CN107098852B - Di (2-methylpyridine) amine modified pyrene derivative fluorescent probe and synthetic method and application thereof - Google Patents
Di (2-methylpyridine) amine modified pyrene derivative fluorescent probe and synthetic method and application thereof Download PDFInfo
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Abstract
The invention discloses a pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine and a synthesis method and application thereof, wherein the structural formula of the fluorescent probe is shown in the specification
Wherein n is 2, 3 or 4. The fluorescent probe connects a fluorescent reporter group pyrene with a metal ion receptor through a flexible connecting arm, and realizes the regulation and control of 13 metal ions Cu by utilizing the regulation and control function of a sodium dodecyl sulfate assembly and the combination function of the receptor2+、Co2+、Ni2+、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+The discrimination detection of (1). The fluorescent probe has the advantages of good chemical stability, high response speed, high sensitivity, good distinguishability, small sample consumption, simple data acquisition and the like, and can be used for measuring metal ions in real time and on line.
Description
Technical Field
The invention belongs to the technical field of metal ion detection, and particularly relates to a bis (2-methylpyridine) amine modified pyrene derivative fluorescent probe for detecting metal ions in a water phase and a synthesis method thereof.
Background
The heavy metal ion permeation has high toxicity and is difficult to remove in various aspects of production and life, so the detection of the heavy metal ion is concerned by people. The method can accurately and quickly detect and identify the heavy metal ions in the environment, and has extremely important significance for food safety, ecological environment improvement and human health. However, the use of conventional "lock-and-key" type highly selective sensors cannot meet the detection requirement of complex samples, and therefore, the development of high-throughput detection means capable of effectively analyzing complex samples is urgently needed.
The sensor array is developed based on understanding of the working principle of an animal olfactory system and consists of a plurality of sensing units with interactive responsiveness, each sensing unit in the array can respond to different analytes in different degrees, and each sensing unit can respond to the same analyte in different degrees, so that a characteristic fingerprint spectrum aiming at a specific analyte can be formed, and the distinguishing and the identification of multiple analytes are realized. The traditional sensor array mostly utilizes a large number of sensing units to realize interactive response, and has good fingerprint spectrum identification capability, but the problems of large sample consumption, complex data acquisition and processing process and the like are often caused. Therefore, a single fluorescence sensing system based on multi-wavelength interactive response is developed, the single fluorescence sensing system also has fingerprint spectrum identification capability, the consumption of samples is greatly reduced, data acquisition of the same analyte can be realized through one-time scanning, the data acquisition process is simplified, and the single fluorescence sensing system gradually becomes a new research hotspot.
Disclosure of Invention
The invention aims to provide a pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine and having the advantages of good distinguishability, wide test range, small sample consumption, simple data acquisition and the like with the aid of a Sodium Dodecyl Sulfate (SDS) aggregate, and provide a synthesis method and application for the fluorescent probe.
The structural formula of the pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine used for solving the technical problems is shown as follows:
wherein n is 2, 3 or 4.
The preparation method of the pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine comprises the following steps:
1. synthesis of pyrenesulfonyl derivatives
Under the conditions of inert atmosphere and ice bath, dropwise adding a trichloromethane solution of pyrenesulfonyl chloride into a trichloromethane solution of diamino oxygen-containing alkane, stirring at room temperature for reacting for 2-8 hours after dropwise adding, and separating and purifying to obtain the pyrenesulfonyl derivative with the structural formula as follows:
the diamino oxygen-containing alkane is 1, 8-diamino-3, 6-dioxyoctane, 3,6, 9-trioxaundecane-1, 11-diamine or 3,6,9, 12-tetraoxahexadecane-1, 16-diamine.
2. Synthesis of bis (2-methylpyridine) amine derivatives
Under the protection of nitrogen, dissolving 2-chloromethylpyridine hydrochloride in ultrapure water, sequentially adding aniline, sodium hydroxide and hexadecyltrimethylammonium chloride, stirring at room temperature for 24 hours, and separating and purifying to obtain di (2-methylpyridine) aniline; then under the ice bath condition, dripping a dimethyl formamide solution of bis (2-methylpyridine) aniline into dimethyl formamide of phosphorus oxychloride, heating at 90 ℃ for reaction for 3 hours after dripping, pouring the reaction solution into water after the reaction is finished, and then using K to react2CO3Neutralizing until the pH value is 6-8, separating and purifying to obtain a di (2-methylpyridine) amine derivative with the structural formula as follows:
3. synthesis of di (2-methylpyridine) amine modified pyrene derivative fluorescent probe
Adding pyrenesulfonyl derivative and di (2-methylpyridine) amine derivative into dichloromethane-methanol mixture at volume ratio of 2:1Adding anhydrous sodium sulfate into the mixed solution, stirring at room temperature for 12 hours, filtering out the sodium sulfate, and spin-drying the solvent to obtain an oily substance; the oil was dissolved in methanol at 0 ℃ and sodium borohydride was added, stirred for 45 minutes at room temperature with saturated NaHCO3And (3) quenching the aqueous solution, separating and purifying to obtain the pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine.
In the step 1, the mol ratio of pyrenesulfonyl chloride to diamino oxygen-containing alkane is preferably 1 (8-12).
In the step 2, the molar ratio of the aniline to the 2-chloromethylpyridine hydrochloride, the sodium hydroxide and the hexadecyltrimethylammonium chloride is preferably 1 (1.5-3) to 2-3 (0.02-0.1), and the molar ratio of the di (2-methylpyridine) aniline to the phosphorus oxychloride is preferably 1 (7-8).
In the step 3, the molar ratio of the di (2-methylpyridine) amine derivative to the pyrenesulfonyl derivative, the anhydrous sodium sulfate and the sodium borohydride is preferably 1 (1.1-1.5) to 1 (1-1.3) to 0.3-0.8.
The fluorescent probe is applied to distinguishing and detecting metal ions, wherein the metal ions are Cu2+、Co2+、Ni2 +、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+The specific detection method comprises the following steps:
1. preparing solution
Uniformly mixing a methanol solution of a 2.5mmol/L bis (2-methylpyridine) amine modified pyrene derivative fluorescent probe and a secondary distilled water solution of 5mmol/L sodium dodecyl sulfate to ensure that the concentration of the bis (2-methylpyridine) amine modified pyrene derivative fluorescent probe in the mixed solution is 10 mu mol/L, and taking the mixed solution as a fluorescent probe sensor.
2. Drawing standard classification atlas
Adding different concentrations of known metal ions to the fluorescent probe sensor, measuring fluorescence intensity with a fluorometer, and determining log (I/I) at different emission wavelengths0) And drawing a standard classification map of the metal ions by a principal component analysis data processing method.
3. Detecting a sample to be tested
Measuring the fluorescence intensity of the metal ion sample to be measured by a fluorometer according to the method of the step 2, and calculating log (I/I)0) The value, processing data according to principal component analysis data processing method, can determine Cu by combining standard classification map2+、Co2+、Ni2+、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+The kind of (2).
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention takes chain molecules containing oligomeric ethoxy and secondary amino as hydrophilic connecting arms, introduces a receptor group di (2-methylpyridine) amine which can be specifically combined with metal ions, and prepares the di (2-methylpyridine) amine modified pyrene derivative fluorescent probe, the fluorescent probe takes pyrene which has high fluorescence quantum yield, is sensitive to microenvironment and rich in fluorescence output signals as a report group, has the characteristic of multiple fluorescence emission of monomers and excimer, is expected to endow an aggregation system with multi-wavelength interactive response recognition performance, and provides possibility for creating a novel supramolecular fluorescent sensing system.
2. According to the invention, the bis (2-methylpyridine) amine modified pyrene derivative fluorescent probe is assembled with the anionic surfactant sodium dodecyl sulfate to prepare the supramolecular fluorescent sensor, the fluorescent sensor has good chemical stability and biocompatibility, and has the advantages of multi-wavelength interactive responsiveness, high response speed and good distinguishability, and a single sensing system can be used for carrying out Cu detection on 13 metal ions2+、Co2+、Ni2+、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+The distinguishing and identifying.
3. The synthetic method of the fluorescent probe is simple to operate, has low requirements on equipment, and is suitable for instrumentation.
Drawings
FIG. 1 shows that a pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine prepared in example 1 detects Cu2+Graph of change in fluorescence intensity of the solution.
FIG. 2 shows that the pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine prepared in example 1 detects Co2+Graph of change in fluorescence intensity of the solution.
FIG. 3 shows that the pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine prepared in example 1 detects Ni2+Graph of change in fluorescence intensity of the solution.
FIG. 4 shows that the pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine prepared in example 1 detects Cr3+Graph of change in fluorescence intensity of the solution.
FIG. 5 shows that the pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine prepared in example 1 detects Hg2+Graph of change in fluorescence intensity of the solution.
FIG. 6 shows that the pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine prepared in example 1 detects Fe3+Graph of change in fluorescence intensity of the solution.
FIG. 7 shows that the pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine prepared in example 1 detects Zn2+Graph of change in fluorescence intensity of the solution.
FIG. 8 shows Cd detection by a pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine prepared in example 12+Graph of change in fluorescence intensity of the solution.
FIG. 9 shows that the pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine prepared in example 1 detects Al3+Graph of change in fluorescence intensity of the solution.
FIG. 10 shows the detection of Pb by the fluorescent probe for pyrene derivatives modified by bis (2-methylpyridine) amine prepared in example 12+Graph of change in fluorescence intensity of the solution.
FIG. 11 shows that the pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine prepared in example 1 detects Ca2+Graph of change in fluorescence intensity of the solution.
FIG. 12 is a graph showing the detection of the pyrene derivative fluorescence probe modified with di (2-methylpyridine) amine prepared in example 1Measuring Mg2+Graph of change in fluorescence intensity of the solution.
FIG. 13 shows the detection of Ba by the pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine prepared in example 12+Graph of change in fluorescence intensity of the solution.
FIG. 14 is the log (I/I) of the fluorescence change of the pyrene derivative fluorescence probe modified with di (2-methylpyridine) amine prepared in example 1 at different wavelengths (379, 399, 460, 501nm) for 13 metal ions (concentration 10. mu. mol/L)0) Histogram of values.
FIG. 15 is the log (I/I) of the fluorescence change of the pyrene derivative fluorescence probe modified with di (2-methylpyridine) amine prepared in example 1 at different wavelengths (379, 399, 460, 501nm) for 13 metal ions (concentration 50. mu. mol/L)0) Histogram of values.
FIG. 16 is the log (I/I) of the fluorescence change of the pyrene derivative fluorescence probe modified with di (2-methylpyridine) amine prepared in example 1 at different wavelengths (379, 399, 460, 501nm) for 13 metal ions (concentration 100. mu. mol/L)0) Histogram of values.
FIG. 17 is log (I/I) of FIG. 140) And the data is a standard classification map drawn according to a principal component analysis data processing method.
FIG. 18 is log (I/I) of FIG. 150) And the data is a standard classification map drawn according to a principal component analysis data processing method.
FIG. 19 is log (I/I) of FIG. 160) And the data is a standard classification map drawn according to a principal component analysis data processing method.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
1. Synthesis of pyrenesulfonyl derivatives
Under the conditions of nitrogen protection and ice-bath stirring at the flow rate of 0.6mL/s, adding 1.48g (9.97mmol) of 1, 8-diamino-3, 6-dioxyoctane into a three-neck flask containing 60mL of trichloromethane, then dissolving 0.3g (0.997mmol) of pyrene sulfonyl chloride in 50mL of trichloromethane, dropwise adding into the three-neck flask at the speed of 6 s/drop, stirring at room temperature for reaction for 2 hours after dropwise adding, washing the reaction liquid with saturated salt water for 5-8 times, then drying with anhydrous sodium sulfate overnight, washing with 1mol/L hydrochloric acid, then neutralizing with 3mol/L sodium hydroxide aqueous solution, extracting with trichloromethane after the pH value of the solution is 7, collecting an organic layer, and drying to obtain a pyrene sulfonyl derivative (Py-EOA), wherein the reaction equation is as follows:
2. synthesis of bis (2-methylpyridine) amine derivatives
Under the protection of nitrogen, 1.524g (12mmol) of 2-chloromethylpyridine hydrochloride is dissolved in 2.5mL of ultrapure water, 0.558g (6mmol) of aniline, 3mL of 5mol/L aqueous sodium hydroxide solution and 20mg (0.15mmol) of hexadecyltrimethylammonium chloride are added, the mixture is stirred at room temperature for 24 hours, dichloromethane is used for extraction, the extract is washed with water and dried by anhydrous sodium sulfate, dichloromethane is removed to obtain a crude product, the crude product is purified by column chromatography by using a mixed solvent of dichloromethane and ethyl acetate according to a volume ratio of 4:1 as an eluent, and the obtained beige solid is pure bis (2-methylpyridine) aniline (BPA).
1mL (17mmol) of phosphorus oxychloride was added dropwise to 2mL of dimethylformamide and cooled in an ice bath, and then the solution was stirred for 0.5 hour. Dissolving 0.600g (2.18mmol) of bis (2-methylpyridine) aniline in 1mL of dimethylformamide, placing the solution in a separating funnel, dropwise adding the solution into dimethylformamide containing phosphorus oxychloride, heating the solution at 90 ℃ for reaction for 3 hours after the dropwise addition is finished, pouring the reaction solution into 5mL of water after the reaction is finished, and adding K2CO3Neutralizing until the pH value is 6-8, stirring, extracting with dichloromethane, drying with anhydrous sodium sulfate, and removing an organic solvent to obtain a crude product; and (3) purifying the crude product by using acetone and n-hexane as eluent column chromatography according to the volume ratio of 1:1 to obtain a bis (2-methylpyridine) amine modified pyrene derivative (BPAB), wherein the reaction equation is as follows:
3. synthesis of di (2-methylpyridine) amine modified pyrene derivative fluorescent probe
0.31g (1mmol) of a pyrene derivative modified with di (2-methylpyridine) amine and 0.45g (1.1mmol) of a pyrene sulfonyl derivative were added to 2mL of a mixed solution of dichloromethane and methanol at a volume ratio of 2:1, 0.14g (1mmol) of anhydrous sodium sulfate was further added, the mixture was stirred at room temperature for 12 hours, the sodium sulfate was filtered off, and the solvent was dried by spinning to obtain an oil. The oil was added to 50mL of methanol at 0 deg.C, 0.02g (0.5mmol) of sodium borohydride was added, the mixture was stirred at room temperature for 45 minutes, and the reaction was quenched with saturated NaHCO3The aqueous solution was quenched, methanol was removed under reduced pressure and the residue was dissolved in water. Extracting the water phase with dichloromethane for 3 times, washing the combined organic phase with brine, drying with anhydrous sodium sulfate, filtering, removing the solvent in vacuum to obtain a crude product, and purifying by using a mixed solvent of dichloromethane and methanol in a volume ratio of 8:1 as an eluent column chromatography to obtain the bis (2-methylpyridine) amine modified pyrene derivative fluorescent Probe (PB), wherein the yield is 86%, and the reaction equation is as follows:
the nuclear magnetic data of the pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine are as follows:1H NMR(400MHz,CDCl3,ppm):δ9.04(s,1H),8.66(s,1H),8.56(s,2H),8.18(m,7H),7.58(s,2H),7.20(m,6H),6.67(s,2H),4.77(s,4H),3.95(s,2H),3.67(s,2H),3.45(s,6H),3.08(s,2H),2.89(s,2H)。
example 2
Synthesizing a pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine with the following structural formula:
in the synthesis of pyrenesulfonyl derivative step 1 of example 1, 8-diamino-3, 6-dioxyoctane used was replaced with an equimolar amount of 3,6, 9-trioxaundecane-1, 11-diamine, and the other steps were the same as in example 1 to obtain a bis (2-methylpyridine) amine-modified pyrene derivative fluorescent probe.
Example 3
Synthesizing a pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine with the following structural formula:
in the synthesis pyrene sulfonyl derivative step 1 of example 1, 8-diamino-3, 6-dioxyoctane used was replaced with an equimolar amount of 3,6,9, 12-tetraoxahexadecane-1, 16-diamine, and the other steps were the same as in example 1 to obtain a bis (2-methylpyridine) amine modified pyrene derivative fluorescent probe.
Example 4
Cu differential detection by using bis (2-methylpyridine) amine modified pyrene derivative fluorescent probe of example 12+、Co2+、Ni2 +、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+The detection method comprises the following steps:
1. preparing solution
Uniformly mixing a methanol solution of a 2.5mmol/L bis (2-methylpyridine) amine modified pyrene derivative fluorescent probe and a secondary distilled water solution of 5mmol/L sodium dodecyl sulfate to ensure that the concentration of the bis (2-methylpyridine) amine modified pyrene derivative fluorescent probe in the mixed solution is 10 mu mol/L, and taking the mixed solution as a fluorescent probe sensor.
2. Drawing standard classification atlas
Respectively putting 2.5mL of fluorescent probe sensors in cuvettes, and measuring the fluorescence intensity I of the fluorescent probes by using a single photon fluorescence spectrometer (FS5, Edinburgh)0The light source is a 150W xenon lamp, the excitation wavelength of the sample is 351nm, and the excitation and emission slits are 5.5 nm and 1.3nm respectively. Respectively dropwise adding 2.5 × 10-3mol/L of Cu (NO)3)2、Co(NO3)2、Ni(NO3)2、Cr(NO3)2、HgCl2、Fe(NO3)3、Zn(NO3)2、Cd(NO3)2、Al(NO3)3、Pb(NO3)2、Ca(NO3)2、Mg(NO3)2、Ba(NO3)2The aqueous solution is stirred by a capillary tube to be uniformly mixed, the concentration of metal ions in the obtained solution is 0-200 mu mol/L, and a single photon fluorescence spectrometer is adopted to measure the fluorescence intensity I of the solution. After the solution reaches equilibrium, respectively plotting the fluorescence intensity along with Cu2+、Co2+、Ni2+、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+The result of the fluorescence spectrogram with concentration change is shown in figures 1-13, and the log (I/I) of different metal ion concentrations is calculated by collecting the fluorescence intensity of two monomer peaks 379nm and 399nm of a pyrene derivative fluorescence probe modified by di (2-methylpyridine) amine, an emission peak 460nm of a distorted excimer and an emission peak 501nm of a perfect excimer0) Values, log (I/I) at wavelengths of 379, 399, 460 and 501nm, respectively, when the metal ion concentration is 10. mu. mol/L, 50. mu. mol/L and 100. mu. mol/L, respectively0) Standard histograms of values, see FIGS. 14-16. And (3) reducing the four-dimensional data into two dimensions according to a principal component analysis data processing method, drawing the two-dimensional data into a standard classification atlas, and obtaining results shown in figures 17-19.
As can be seen from FIGS. 14 to 19, the fluorescent probe sensor of the present invention can achieve an interactive response to 13 metal ions, and log (I/I) is obtained by collecting fluorescence intensities at different wavelengths0) The fingerprint spectrum recognition of 13 metal ions can be realized by the histogram of the metal ion concentration, the four-dimensional data is reduced to two dimensions by a principal component analysis data processing method, and the distinguishing recognition of the 13 metal ions is realized by comparing with a standard classification spectrum.
3. Detecting a sample to be tested
According to the method, the fluorescence intensity I of the metal ion sample to be detected is added into the probe measured by the fluorometer, and the log (I/I) is calculated0) The value, processing data according to principal component analysis data processing method, can determine Cu by combining standard classification map2+、Co2+、Ni2+、Cr3+、Hg2+、Fe3+、Zn2+、Cd2+、Al3+、Pb2+、Ca2+、Mg2+、Ba2+The kind of (2).
Claims (5)
1. A synthetic method of a pyrene derivative fluorescent probe modified by di (2-methylpyridine) amine is characterized by comprising the following steps:
(1) synthesis of pyrenesulfonyl derivatives
Under the conditions of inert atmosphere and ice bath, dropwise adding a trichloromethane solution of pyrenesulfonyl chloride into a trichloromethane solution of diamino oxygen-containing alkane, stirring at room temperature for reacting for 2-8 hours after dropwise adding, and separating and purifying to obtain a pyrenesulfonyl derivative with the structural formula shown below;
the diamino oxygen-containing alkane is 1, 8-diamino-3, 6-dioxyoctane, 3,6, 9-trioxaundecane-1, 11-diamine or 3,6,9, 12-tetraoxahexadecane-1, 16-diamine, and n is 2, 3 or 4 in the corresponding pyrenesulfonyl derivative structural formula;
(2) synthesis of bis (2-methylpyridine) amine derivatives
Under the protection of nitrogen, dissolving 2-chloromethylpyridine hydrochloride in ultrapure water, sequentially adding aniline, sodium hydroxide and hexadecyltrimethylammonium chloride, stirring at room temperature for 24 hours, and separating and purifying to obtain di (2-methylpyridine) aniline; then under the ice bath condition, dripping a dimethyl formamide solution of bis (2-methylpyridine) aniline into a dimethyl formamide solution of phosphorus oxychloride, heating at 90 ℃ for reaction for 3 hours after dripping, pouring the reaction solution into water after the reaction is finished, and then using K to react2CO3Neutralizing until the pH value is 6-8, separating and purifying to obtain a di (2-methylpyridine) amine derivative with the structural formula as follows:
(3) synthesis of di (2-methylpyridine) amine modified pyrene derivative fluorescent probe
Adding pyrenesulfonyl derivative and di (2-methylpyridine) amine derivative into a mixed solution of dichloromethane and methanol in a volume ratio of 2:1, adding anhydrous sodium sulfate, stirring at room temperature for 12 hours, filtering out sodium sulfate, and spin-drying a solvent to obtain an oily substance; the oil was dissolved in methanol at 0 ℃ and sodium borohydride was added, stirred for 45 minutes at room temperature with saturated NaHCO3Quenching reaction of aqueous solution, separating and purifying to obtain the pyrene derivative fluorescent probe modified by bis (2-methylpyridine) amine with the structural formula as follows:
2. the method for synthesizing a bis (2-methylpyridine) amine modified pyrene derivative fluorescent probe according to claim 1, wherein: in the step (1), the molar ratio of pyrene sulfonyl chloride to diamino oxygen-containing alkane is 1 (8-12).
3. The method for synthesizing a pyrene derivative fluorescence probe modified by bis (2-methylpyridine) amine as claimed in claim 1, wherein in step (2), the molar ratio of aniline to 2-chloromethylpyridine hydrochloride, sodium hydroxide, and cetyltrimethylammonium chloride is 1 (1.5-3): 2-3: 0.02-0.1.
4. The method for synthesizing the bis (2-methylpyridine) amine modified pyrene derivative fluorescent probe according to claim 1, wherein in the step (2), the molar ratio of bis (2-methylpyridine) aniline to phosphorus oxychloride is 1 (7-8).
5. The method for synthesizing a bis (2-methylpyridine) amine modified pyrene derivative fluorescent probe according to claim 1, wherein: in the step (3), the molar ratio of the bis (2-methylpyridine) amine derivative to the pyrenesulfonyl derivative, the anhydrous sodium sulfate and the sodium borohydride is 1 (1.1-1.5) to (1-1.3) to (0.3-0.8).
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