.45 (m, 2H), 2.14-2.03 (m, 1H), 1.85-1.70 (m, 2H), 1.65-1.55 (m, 2H),1.37-1.23 (m, 3H), 1.23-0.93 (m, 15H), 0.83-0.71 (m, 1H). 13 C NMR (101 MHz, CDCl 3 ) δ 197.88, 156.31, 152.09, 150.05, 148.55, 146.87, 145.97, 137.98, 136.59, 134.53, 134.10, 132.91, 129.72, 129.61, 128.83, 128.56, 128.33, 126.75, 124.95, 123.66, 122.81, 120.04, 110.79, 108.60, 107.93, 106.83, 104.62, 102.71, 102.65, 100.53, 98.49, 97.69, 66.85, 55.93, 54.65, 44.55, 42.34, 42.19, 29.81, 27.88, 27.31, 27.23, 26.13, 24.81, 22.73, 22.54, 22.37, 12.79, 11.88, 11.33. MS (ESI): calcd for [C 51 H 53 N 3 O 3 S] + 787.38, found 787.27, example 3
Taking the near infrared two-region fluorescent dye and thionyl chloride respectively according to the molar ratio of 1:3, and then taking 1mol of the near infrared two-region fluorescent dyeTaking dichloromethane according to the proportion of 10L of dichloromethane; adding the near infrared two-region fluorescent dye into dichloromethane, and stirring until the near infrared two-region fluorescent dye is completely dissolved to obtain a mixed solution; stirring the mixed solution at the temperature of 0 ℃, dropwise adding thionyl chloride, heating to the temperature of 20 ℃ after the dropwise adding is completed, carrying out reflux reaction on the mixture for 8h, changing the color of the solution from green to blue, naturally cooling to room temperature, and removing the solvent under reduced pressure to obtain an acyl chloride intermediate; taking the acyl chloride intermediate, tetrahydrofuran and sodium sulfide aqueous solution respectively according to the proportion that 10L tetrahydrofuran and 3.5L sodium sulfide aqueous solution with the molar concentration of 2M are needed for 1mol of the acyl chloride intermediate; the acyl chloride intermediate is completely dissolved in tetrahydrofuran, then sodium sulfide aqueous solution is added, stirring reaction is carried out for 4 hours at the temperature of 40 ℃, the color of the reaction solution is changed from blue to brown, saturated sodium bicarbonate solution is used for regulating the reaction solution to be neutral, suspension is obtained, the suspension is filtered, filter residues are collected, the filter residues are completely dissolved in dichloromethane, anhydrous sodium sulfate is used for drying, and the solvent is removed under reduced pressure; separating and purifying the obtained solid by silica gel column chromatography (200-300 meshes), wherein the eluent is petroleum ether and ethyl acetate (volume ratio V) Petroleum ether ︰V Acetic acid ethyl ester =20:1) to prepare a near infrared two-zone methyl mercury ion detection probe.
Example 4
Taking the near infrared two-region fluorescent dye and thionyl chloride respectively according to the molar ratio of 1:6, and taking dichloromethane according to the proportion that 15L dichloromethane is needed for 1mol of the near infrared two-region fluorescent dye; adding the near infrared two-region fluorescent dye into dichloromethane, and stirring until the near infrared two-region fluorescent dye is completely dissolved to obtain a mixed solution; stirring the mixed solution at the temperature of 0 ℃, dropwise adding thionyl chloride, heating to the temperature of 40 ℃ after the dropwise adding is completed, carrying out reflux reaction on the mixture for 5 h, changing the color of the solution from green to blue, naturally cooling to room temperature, and removing the solvent under reduced pressure to obtain an acyl chloride intermediate; respectively taking the acyl chloride intermediate, tetrahydrofuran and sodium sulfide aqueous solution according to the proportion that 1mol of the acyl chloride intermediate needs 15L of tetrahydrofuran and 5L of sodium sulfide aqueous solution with the molar concentration of 2M; the acyl chloride intermediate is completely dissolved in tetrahydrofuran, then added with sodium sulfide aqueous solution and stirred for reaction for 8 hours at the temperature of 30 ℃, the color of the reaction solution changes from blue to brown, and saturated sodium bicarbonate solution is used for regulating the reactionThe obtained solution is neutral to obtain suspension, the suspension is filtered, filter residues are collected, the filter residues are completely dissolved in dichloromethane, and the solution is dried by anhydrous sodium sulfate and removed under reduced pressure; separating and purifying the obtained solid by silica gel column chromatography (200-300 meshes), wherein the eluent is petroleum ether and ethyl acetate (volume ratio V) Petroleum ether ︰V Acetic acid ethyl ester =20:1) to prepare a near infrared two-zone methyl mercury ion detection probe.
Claims (5)
1. The near infrared two-region methyl mercury ion detection probe is characterized by comprising the following structural formula:
2. a method for preparing the near infrared two-zone methyl mercury ion detection probe as claimed in claim 1, which is characterized by comprising the following steps:
1) Taking the near infrared two-region fluorescent dye and the acyl chloridizing reagent according to the molar ratio of 1:3-6, and taking dichloromethane according to the proportion that 10-20L dichloromethane is needed for 1mol of the near infrared two-region fluorescent dye;
adding the near infrared two-region fluorescent dye into dichloromethane, and stirring until the near infrared two-region fluorescent dye is completely dissolved to obtain a mixed solution; stirring the mixed solution at the temperature of 0-5 ℃, dropwise adding an acyl chloride reagent, heating to the temperature of 20-40 ℃ after the dropwise adding is completed, carrying out reflux reaction for 2-8 h, naturally cooling to the room temperature, and removing the solvent under reduced pressure to obtain an acyl chloride intermediate;
the structural formula of the near infrared two-region fluorescent dye is as follows:
the structural formula of the acyl chloride intermediate is as follows:
taking the acyl chloride intermediate, tetrahydrofuran and sodium sulfide aqueous solution respectively according to the proportion that 10-20L of tetrahydrofuran and 2.5-5L of sodium sulfide aqueous solution with the molar concentration of 2M are needed for 1mol of the acyl chloride intermediate;
completely dissolving an acyl chloride intermediate in tetrahydrofuran, adding a sodium sulfide aqueous solution, stirring at 20-40 ℃ for reaction for 4-12 h, regulating the reaction liquid to be neutral to obtain a suspension, carrying out suction filtration, completely dissolving filter residues in dichloromethane, drying with anhydrous sodium sulfate, and removing the solvent under reduced pressure; separating and purifying the obtained solid by using a silica gel column chromatography to prepare a near infrared two-zone methyl mercury ion detection probe;
the synthetic route of the near infrared two-zone methyl mercury ion detection probe is as follows:
3. the method for preparing a near infrared two-zone methyl mercury ion detection probe according to claim 2, wherein in the step 1), thionyl chloride, oxalyl chloride or phosphorus oxychloride is adopted as an acyl chloride reagent.
4. The method for preparing a near infrared two-zone methyl mercury ion detection probe according to claim 2, wherein in the step 2), sodium bicarbonate is used to adjust the reaction solution to be neutral.
5. Use of the near infrared two-region methylmercury ion detection probe according to claim 1 in methylmercury ion fluorescence detection.
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