CN111533692B - Fluorescent molecular probe for detecting mercury ions and preparation method and application thereof - Google Patents

Fluorescent molecular probe for detecting mercury ions and preparation method and application thereof Download PDF

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CN111533692B
CN111533692B CN202010493355.4A CN202010493355A CN111533692B CN 111533692 B CN111533692 B CN 111533692B CN 202010493355 A CN202010493355 A CN 202010493355A CN 111533692 B CN111533692 B CN 111533692B
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naphthalimide
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CN111533692A (en
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马福东
张玲
吴怡敏
阿布力克木·吾布力达
李俊芳
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Xinjiang Agricultural University
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    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
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    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N2021/6417—Spectrofluorimetric devices

Abstract

The invention discloses a fluorescent molecular probe for detecting mercury ions and a preparation method and application thereof, and belongs to the technical field of fluorescent probes. The invention synthesizes N-phenyl-4- (di (ethylsulfanylethyl) amino) -1, 8-naphthalimide which is opposite to Hg2+Has better recognition function, and the absorbance in the ultraviolet absorption spectrum is along with Hg2+The concentration increases with increasing concentration, and the fluorescence intensity in the fluorescence spectrum follows Hg2+The concentration is increased and decreased, and the probe molecule is opposite to Hg2+The detection has better selectivity and short response time.

Description

Fluorescent molecular probe for detecting mercury ions and preparation method and application thereof
Technical Field
The invention belongs to the technical field of fluorescent probes, and particularly relates to a fluorescent molecular probe for detecting mercury ions, and a preparation method and application thereof.
Background
A fluorescent molecular probe refers to a molecule in a system, wherein when a physical property in a substance or system is changed, the fluorescence intensity of the molecule can be correspondingly changed, and the substance or the physical property can be referred to as the fluorescent molecular probe. The identification principle of the fluorescent molecular probe mainly comprises the following steps: photoinduced electron transfer, intramolecular charge transfer, fluorescence resonance energy transfer, excited intramolecular proton transfer, excimer and structural functional group (such as C ═ N) isomerization and the like. Intramolecular charge transfer fluorescent molecular probes are generally prepared by direct attachment of a fluorophore to an acceptor without a significant linker arm. Fluorescent molecular probes have many advantages such as good selectivity and high sensitivity when used for detecting metal ions, so that the research is numerous.
Mercury ion fluorescent molecular probes have attracted extensive research interest in this area by chemists over the past few decades due to contamination with heavy and transition metals. Identification and sensing of heavy metal ions by fluorescence has become an important approach and method for biological and environmental aspects. The detection of various cations based on fluorescence sensor technology has many advantages, such as high sensitivity and selectivity, low cost, simple operation, and short response time. Due to Hg2+High toxicity, a great deal of scientists are dedicated toDevelopment of fluorescence chemical sensor2+Small molecules, conjugated polymers, nanoparticles, biomolecules. However, practical applications still suffer from cross sensitivity to other metal ions, narrow pH span, delayed reactions, and the like. Therefore, the development of new and practical, sensitive mercury ion selective chemical sensors remains a challenge.
The fluorescent probe of mercury ions has applications in various aspects, such as rhodamine, polycyclic aromatic hydrocarbons, dansyl, fluorescein and naphthalimide. Naphthalimide derivatives are widely used in various fields, such as fluorescence sensors, medicine, biology and detection of water systems. The derivative of 1, 8-naphthalimide with 4-substituted amide or alkoxy can be used as fluorescent whitening agent and has good light resistance. The naphthalimide polymerization type fluorescent whitening agent has polymer material performance and optical performance of the whitening agent, so that the problems that the traditional whitening agent is poor in solubility, heat resistance and processability and cannot independently form a film can be solved, and researches on the fluorescent whitening agent by researchers are rapidly developed in recent years. The naphthalimide derivative has good dyeing performance, so that the naphthalimide derivative has considerable research potential as a fluorescent dye, and mainly comprises research on water-soluble materials, research on laser dyes and the like. In the prior art, a plurality of naphthalimide fluorescent molecular probes are reported, and are suitable for detection of different ions and different application scenes. Is suitable for Hg2+Few reports of the detected probes are reported.
Disclosure of Invention
The invention aims to: aiming at the defects in the prior art, the fluorescent molecular probe for detecting mercury ions and the preparation method and the application thereof are provided.
The technical scheme adopted by the invention is as follows:
a preparation method of a fluorescent molecular probe for detecting mercury ions comprises the following steps:
s1, dissolving 4-bromo-1, 8-naphthalic anhydride in absolute ethyl alcohol, adding aniline, heating to reflux, reacting for 6-10h, and concentrating the filtrate to obtain N-phenyl-4-bromo-1, 8-naphthalimide, wherein the reaction formula is as follows:
Figure 1
s2, dissolving the N-phenyl-4-bromine-1, 8-naphthalimide obtained in the step S1 in ethylene glycol monomethyl ether, adding diethanol amine, heating to reflux, reacting for 5-8h to obtain the N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide, wherein the reaction formula is as follows:
Figure 2
s3, dissolving the N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide obtained in the step S2 in toluene, adding thionyl chloride, heating to reflux, reacting for 6-10h, concentrating and drying to obtain the N-phenyl-4- (N, N-dichloroethyl) amino-1, 8-naphthalimide, wherein the reaction formula is as follows:
Figure BDA0002521940430000023
s4, mixing sodium and ethanethiol, adding dried tetrahydrofuran, heating to reflux, and reacting for 2-4h to obtain sodium ethanethiol, wherein the reaction formula is as follows:
C2H5SH+Na→C2H5SNa；
s5, mixing the N-phenyl-4- (N, N-dichloroethyl) amino) -1, 8-naphthalimide obtained in the step S3 with sodium ethanethiol obtained in the step S4, carrying out reflux reaction for 40-55h, removing a solvent in a product, dissolving the product with dichloromethane, washing with water, concentrating and drying to obtain the compound N-phenyl-4- (N, N-dichloroethyl) amino) -1, 8-naphthalimide, wherein the reaction formula is as follows:
Figure BDA0002521940430000024
the invention synthesizes N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide (PDAN) by using 4-bromo-1, 8-naphthalic anhydride through a chemical synthesis method, and then converts dihydroxy into diethylthio to synthesize the fluorescent naphthalimide derivative. Finally synthesizing N-phenyl-4- (di (ethylsulfanylethyl) amino) -1, 8-naphthalimide (FTAN).
The fluorescent molecular probe of the invention, with the addition of mercury ions,
Figure BDA0002521940430000031
and the sulfur and mercury ions form a coordinate bond, so that the charge of the main body part of the naphthalimide is changed, the ultraviolet absorption of the naphthalimide is enhanced, the fluorescence of the naphthalimide is weakened, and the mercury ions can be identified.
Further, the molar ratio of 4-bromo-1, 8-naphthalic anhydride to aniline in S1 is 1: 1-2; preferably 1: 1.5.
Further, the molar ratio of the N-phenyl-4-bromo-1, 8-naphthalimide to the diethanolamine in S2 is 1: 6-9; preferably 1: 7.
Further, in S2, pouring the reaction solution after reaction into water, adding ethyl acetate, shaking, standing for layering, extracting a water layer with ethyl acetate, concentrating and drying to obtain the N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide.
Further, the ratio of the N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide to the thionyl chloride in the S3 is 1g:3-7 mL; preferably 1g:5 mL.
Further, the molar ratio of sodium to ethanethiol in S4 is 1-2: 1; preferably 1.5: 1.
Further, the molar ratio of the N-phenyl-4- (N, N-dichloroethyl) amino) -1, 8-naphthalimide to the sodium ethyl mercaptide in the S5 is 1: 1-2; preferably 1: 1.5.
Further, nitrogen is introduced into both S1 and S2 for 5-15min before heating to reflux; preferably 10 min; used for exhausting air and avoiding influencing the reaction.
The fluorescent molecular probe prepared by the method is adopted.
The fluorescent molecular probe is applied to the preparation of products for detecting mercury ions.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
the invention uses 4-bromo-1, 8-naphthalene diN-phenyl-4- (di (ethylthioethyl) amino) -1, 8-naphthalimide (FTAN) is synthesized by using formic anhydride as a raw material, and the optical identification performance of the N-phenyl-4- (di (ethylthioethyl) amino) -1, 8-naphthalimide (FTAN) on metal ions is measured to find that the N-phenyl-4- (di (ethylthioethyl) amino) -1, 8-naphthalimide (FTAN) on Hg2+Has better recognition function, and the absorbance in the ultraviolet absorption spectrum is along with Hg2+The concentration increases with increasing concentration, and the fluorescence intensity in the fluorescence spectrum follows Hg2+The concentration is increased and decreased, and the probe molecule is opposite to Hg2+The detection has the advantages of good selectivity, short response time and the like. Therefore, the N-phenyl-4- (di (ethylthio ethyl) amino) -1, 8-naphthalimide (FTAN) prepared by the invention can be used as an optical probe material for Hg2+The rapid detection of (2).
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an infrared spectrum of PBN;
FIG. 2 is an infrared spectrum of PDAN;
FIG. 3 is a mass spectrum of PDAN;
FIG. 4 is an infrared spectrum of PCAN;
FIG. 5 is an infrared spectrum of FTAN;
FIG. 6 is a mass spectrum of FTAN;
FIG. 7 is a UV spectrum of FTAN;
FIG. 8 is a graph of the fluorescence spectrum of FTAN;
FIG. 9 is a graph of the UV absorbance values of FTAN when different metal ions are added;
FIG. 10 is a chart of the UV-Vis spectra of FTAN at different concentrations of mercury ions;
FIG. 11 is a graph of the fluorescence spectra of FTAN at different concentrations of mercury ions;
FIG. 12 is a graph of a fit of the lowest detection limit of mercury ion concentration;
FIG. 13 is a graph showing response time of FTAN to mercury ions in fluorescence spectrum detection.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The features and properties of the present invention are described in further detail below with reference to examples.
Examples
The preferred embodiment of the invention provides a preparation method of a fluorescent molecular probe for detecting mercury ions, which comprises the following specific steps:
(1) weighing 4.00g of 4-bromo-1, 8-naphthalic anhydride, placing the 4.00g into a 250mL three-neck flask, adding 120mL of absolute ethyl alcohol, adding 8mL of aniline, slowly introducing nitrogen for 10 minutes, stirring and heating in an oil bath kettle until reflux reaction is carried out, and reacting for 7 hours. Thin Layer Chromatography (TLC) to confirm complete reaction of the reactants. Standing overnight, and filtering to obtain light yellow product N-phenyl-4-bromo-1, 8-naphthalimide (PBN). The filtrate was concentrated to give a pale yellow product, N-phenyl-4-bromo-1, 8-naphthalimide (PBN).
The product N-phenyl-4-bromo-1, 8-naphthalimide (PBN)3.33g, yield 83.3%, melting range 188 ℃ -190 ℃. IR (KBr)550cm-1、700cm-1、770cm-1、885cm-1、1070cm-1、1193cm-1、1379cm-1、1430cm-1、 530cm-1、1656cm-1、3078cm-1。
(2) Weighing 4.00g N-phenyl-4-bromo-1, 8-naphthalimide (PBN), putting into a 250mL three-neck flask, adding 160 mL ethylene glycol monomethyl ether, then adding 8mL diethanolamine, slowly introducing nitrogen for 10 minutes, stirring and heating in an oil bath kettle until reflux reaction, and reacting for 6 hours. The reaction was followed by Thin Layer Chromatography (TLC) to determine if the reaction was complete. Taking down and standing to room temperature after the reaction is completed. Pouring the reaction solution into 50mL of distilled water, adding 30mL of ethyl acetate, fully shaking, standing and demixing. The aqueous layer was extracted with ethyl acetate (20mL), concentrated and dried to give N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide (PDAN) as a pale yellow product.
The product, N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide (PDAN), 2.012g, in 50.3% yield and a melting point of 174 ℃. IR (KBr)3182cm-1、3317cm-1、1678cm-1、2930cm-1、1590cm-1、1430cm-1、 1350cm-1、1280cm-1、1590cm-1、751cm-1、779cm-1。
(3) Weighing 1.00g N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide (PDAN) and placing the PDAN into a 100mL three-neck flask, adding 50mL of purified toluene, stirring and dissolving, then adding 5mL of thionyl chloride, stirring and heating in an oil bath kettle until reflux reaction is carried out, and reacting for 7 hours. The reaction was followed by Thin Layer Chromatography (TLC). After the reaction was completed, the reaction mixture was taken down and allowed to stand at room temperature to obtain a tan oily liquid. Concentration and drying gave a tan-colored product, N-phenyl-4- (N, N-dichloroethyl) amino-1, 8-naphthalimide (PCAN), 0.503g, at a yield of 50.3%. IR (KBr)1678cm-1, 2930cm-1, 1590cm-1, 1430 cm-1, 1350cm-1, 1280cm-1, 1590cm-1, 751cm-1, 779 cm-1.
(4) Weighing 0.931g of metal sodium, putting the metal sodium into a 100mL three-neck flask, adding 0.5mL of ethanethiol, adding 12mL of tetrahydrofuran dried by a molecular sieve into the three-neck flask, stirring in an oil bath kettle, heating to reflux reaction for about 3 hours, and obtaining the sodium ethanethiol after the reaction is completed. 0.22g of N-phenyl-4- (N, N-dichloroethyl) amino) -1, 8-naphthalimide (PCAN) was added to the reaction flask and reacted under reflux for 48 hours. The reaction was followed by Thin Layer Chromatography (TLC). And after the reaction is finished, taking down and standing to room temperature to obtain yellow reaction liquid. The yellow reaction solution was freed of solvent, dissolved in 10mL of dichloromethane and washed three times with deionized water. Concentration and drying gave 0.052g of N-phenyl-4- (bis (ethylsulfanylethyl) amino) -1, 8-naphthalimide (FTAN) as a yellow product in 23.4% yield. IR (KBr))1678cm-1、1695cm-1、1655cm-1、2930cm-1、1590cm-1、 1430cm-1、1350cm-1、1280cm-1、1590cm-1、751cm-1、779cm-1。
Experimental example 1
Infrared spectrum characterization of the N-phenyl-4-bromo-1, 8-naphthalimide (PBN) prepared in the examples was performed. As shown in FIG. 1, the infrared spectrogram has main characteristic peaks of IR (KBr): V550 cm-1Is C-C ═ O peak, 700cm-1、770cm-1Is C-H peak of naphthalene ring, 885cm-1Is Br peak on naphthalene ring, 1070cm-1Is C ═ O peak, 1193cm-1、1379cm-1、1430cm-1Is a characteristic peak of a benzene ring characteristic skeleton, 1530cm-1The peak value is N-H, 1656cm-1Is amide N-C ═ O peak, 3078cm-1Is a benzene ring peak, meets the literature value and determines that the functional group of the product is correct.
The structure of N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide (PDAN) was characterized by infrared spectroscopy. As shown in FIG. 2, the infrared spectrogram has main characteristic peaks of IR (KBr): v 3182cm-1is-CH 2 peak at 1678cm-1Is the peak of N-C ═ O in the amide, 2930cm-1Peak at 1590cm for C-H-1、1430cm-1、1350cm-1Is a characteristic peak of a benzene ring characteristic skeleton, 1280cm-1Peak at 1590cm for C-N-1Is C ═ C peak, 751cm-1、779cm-1Is a naphthalene ring C-H peak, 3487 cm-1Is the-OH peak, which corresponds to literature values and thus determines that the product functionality is correct.
As shown in fig. 3, the mass spectrum of N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide (PDAN) was measured, and the PDAN had a theoretical mass-to-charge ratio of m/e ═ 375.20923 in the negative ion mode, whereas the mass-to-charge ratio of m/e ═ 375.209 in the negative ion mode was obtained, indicating that the target product was successfully synthesized.
The structure of N-phenyl-4- (N, N-dichloroethyl) amino-1, 8-naphthalimide (PCAN) was characterized by infrared spectroscopy. As shown in FIG. 4, the infrared spectrogram has main characteristic peak IR (KBr): v 1678cm-1Is the peak of N-C ═ O in the amide, 2930cm-1Peak at 1590cm for C-H-1、1430cm-1、1350cm-1Is a characteristic peak of a benzene ring characteristic skeleton, 1280cm-1Peak at 1590cm for C-N-1Is C ═ C peak, 751cm-1、779cm-1Is a naphthalene ring C-H peak, 655cm-1Is a Cl peak, which corresponds to literature values and thus determines that the product functionality is correct.
The structure of N-phenyl-4- (bis (ethylthioethyl) amino) -1, 8-naphthalimide was characterized by infrared spectroscopy. As shown in FIG. 5, the infrared spectrogram has main characteristic peak IR (KBr): v 1678cm-1Is the peak of N-C ═ O in the amide, 1695cm-1、 1655cm-1Is the absorption peak of carbonyl in imide, 2930cm-1Peak at 1590cm for C-H-1、1430cm-1、1350cm-1Is a characteristic peak of a benzene ring characteristic skeleton, 1280cm-1Peak at 1590cm for C-N-1Is C ═ C peak, 751cm-1、779cm-1Is a naphthalene ring C-H peak of 689cm-1The ethylthio peak is in agreement with literature values and thus confirms that the product functionality is correct.
The mass spectrum of N-phenyl-4- (bis (ethylthioethyl) amino) -1, 8-naphthalimide (FTAN) was measured and as shown in fig. 6, the bis (ethylthioethyl) amino group was theoretically at a mass to charge ratio of m/e 192.08796 as obtained in the positive ion mode at a mass to charge ratio of m/e 192.087, indicating the presence of the bis (ethylthioethyl) amino group in this group. N-phenyl-1, 8-naphthalimide theoretically has a mass to charge ratio of m/e-273.07898 indicating the presence of this group N-phenyl-1, 8-naphthalimide as obtained in positive ion mode with a mass to charge ratio of m/e-273.078.
Experimental example 2
N-phenyl-4- (bis (ethylsulfanylethyl) amino) -1, 8-naphthalimide reacted with absolute ethanol: deionized water 2:1 was formulated at a concentration of 1.0x10-5mol/L solution. Hg is a mercury vapor2+、Cu2+、Cr3+、Co2+、Ca2+、K+、Na+、Ba2+Salts of other metal ions were made up to 1.0x10 with deionized water-1mol/L solution.
Measurement of ultraviolet-visible absorption spectrum and fluorescence spectrum: pouring the prepared solution into a cuvette, and adding absolute ethyl alcohol: and (3) taking deionized water as a reference solution at a ratio of 2:1, testing an ultraviolet-visible absorption spectrum on a TU-1810PC ultraviolet-visible spectrophotometer, and testing a fluorescence spectrum on a fluorescence spectrophotometer at room temperature.
In the ultraviolet spectrum of N-phenyl-4- (bis (ethylthioethyl) amino) -1, 8-naphthalimide shown in FIG. 7 and the fluorescence spectrum shown in FIG. 8, Ca was observed2+、Ba2+、Co2+、Cu2+、K+、Mg2+、Na+、Ni2+、Pb2+、Zn2+The ultraviolet absorption and the fluorescence emission intensity of the N-phenyl-4- (di (ethylsulfanylethyl) amino) -1, 8-naphthalimide (FTAN) are basically not influenced, and Hg is added2+Rear suctionThe increase of the luminosity and the decrease of the fluorescence intensity indicate that the N-phenyl-4- (di (ethylsulfanylethyl) amino) -1, 8-naphthalimide (FTAN) is opposite to Hg2+Has specific selectivity.
From FIG. 9, it can be observed that a large amount of background ions (Ca) are present2+、Ba2+、Co2+、Cu2+、K+、Mg2+、Na+、Ni2+、 Pb2+、Zn2+) Hg is added to a solution of N-phenyl-4- (bis (ethylthioethyl) amino) -1, 8-naphthalimide in the presence of2+The ultraviolet absorption value of the solution is obviously enhanced. Description of FTAN vs Hg2+Has good interference immunity.
FIG. 10 shows that N-phenyl-4- (bis (ethylsulfanylethyl) amino) -1, 8-naphthalimide (FTAN) is dependent on Hg in UV2+The absorbance gradually increased with increasing concentration.
FIG. 11 shows that N-phenyl-4- (bis (ethylsulfanylethyl) amino) -1, 8-naphthalimide (FTAN) follows Hg in fluorescence2+The fluorescence intensity gradually decreased with increasing concentration.
From Hg in FIG. 122+The Hg can be known from a curve fitted to the concentration sensitivity2+The concentration sensitivity can detect 5.78x10-5Target concentrations of the order of mol/L.
FIG. 13 shows that N-phenyl-4- (bis (ethylsulfanylethyl) amino) -1, 8-naphthalimide (FTAN) has a fluorescence spectroscopy detection vs. Hg2+It can be seen that the fluorescence intensity does not substantially change from 7min, so 7min is the optimal response time.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A preparation method of a fluorescent molecular probe for detecting mercury ions is characterized by comprising the following steps:
s1, dissolving 4-bromo-1, 8-naphthalic anhydride in absolute ethyl alcohol, adding aniline, heating to reflux, reacting for 6-10h, and concentrating the filtrate to obtain N-phenyl-4-bromo-1, 8-naphthalimide;
s2, dissolving the N-phenyl-4-bromine-1, 8-naphthalimide obtained in the step S1 in ethylene glycol monomethyl ether, adding diethanol amine, heating to reflux, and reacting for 5-8h to obtain N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide;
s3, dissolving the N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide obtained in the step S2 in toluene, adding thionyl chloride, heating to reflux, reacting for 6-10h, concentrating and drying to obtain N-phenyl-4- (N, N-dichloroethyl) amino-1, 8-naphthalimide;
s4, mixing sodium and ethanethiol, adding dried tetrahydrofuran, heating to reflux, and reacting for 2-4h to obtain sodium ethanethiol;
s5, mixing the N-phenyl-4- (N, N-dichloroethyl) amino-1, 8-naphthalimide obtained in the step S3 with sodium ethanethiol obtained in the step S4, carrying out reflux reaction for 40-55h, removing a solvent in a product, dissolving the product with dichloromethane, washing with water, concentrating and drying to obtain the fluorescent molecular probe;
wherein, the chemical structural formula of the fluorescent molecular probe is as follows:
Figure FDA0003238842720000011
2. the method for preparing a fluorescent molecular probe for detecting mercury ions according to claim 1, wherein the molar ratio of 4-bromo-1, 8-naphthalic anhydride to aniline in S1 is 1: 1-2.
3. The method for preparing a fluorescent molecular probe for detecting mercury ions according to claim 1, wherein the molar ratio of N-phenyl-4-bromo-1, 8-naphthalimide to diethanolamine in S2 is 1: 6-9.
4. The method for preparing a fluorescent molecular probe for detecting mercury ions according to claim 1, wherein in S2, the reacted reaction solution is poured into water, ethyl acetate is added, the mixture is shaken and then stands for layering, the ethyl acetate is used for extracting a water layer, and the water layer is concentrated and dried to obtain the N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide.
5. The method for preparing a fluorescent molecular probe for detecting mercury ions according to claim 1, wherein the ratio of N-phenyl-4- (N, N-dihydroxyethyl) amino-1, 8-naphthalimide to thionyl chloride in S3 is 1g:3-7 mL.
6. The method for preparing a fluorescent molecular probe for detecting mercury ions according to claim 1, wherein the molar ratio of sodium to ethanethiol in S4 is 1-2: 1.
7. The method for preparing a fluorescent molecular probe for detecting mercury ions according to claim 1, wherein the molar ratio of N-phenyl-4- (N, N-dichloroethyl) amino-1, 8-naphthalimide to sodium ethyl mercaptide in S5 is 1: 1-2.
8. The method of claim 1, wherein nitrogen is introduced into both S1 and S2 for 5-15min before heating to reflux.
9. The fluorescent molecular probe prepared by the method of any one of claims 1 to 8, wherein the chemical structural formula of the fluorescent molecular probe is as follows:
Figure FDA0003238842720000021
10. use of the fluorescent molecular probe of claim 9 in the preparation of a product for detecting mercury ions.
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