CN117447335A - PFOS fluorescent probe and application and preparation method thereof - Google Patents

PFOS fluorescent probe and application and preparation method thereof Download PDF

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CN117447335A
CN117447335A CN202311798498.6A CN202311798498A CN117447335A CN 117447335 A CN117447335 A CN 117447335A CN 202311798498 A CN202311798498 A CN 202311798498A CN 117447335 A CN117447335 A CN 117447335A
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pfos
fluorescent probe
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CN117447335B (en
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陈培瑶
于亚宁
庄爽
王滨
李荣振
杨亮
刘慧敏
王帅
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Tianjin Fire Research Institute of MEM
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    • C07—ORGANIC CHEMISTRY
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    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
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    • C07C217/16—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to a carbon atom of a six-membered aromatic ring the six-membered aromatic ring or condensed ring system containing that ring not being further substituted
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    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract

The invention relates to the technical field of fluorescence detection, in particular to a PFOS fluorescent probe and an application and a preparation method thereof. The PFOS fluorescent probe can be used for detecting the content of PFOS and derivatives thereof in water, soil or water-based foam extinguishing agents, the detection method is simple and quick, no dependence is caused on large-scale instruments and equipment, quantitative detection can be realized by using a portable fluorescence spectrophotometer, and the detection efficiency is obviously improved. The invention also provides a preparation method of the PFOS fluorescent probe, which has the advantages of simple steps, mild conditions and easy realization of large-scale production.

Description

PFOS fluorescent probe and application and preparation method thereof
Technical Field
The invention relates to the technical field of fluorescence detection, in particular to a PFOS fluorescent probe and an application and a preparation method thereof.
Background
Perfluorooctanesulfonyl compounds (Perfluorooctane sulfonate, PFOS) are representative synthetic fluorine-containing organic compounds whose molecules are composed of a hydrophobic fully fluorinated alkyl chain and hydrophilic sulfonic acid ends, and thus PFOS and its derivatives have excellent chemical stability, amphiphilicity and high surface activity, and their properties are far superior to those of conventional hydrocarbon surfactants in many fields of application. PFOS was first a synthetic organofluoro chemical product developed by 3M in 1952 and then widely used in textile, leather cosmetics, packaging materials, fire fighting foam, and other manufacturing processes. However, perfluorooctane sulfonate and its salts have been under the Stockholm convention for persistent contaminants in month 5 of 2009 because of their non-degradability and persistent contamination. While PFOS has been banned by most countries, it is still used in many fields, for example, as a typical fluorinated surfactant, perfluorooctane sulfonyl fluoride (POSF) is used in commercial water film foam extinguishing agents, entering the environment and degrading to PFOS in a manner accompanied by the use of water film foam extinguishing agents, and thus causing environmental pollution, up to 3.5 ten thousand tons of fluorocarbon surfactant-containing foam extinguishing agents sold annually in our country. In addition, PFOS is difficult to exclude after being ingested by living things, and causes serious interference with organ functions of liver, brain, kidney, etc. along with food chain transfer, bioaccumulation and bioamplification, with carcinogenicity, teratogenicity and genotoxicity. Therefore, to effectively control PFOS's large area pollution of the surrounding water environment and pose a potential threat to human health, detection of PFOS content in waters becomes necessary.
Currently, the analysis and detection methods for PFOS mainly include chromatography-mass spectrometry and nuclear magnetic resonance analysis. The method can perform qualitative and quantitative analysis on the PFOS, has low detection limit and high reliability, but depends on large-scale equipment which is expensive and inconvenient to carry, has complex sample pretreatment and instrument operation processes, and is not suitable for on-site rapid detection on the PFOS in an outdoor environment. In recent years, with the generation and development of new technologies, PFOS detection technologies are advancing toward diversification, and are focused on improving sensitivity, improving detection throughput, and improving instrument portability. Fluorescence sensing is an important analysis method, has the advantages of good universality, low detection limit, large detection flux, simple sample pretreatment and the like, and receives wide attention of technological workers. Fluorescent probes in fluorescent sensing systems typically exhibit a change in fluorescence intensity or color upon interaction with a target analyte, and these signal changes are readily identifiable to the naked eye. In addition, the fluorescence sensing system can also realize rapid quantitative or semi-quantitative analysis of analytes with the aid of small-sized equipment such as a portable fluorescence spectrophotometer or an ultraviolet camera bellows. The advantages enable the fluorescence sensing to have wide application prospect in the field of environmental pollution detection, in particular to the field of on-site rapid detection of pollutants in sudden environmental pollution events.
Some subject groups have performed prospective research work in the field of PFOS fluorescence sensors. The cationic porphyrin/cadmium perchlorate quantum dots and PFOS are used for forming a compound under the action of electrostatic force, and the fluorescence intensity of the system is gradually reduced along with the increase of the concentration of the PFOS; research has also found that PFOS can quench the fluorescence of cadmium telluride quantum dot, nile blue A and other fluorescent substances with high efficiency, and the system fluorescence intensity has a linear relation with PFOS concentration; in addition, the PFOS has been shown to enhance fluorescence of a plurality of fluorescence pre-quenching systems such as the sodium hypochlorite, the erythrosine B, the berberine hydrochloride, the polyethylenimine, the cetyltrimethylammonium bromide and the like, and realize fluorescence off-on. However, when the water body to be detected also contains components such as short-chain fluorocarbon surfactant such as potassium perfluorobutyl sulfonate, perfluorohexyl sulfonate or other anionic hydrocarbon surfactants (wherein the potassium perfluorobutyl sulfonate and the perfluorohexyl sulfonate are components contained in foam extinguishing agents or fire-fighting wastewater), the components and the fluorescent probe have action mechanisms similar to those of PFOS and the fluorescent probe, so that obvious interference can be generated on the fluorescent sensing process, and the PFOS cannot be accurately quantified by the current detection method due to the interference of the other components. Therefore, it is of great importance to develop a simple, rapid and sensitive PFOS detection method.
Disclosure of Invention
In view of the above, the invention provides a PFOS fluorescent probe, and an application and a preparation method thereof, wherein the PFOS fluorescent probe has excellent water solubility and good selectivity to PFOS, and the accurate quantification of PFOS and derivatives thereof in a liquid to be detected with complex components is realized by a fluorescence detection method.
In order to solve the technical problems, the invention provides a PFOS fluorescent probe, wherein the chemical structural formula of the PFOS fluorescent probe is shown as formula I:
formula I.
The chemical structure of the PFOS fluorescent probe provided by the invention contains a typical aggregation-induced emission fluorescent chromophore tetraphenyl ethylene, the tetraphenyl ethylene hardly shows fluorescence when in a monodisperse state in a solution, and the fluorescence is obviously enhanced in a solid state or an aggregation state; the chemical structure of the fluorescent probe provided by the invention also comprises a polyalcohol amine structure, the polyalcohol amine structure has good hydrophilicity, and under the acidic condition, the polyalcohol amine has positive charges, and electrostatic binding force can be generated between the polyalcohol amine and sulfonic anions in fluorocarbon surfactant in water body. Therefore, the good hydrophilicity of the polyalcohol amine enables the PFOS fluorescent probe to have excellent water solubility, and the fluorescent chromophore tetraphenyl ethylene enables the PFOS fluorescent probe to have different fluorescence emission capacities under different dispersion states in the aqueous solution.
The inventors have found during experiments that by chance, the fluorescent probe only shows fluorescence when mixed with water containing PFOS and its derivatives, but does not show fluorescence when mixed with water not containing PFOS and its derivatives. For this reason, the inventors speculate that this phenomenon may be related to the number of carbon atoms in the fluorocarbon surfactant, specifically: compared with other short fluorocarbon surfactants (such as potassium perfluorobutyl sulfonate and potassium perfluorohexyl sulfonate), the PFOS serving as a long fluorocarbon surfactant has higher hydrophobicity, and after the PFOS and the fluorescent probe are combined by static electricity, the high hydrophobicity of the PFOS enables the solubility of the fluorescent probe to be obviously reduced, so that the fluorescent probe is aggregated and fluorescence is generated; for other short fluorocarbon surfactants (such as potassium perfluorobutyl sulfonate and potassium perfluorohexyl sulfonate), after the short fluorocarbon surfactants are combined with the fluorescent probe through static electricity, the hydrophobicity is insufficient to reduce the solubility of the fluorescent probe in water, and the fluorescent probe cannot be aggregated to generate fluorescence; the acting force between the anionic hydrocarbon surfactant and the fluorescent probe is weak for the anionic hydrocarbon surfactant possibly existing in the water body at the same time, so that the solubility of the fluorescent probe in water cannot be changed to gather the anionic hydrocarbon surfactant; in addition, other cationic hydrocarbon surfactants and nonionic surfactants which may exist simultaneously in the water body do not electrostatically bind to the fluorescent probes, so that the fluorescent probes are not aggregated. Therefore, the fluorescent probe provided by the invention has excellent selectivity to PFOS and derivatives thereof in water.
The second aspect of the invention provides an application of the PFOS fluorescent probe in detecting PFOS and derivatives thereof in water, soil or water-based foam extinguishing agents.
With reference to the second aspect, the application includes:
dissolving a fluorescent probe shown in a formula I in an acidic buffer solution to prepare a fluorescent probe detection solution;
pretreating an object to be detected to obtain liquid to be detected;
and uniformly mixing the fluorescent probe detection liquid and the liquid to be detected, and performing fluorescent detection.
The fluorescent probe of the fluorescent probe shown in the formula I has positive charge under an acidic condition, can be combined with electronegative PFOS and derivatives thereof in a liquid to be detected to generate static electricity, and utilizes the hydrophobicity of the PFOS and the derivatives thereof to aggregate tetraphenyl ethylene groups in the fluorescent probe so as to display fluorescence.
With reference to the second aspect, the application further includes quantitative detection, and the specific steps include:
the PFOS standard substance is weighed to prepare PFOS solution with serial concentration as standard solution, deionized water is used as blank solution, and the standard solution and the blank solution are respectively mixed with the fluorescent probe detection solution according to the following ratio of 1:1, respectively measuring the fluorescence intensity;
and drawing a standard curve by taking the concentration of PFOS as an abscissa and the ratio of the fluorescence intensity of each standard solution to that of the blank solution as an ordinate, and determining the concentration of PFOS and derivatives thereof in the object to be detected based on the standard curve.
The fluorescence detection method provided by the invention can be used for rapidly and accurately quantifying the PFOS and the derivatives thereof, and the dependence of the existing quantification method on large-scale equipment is reduced.
With reference to the second aspect, the fluorescence detection conditions include: excitation slit 5nm, emission slit 5nm, voltage 700V, test fluorescence spectrum in 400~600nm scope, record 470nm department fluorescence intensity.
With reference to the second aspect, the pH of the acidic buffer solution is 3-4, and the acidic buffer solution in the pH range can ensure accurate quantification.
Preferably, the pH of the acidic buffer solution is 3.5.
With reference to the second aspect, the acidic buffer solution is selected from acetic acid/sodium acetate buffer solution, disodium hydrogen phosphate/citric acid buffer solution, citric acid/sodium hydroxide/hydrochloric acid buffer solution, glycine/hydrochloric acid buffer solution, phthalic acid/hydrochloric acid buffer solution, or citric acid/sodium citrate buffer solution.
With reference to the second aspect, the concentration of the fluorescent probe detection solution is 0.2-0.3 mg/mL, and the concentration range can ensure the accuracy of a fluorescent detection method.
Preferably, the concentration of the fluorescent probe detection solution is 0.25mg/mL.
With reference to the second aspect, the fluorescent probe detection solution and the test solution or standard solution are both prepared according to 1:1 by volume.
With reference to the second aspect, when the object to be detected is a natural water body or fire-fighting wastewater, the natural water body or fire-fighting wastewater is filtered by a filter membrane to obtain the liquid to be detected.
In combination with the second aspect, when the object to be detected is a water-based foam extinguishing agent, the water-based foam extinguishing agent is diluted to obtain the liquid to be detected. Because the water-based foam extinguishing agent contains high PFOS content, dilution is needed according to actual conditions, so that the diluted concentration falls within the concentration range of a standard curve, and accurate quantification is realized.
With reference to the second aspect, when the object to be detected is soil, the soil is leached with water and the leaching solution is filtered to obtain the liquid to be detected.
The third aspect of the present invention provides a method for preparing the PFOS fluorescent probe, which comprises the following steps:
preparing monohydroxy tetraphenyl ethylene by taking diphenyl ketone and 4-hydroxy diphenyl ketone as raw materials;
reacting the monohydroxy tetraphenyl ethylene, N-Boc bromoethylamine and a base catalyst to prepare a first intermediate product;
the first intermediate obtained is added to HCl and CH 3 Continuously reacting the mixed solution of OH, and pulping to obtain a second intermediate product;
and (3) reacting the second intermediate product with glycidol to obtain the fluorescent probe shown in the formula I.
。
The preparation method of the fluorescent probe provided by the invention has the advantages of simple steps, mild reaction conditions, easily available reaction raw materials and easiness in realizing large-scale production.
Further, the invention provides a preparation method of the PFOS fluorescent probe, which comprises the following preparation steps: by using tetrahydrofuran as solvent, zinc powder and TiCl are first made 4 Adding diphenyl ketone and 4-hydroxy diphenyl ketone to react, and continuing to react to obtain monohydroxy tetraphenyl ethylene; then N, N-dimethylformamide is taken as a solvent, and the monohydroxy tetraphenyl is respectively addedEthylene, N-Boc bromoethylamine and a base catalyst react to obtain a first intermediate product; the first intermediate obtained is then added to HCl and CH 3 Continuing to react in the OH mixed solution, and pulping to obtain a second intermediate product; and finally, adding the second intermediate product and glycidol into methanol for reaction to obtain the fluorescent probe.
Preferably, the base catalyst is selected from potassium carbonate, sodium bicarbonate, cesium carbonate, triethylamine or N, N-dimethylbenzylamine.
Furthermore, the invention provides a preparation method of the PFOS fluorescent probe, which comprises the following preparation steps:
s1, mixing zinc powder and tetrahydrofuran, cooling to-5~0 ℃ in a nitrogen atmosphere, adding titanium tetrachloride, ensuring that the temperature of the mixture is lower than 10 ℃, stirring at room temperature for 0.4-0.6 h, heating and refluxing for 2-3 h under stirring, cooling the mixture to-5~0 ℃ after the refluxing is finished, adding benzophenone and 4-hydroxybenzophenone, heating and refluxing under a nitrogen condition for 10-14 h, quenching the reaction by using a water phase, separating solid from liquid, removing an organic phase to obtain a water phase, extracting the water phase by using dichloromethane, removing water, filtering and evaporating the dichloromethane to obtain yellow powder, and purifying by using a column chromatography to obtain light yellow powder monohydroxy tetraphenyl ethylene;
s2, adding the monohydroxy tetraphenyl ethylene obtained in the step S1, N-Boc bromoethylamine and a base catalyst into N, N-dimethylformamide, stirring for 10-14 hours at normal temperature, adding water after the reaction is finished, extracting with ethyl acetate, washing an organic phase with a saturated sodium chloride solution, and removing water, filtering and evaporating the organic phase to obtain a first intermediate product;
s3, adding the obtained product to HCl and CH 3 Stirring the mixture in the OH mixed solution for 10-14 h at room temperature, and pulping after the reaction is finished to obtain a second intermediate product;
and S4, adding the obtained second intermediate product and glycidol into methanol, stirring for 10-14 hours at 38-42 ℃, evaporating to remove the methanol after the reaction is finished, washing the residual solid with diethyl ether to remove unreacted glycidol, and drying after solid-liquid separation to obtain the PFOS fluorescent probe.
Preferably, in step S1, the ratio of the mass of the zinc powder to the volume of tetrahydrofuran is 1: (15-35); the molar ratio of titanium tetrachloride to zinc powder is 1: (1.5-3); the molar ratio of the diphenyl ketone to the 4-hydroxy diphenyl ketone is 1: 1-2; wherein the unit of mass is g and the unit of volume is mL.
Preferably, in the step S2, the molar ratio of the monohydroxy tetrastyrene, the N-Boc bromoethylamine to the cesium carbonate is sequentially 1: (2-3): (1-2).
Preferably, in step S3, the mass of the first intermediate product is combined with HCl and CH 3 The volume ratio of the OH mixed solution is 1: (6-8); the HCl and CH 3 The preparation method of the OH mixed solution comprises the following steps: acetyl chloride and methanol were mixed according to 1: (5-8) mixing under ice bath condition, and reacting at room temperature to obtain HCl and CH 3 OH mixture.
Preferably, in step S4, the molar ratio of the second intermediate product to glycidol is 1: (1.5-3).
The invention has the beneficial effects that: the PFOS fluorescent probe provided by the invention has good selectivity to PFOS and derivatives thereof in the liquid to be detected, and the PFOS and derivatives thereof are accurately quantified by a fluorescence detection method and are not interfered by other surfactants; meanwhile, the fluorescence change in the fluorescence detection method is 'from nothing to nothing', so that naked eye observation and judgment are facilitated, and quick qualitative detection of PFOS and derivatives thereof is realized. The PFOS fluorescent probe provided by the invention is used for carrying out fluorescent detection on PFOS and derivatives thereof, the detection method is simple in operation, convenient and quick, no dependence on large-scale instruments and equipment is caused, quantitative detection can be realized only by using a portable fluorescence spectrophotometer, and the detection efficiency is greatly improved.
Drawings
FIG. 1 is a photograph of the PFOS fluorescent probe of example 1 for verifying selectivity;
FIG. 2 is a graph showing fluorescence spectra corresponding to PFOS standard solutions of different concentrations in example 2;
FIG. 3 is a standard curve obtained in example 2;
FIG. 4 is a nuclear magnetic resonance spectrum of the PFOS fluorescent probe obtained in example 5.
Detailed Description
To make the objects, technical solutions and advantages of the present invention more apparent, the following is combined with the detailed description
The present invention will be described in further detail with reference to examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In view of the problems that the existing PFOS detection method is easy to be interfered by other surfactants and cannot realize accurate quantification and the existing detection method is too dependent on large equipment, the invention provides the PFOS fluorescent probe with good selectivity on PFOS and derivatives thereof under the condition that a plurality of surfactants exist simultaneously, and the PFOS fluorescent probe is combined with a portable fluorescence spectrophotometer to realize qualitative and quantitative analysis on the PFOS and the derivatives thereof by the fluorescence detection method.
The use of the PFOS fluorescent probe in detection is described below by way of specific examples. HCl/CH used in the examples below 3 The preparation method of the OH solution comprises the following steps: slowly dripping 8 mL acetyl chloride into a flask containing 50 mL methanol under ice bath condition, and stirring at room temperature for 1 h to obtain HCl/CH 3 And (3) an OH solution, and refrigerating for standby.
Example 1
To verify that PFOS fluorescent probes are selective for PFOS and its derivatives, the following experiments were performed, specifically:
the PFOS fluorescent probe is dissolved in acetic acid/sodium acetate buffer solution with pH of 3.5 to prepare a fluorescent probe detection solution with the concentration of 0.25mg/mL, and then the fluorescent probe detection solution is respectively mixed with PFOS solution, perfluorooctanoic acid solution, perfluorobutyl potassium sulfonate solution, perfluorohexyl potassium sulfonate solution and deionized water with the concentration of 50ppm according to the following ratio of 1:1, and then taking an equal amount of mixed solution and a cuvette, and irradiating under an ultraviolet lamp, wherein a photo is shown as a picture in fig. 1, and the fluorescent probe provided by the invention has good selectivity to PFOS, and can accurately determine the PFOS in a water body containing various surfactants.
Example 2
The embodiment provides an application of a PFOS fluorescent probe in fire-fighting wastewater detection, which comprises the following specific application methods:
the PFOS fluorescent probe is dissolved in acetic acid/sodium acetate buffer solution with pH of 3.5 to prepare 0.25mg/mL fluorescent probe detection solution, and the fluorescent probe detection solution and fire control wastewater filtered by 0.45 mu m are mixed according to the following ratio of 1:1 to obtain a liquid to be tested, and testing according to the following detection conditions:
(1) Drawing a standard curve:
PFOS was dissolved in deionized water at concentrations of 10ppm, 8ppm, 6ppm, 4ppm, 2ppm, 1ppm, 0.8ppm, 0.6ppm, 0.4ppm, 0.2ppm, 0.1ppm, 0ppm, and then the solutions at the respective concentrations were mixed with a fluorescent probe test solution according to a ratio of 1:1, and placing the mixture in a cuvette after uniform mixing, scanning the mixture by using a fluorescence spectrophotometer (F-7000 fluorescence spectrophotometer, hitachi, japan), wherein the excitation slit is 5nm, the emission slit is 5nm, the voltage is 700V, and fluorescence spectra in the range of 400-600 nm are recorded, and the fluorescence spectra of different concentrations are shown in figure 2 (the concentration is sequentially reduced from top to bottom). And drawing a standard curve by taking the concentration of PFOS as an abscissa and taking the ratio of the fluorescence intensity corresponding to each standard concentration at 470nm to the fluorescence intensity corresponding to a blank solution (obtained by mixing deionized water and fluorescent probe detection solution according to the volume ratio of 1:1) at 470nm as an ordinate, wherein the standard curve is shown in figure 3.
(2) And (3) water body detection:
and (3) testing the fluorescence intensity of the liquid to be tested by using a fluorescence spectrophotometer, and calculating the content of PFOS and derivatives thereof in the liquid to be tested according to a standard curve.
Example 3
The embodiment provides an application of a PFOS fluorescent probe in detecting a water-based foam extinguishing agent, which comprises the following specific application methods:
the PFOS fluorescent probe is dissolved in acetic acid/sodium acetate buffer solution with pH value of 3 to prepare 0.3mg/mL fluorescent probe detection liquid, and the fluorescent probe detection liquid and 100-fold diluted water-based foam extinguishing agent are mixed according to the following ratio of 1:1 to obtain a liquid to be tested, and testing the liquid to be tested according to the same detection conditions as in the example 1.
Example 4
The embodiment provides an application of a PFOS fluorescent probe in natural water body detection, which comprises the following specific application methods:
dissolving a PFOS fluorescent probe in an acetic acid/sodium acetate buffer solution with the pH value of 4 to prepare a fluorescent probe detection solution with the concentration of 0.2 mg/mL, and mixing the fluorescent probe detection solution with a natural water body filtered by 0.45 mu m according to the following ratio of 1:1 to obtain a liquid to be tested, and testing the liquid to be tested according to the same detection conditions as in the example 1.
Example 5
This example provides a method for preparing a PFOS fluorescent probe used in example 2, comprising the steps of:
7.18 g Zinc powder (109.8. Mu. Mol) and 117 mL tetrahydrofuran were added to a three-necked flask and the mixture was cooled to-5~0 ℃under nitrogen. 6 mL TiCl 4 (54.88. Mu. Mol) was slowly added to the flask while maintaining the temperature of the liquid in the flask below 10 ℃. After that, the mixture was stirred at room temperature for 0.5. 0.5 h and then heated to reflux for 2.5. 2.5 h. The mixture was cooled again to-5~0 ℃and 2g of benzophenone (10.98. Mu. Mol) and 2.61 g of 4-hydroxybenzophenone (13.17. Mu. Mol) were slowly added to the flask. And heating and refluxing for 12h under the protection of nitrogen. After the reaction, 10% of K was used 2 CO 3 The reaction was quenched with aqueous solution. The tetrahydrofuran in the liquid phase was removed by suction filtration and rotary evaporation, the product in water was extracted with dichloromethane, the dichloromethane was dried with anhydrous sodium sulfate, the filtrate and the solvent were then rotary dried to give a yellow powder 2.8, g, which was purified by petroleum ether: ethyl acetate according to 9: the mixed solution with the volume ratio of 1 is used as eluent and purified by column chromatography to obtain pale yellow powder monohydroxy tetrastyrene 2.2 g.
0.75. 0.75 g monohydroxy tetraphenyl ethylene (2.14. Mu. Mol), 1.15 g N-BOC bromoethylamine (5.14. Mu. Mol) and 1.25. 1.25 g cesium carbonate were added to a flask containing 25 mL DMF and stirred at ambient temperature for 12h. After the reaction was completed, 5. 5 mL water was added thereto, followed by extraction with ethyl acetate 3 times (10. 10mL each time). The organic phase was then washed with saturated NaCl solution to remove residual DMF, dried with anhydrous sodium sulfate to ethyl acetate, filtered and spin-dried to give the first intermediate 0.9, g.
The first intermediate product 09. 9 g to 10mL HCl and CH 3 In the OH mixed solution, stirring for 12 hours at room temperature, and after the reaction is finished, using the volume ratio of 1:1 and petroleum ether to obtain a second intermediate product of 0.65 g.
0.1g of the second intermediate (255.42. Mu. Mol) and 31.54. Mu.L (510.84. Mu. Mol) of glycidol were added to a flask containing 2.2 mL of methanol and stirred at 40℃for 12 hours, after the reaction was completed, methanol was removed by spin evaporation, and the resultant solid was washed with diethyl ether to remove the excess glycidol, followed by centrifugation and drying to give a PFOS fluorescent probe 0.1g, the nuclear magnetic resonance spectrum of which is shown in FIG. 4.
Example 6
This example provides a method for preparing a PFOS fluorescent probe used in example 3, comprising the steps of:
7.18 g Zinc powder (109.8. Mu. Mol) and 250 mL tetrahydrofuran were added to a three-necked flask and the mixture was cooled to-5~0 ℃under nitrogen. 7 mL TiCl 4 (36.6. Mu. Mol) was slowly added to the flask while maintaining the temperature of the liquid in the flask below 10 ℃. After that, the mixture was stirred at room temperature for 0.4. 0.4 h and then refluxed for 2.2 h. The mixture was again cooled to-5~0 ℃and 2g benzophenone (10.98. Mu. Mol) and 4.35 g 4-hydroxybenzophenone (21.9. Mu. Mol) were slowly added to the flask. And heating and refluxing for 10h under the protection of nitrogen. After the reaction, 10% of K was used 2 CO 3 The reaction was quenched with aqueous solution. The tetrahydrofuran in the liquid phase was removed by suction filtration and rotary evaporation, the product in water was extracted with dichloromethane, the dichloromethane was dried with anhydrous sodium sulfate, the filtrate and the solvent were then rotary dried to give yellow powder 2.1, g, the yellow powder was purified with petroleum ether: ethyl acetate according to 8: the mixed solution with the volume ratio of 1 is used as eluent and purified by column chromatography to obtain pale yellow powder monohydroxy tetrastyrene 1.9 g.
0.75 g monohydroxy tetraphenyl ethylene (2.14. Mu. Mol), 0.96 g N-BOC bromoethylamine (4.3. Mu. Mol) and 1g potassium carbonate were added to a flask containing 25 mL of DMF and stirred at room temperature for 10h. After the reaction was completed, 5. 5 mL water was added thereto, followed by extraction with ethyl acetate 3 times (10. 10mL each time). The organic phase was then washed with saturated NaCl solution to remove residual DMF, dried with anhydrous sodium sulfate in ethyl acetate, filtered and spin-dried to give the first intermediate 0.8, g.
The resulting first intermediate, 0.8g, was added to 10mL of HCl and CH 3 In the mixed solution of OH, stirring at room temperature for 10 hours, and after the reaction is finished, using the volume ratio of 1:1 and petroleum ether to obtain a second intermediate product of 0.6 g.
0.1. 0.1g second intermediate (255.42. Mu. Mol) and 35. Mu.L of 766.26. Mu. Mol) glycidol were added to a flask containing 2.2 mL methanol, and stirred at 38℃for 14 hours, after the reaction was completed, methanol was removed by spin evaporation, and the resultant solid was washed with diethyl ether to remove the excess glycidol, followed by centrifugation and drying to give a PFOS fluorescent probe 0.12. 0.12 g.
Example 7
This example provides a method for preparing the PFOS fluorescent probe used in example 4, comprising the steps of:
7.18 g Zinc powder (109.8. Mu. Mol) and 210 mL tetrahydrofuran were added to a three-necked flask and the mixture was cooled to-5~0 ℃under nitrogen. 6 mL TiCl 4 (54.9. Mu. Mol) was slowly added to the flask while maintaining the temperature of the liquid in the flask below 10 ℃. After that, the mixture was stirred at room temperature for 0.6. 0.6h and then refluxed for 2.2 h. The mixture was cooled again to-5~0 ℃and 2g benzophenone (10.98. Mu. Mol) and 3.26 g of 4-hydroxybenzophenone (16.47. Mu. Mol) were slowly added to the flask. And heating and refluxing for 10h under the protection of nitrogen. After the reaction, 10% of K was used 2 CO 3 The reaction was quenched with aqueous solution. The tetrahydrofuran in the liquid phase is removed by suction filtration and rotary evaporation, the product in water is extracted by dichloromethane, the dichloromethane is dried by adding anhydrous sodium sulfate, the filtrate and the solvent are dried by rotary evaporation, yellow powder 2g is obtained, and the yellow powder is prepared by petroleum ether: ethyl acetate according to 10: the mixed solution with the volume ratio of 1 is used as eluent and purified by column chromatography to obtain pale yellow powder monohydroxy tetrastyrene 1.8 g.
0.75 g monohydroxy tetraphenyl ethylene (2.14. Mu. Mol), 1.21 g N-BOC bromoethylamine (5.38. Mu. Mol) and 0.01 g triethylamine were added to a flask containing 25 mL DMF and stirred at ambient temperature for 14h. After the reaction was completed, 5. 5 mL water was added thereto, followed by extraction with ethyl acetate 3 times (10. 10mL each time). The organic phase was then washed with saturated NaCl solution to remove residual DMF, dried with anhydrous sodium sulfate in ethyl acetate, filtered and spin-dried to give the first intermediate 0.75. 0.75 g.
The resulting first intermediate, 0.75 g, was added to 10mL HCl and CH 3 In the OH mixed solution, stirring for 14h at room temperature, and after the reaction is finished, using the volume ratio of 1:1 and petroleum ether to obtain a second intermediate product of 0.6 g.
0.1. 0.1g of the second intermediate (255.42. Mu. Mol) and 28.38. Mu.L (383.13. Mu. Mol) of glycidol were added to a flask containing 2.2 mL of methanol and stirred at 42℃for 10 hours, after the reaction was completed, methanol was removed by spin evaporation, and the resultant solid was washed with diethyl ether to remove the excess glycidol, followed by centrifugation and drying to obtain the PFOS fluorescent probe 0.1 g.
The foregoing description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical solution of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (10)

1. The PFOS fluorescent probe is characterized in that the chemical structural formula of the PFOS fluorescent probe is shown as formula I:
formula I.
2. Use of the PFOS fluorescent probe of claim 1 for detecting PFOS and derivatives thereof in water, soil or water-based foam extinguishing agents.
3. The application of claim 2, wherein the application comprises:
dissolving a fluorescent probe shown in a formula I in an acidic buffer solution to prepare a fluorescent probe detection solution;
pretreating an object to be detected to obtain liquid to be detected;
and uniformly mixing the fluorescent probe detection liquid and the liquid to be detected, and performing fluorescent detection.
4. The use according to claim 3, wherein the use further comprises quantitative detection, the specific steps comprising:
the PFOS standard substance is weighed to prepare PFOS solution with serial concentration as standard solution, deionized water is used as blank solution, and the standard solution and the blank solution are respectively mixed with the fluorescent probe detection solution according to the following ratio of 1:1, respectively measuring the fluorescence intensity;
and drawing a standard curve by taking the concentration of PFOS as an abscissa and the ratio of the fluorescence intensity of each standard solution to that of the blank solution as an ordinate, and determining the concentration of PFOS and derivatives thereof in the object to be detected based on the standard curve.
5. The use of claim 3 or 4, wherein the fluorescence detection conditions comprise: excitation slit 5nm, emission slit 5nm, voltage 700V, test fluorescence spectrum in 400~600nm scope, record 470nm department fluorescence intensity.
6. The use according to claim 3, wherein the pH of the acidic buffer solution is 3 to 4.
7. The use according to claim 6, wherein the acidic buffer solution is selected from acetic acid/sodium acetate buffer solution, disodium hydrogen phosphate/citric acid buffer solution, citric acid/sodium hydroxide/hydrochloric acid buffer solution, glycine/hydrochloric acid buffer solution, phthalic acid/hydrochloric acid buffer solution or citric acid/sodium citrate buffer solution; and/or
The concentration of the fluorescent probe detection liquid is 0.2-0.3 mg/mL.
8. The use according to claim 5, wherein the fluorescent probe detection solution and the test solution or standard solution are both prepared according to a ratio of 1:1 by volume.
9. The use according to claim 3, wherein,
when the object to be detected is natural water or fire-fighting wastewater, filtering the natural water or fire-fighting wastewater through a filter membrane to obtain liquid to be detected;
when the object to be detected is a water-based foam extinguishing agent, diluting the water-based foam extinguishing agent to obtain liquid to be detected;
when the object to be detected is soil, leaching the soil by water and filtering the leaching solution to obtain the liquid to be detected.
10. A method of preparing the PFOS fluorescent probe of claim 1, comprising:
preparing monohydroxy tetraphenyl ethylene by taking diphenyl ketone and 4-hydroxy diphenyl ketone as raw materials;
reacting the monohydroxy tetraphenyl ethylene, N-Boc bromoethylamine and a base catalyst to prepare a first intermediate product;
the first intermediate obtained is added to HCl and CH 3 Continuously reacting the mixed solution of OH, and pulping to obtain a second intermediate product;
and (3) reacting the second intermediate product with glycidol to obtain the fluorescent probe shown in the formula I.
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