CN119977965A - A fluorescent probe molecule for detecting perfluorooctanoic acid and its preparation method and application - Google Patents
A fluorescent probe molecule for detecting perfluorooctanoic acid and its preparation method and application Download PDFInfo
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Abstract
The invention relates to the technical field of pollutant detection and discloses a fluorescent probe molecule for detecting perfluorooctanoic acid, a preparation method and application thereof, wherein the fluorescent probe molecule comprises benzyl biphenyl groups connected with tetrastyrene groups, the fluorescent probe molecule is of a hexagonal annular structure, the tetrastyrene groups distributed on the annular structure of the fluorescent probe molecule can be combined with the perfluorooctanoic acid and generate fluorescence, the tetrastyrene groups are luminous color groups, and the molecular general formula of the fluorescent probe molecule is C 100H76F24N4P4. The cyclic structure provides space for the combination of the tetrastyrene group and the perfluoro caprylic acid molecule, so that the combined tetrastyrene group becomes a luminescent group and has obvious fluorescence response. The invention obtains tetraphenyl ethylene monopyridine through coupling reaction, prepares fluorescent probe molecules through dehalogenation reaction and anion replacement, and provides a new synthesis path. The method is used for detecting the perfluorooctanoic acid, and has good detection sensitivity.
Description
Technical Field
The invention relates to the technical field of pollutant detection, in particular to a fluorescent probe molecule for detecting perfluorooctanoic acid, and a preparation method and application thereof.
Background
Perfluorooctanoic acid (PFOA) is widely applied to the fields of textiles, semiconductors, nano-coatings, fire-fighting foams, medical appliances and the like due to high physicochemical stability, strong hydrophobicity and oleophobicity and high surface activity. However, PFOA has environmental persistence, bioaccumulation and long-distance mobility, can enter human body through food, air or water, accumulate and produce toxicity in organs, immunity, endocrine and reproductive development of animals, etc., seriously threaten ecological environment and human health, and has been listed as a list of persistent contaminated organic matters (POPs).
At present, the method for detecting PFOA mainly comprises a high performance liquid chromatography and a gas chromatography-mass spectrometry, and has the defects of complex operation, high instrument cost and long detection period, so that the detection of PFOA is limited.
The fluorescence analysis method in the prior art has the advantages of high sensitivity, high detection rate and simple operation, and becomes one of the most promising detection methods.
Therefore, the design and synthesis of a novel fluorescent probe are of great significance in order to realize high-sensitivity rapid detection of target compounds, especially PFOA.
Disclosure of Invention
In view of the above, a first objective of the present invention is to provide a fluorescent probe molecule for detecting perfluorooctanoic acid, so as to solve the problem of detecting perfluorooctanoic acid.
Further, a second object of the present invention is to provide a method for preparing a fluorescent probe molecule, so as to realize synthesis of the fluorescent probe molecule for detecting perfluorooctanoic acid.
Further, a third object of the present invention is to provide a method for detecting perfluorooctanoic acid in a contaminant by using the perfluorooctanoic acid in acetonitrile aqueous solution of fluorescent probe molecules.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A fluorescent probe molecule for detecting perfluorooctanoic acid, said fluorescent probe molecule comprising a benzylbiphenyl group linked to a tetrastyryl group;
The fluorescent probe molecules are in a hexagonal annular structure, and tetraphenyl groups distributed on the annular structure of the fluorescent probe molecules can be combined with perfluorooctanoic acid to generate fluorescence, wherein the tetraphenyl groups are luminous color groups;
The molecular general formula of the fluorescent probe molecule is C 100H76F24N4P4;
preferably, the plurality of luminescent clusters are distributed in the annular structure in a central symmetry manner.
Furthermore, the invention provides a preparation method of a fluorescent probe molecule, which is used for preparing the fluorescent probe molecule for detecting perfluorooctanoic acid, and comprises the following steps:
S1) respectively adding 4,4' - (2, 2-diphenylethylene-1, 1-diyl) bis (bromobenzene) and 4-pyridineboronic acid into a stirred reaction vessel, adding an N, N-dimethylformamide solution, and uniformly dissolving the N, N-dimethylformamide to prepare a mixed solution;
S2) adding an alkaline agent into the mixed solution, adding a magneton, adding a catalyst, repeatedly vacuumizing and filling nitrogen three times to prepare a reaction solution;
S3) under the protection of nitrogen, controlling the reaction temperature of the reaction liquid, stirring until the coupling reaction is stopped, cooling to room temperature, filtering the reaction liquid, taking filtrate, and removing the residual N, N-dimethylformamide by rotary evaporation to obtain a crude product;
S4) using neutral Al 2O3 as a stationary phase, using a mixed solution of dichloromethane and petroleum ether as an eluent, purifying a crude product through column chromatography, removing an organic solvent through rotary evaporation, and removing residual organic solvent from an obtained solid through vacuum drying to prepare the organic ligand of tetraphenyl ethylene monopyridine;
S5) dissolving an organic ligand in acetonitrile to prepare an organic ligand solution;
S6) dissolving 4, 4-dibromo methyl biphenyl in acetonitrile, slowly dropwise adding the acetonitrile into an organic ligand solution, controlling the reaction temperature, stirring until dehalogenation reaction is stopped, cooling to room temperature, filtering, adding excessive first anion displacer into the obtained filtrate to enable the solution to completely separate out first precipitate, filtering to obtain a filter cake, dissolving the filter cake in deionized water, filtering and obtaining the filtrate, adding excessive second anion displacer into the filtrate to enable the filtrate to completely separate out second precipitate, and purifying the second precipitate to obtain the fluorescent probe molecule.
Preferably, in step S2), the catalyst is palladium tetraphenylphosphine.
Preferably, in step S2), the alkaline agent is potassium carbonate dissolved in deionized water, and the molar ratio of the alkaline agent to the 4,4' - (2, 2-diphenylethylene-1, 1-diyl) bis (bromobenzene) is (4-8): 1.
Preferably, in steps S1) to S2), the molar ratio of 4,4' - (2, 2-diphenylethylene-1, 1-diyl) bis (bromobenzene) to 4-pyridineboronic acid is 1 (2-3).
Preferably, the reaction temperature of step S3) is 90-110℃and the reaction temperature of step S6) is 70-90 ℃;
In step S4), the eluent contains methylene dichloride and petroleum ether in a volume ratio of 3:1.
Preferably, in step S6), the first anionic displacer is tetrabutylammonium chloride or tetrabutylammonium iodide and the second anionic displacer is ammonium hexafluorophosphate.
Furthermore, the invention also provides a method for detecting perfluorooctanoic acid by using the fluorescent probe molecules, and the fluorescent probe molecules prepared by the preparation method of the fluorescent probe molecules comprise the following steps:
t1) respectively adding acetonitrile and deionized water into a container according to the volume ratio of 1:9, and preparing to obtain a detection solvent;
T2) adding 5mL of detection solvent into a cuvette, and then adding perfluorooctanoic acid with the concentration of 10 -4 mol/L to prepare a first control sample;
T3) adding 5mL of detection solvent into a second cuvette, and then adding fluorescent molecular probe with the concentration of 10 -5 mol/L to prepare a second control sample;
T3) taking five cuvettes, respectively adding 5mL of detection solvent, respectively adding 10 -5 mol/L of fluorescent molecular probe, and then respectively adding perfluorooctanoic acid with corresponding molar concentration into the five cuvettes according to the molar concentration ratio of the fluorescent molecular probe to the perfluorooctanoic acid of 100:1, 10:1, 1:1, 1:10 and 1:100 to prepare five detection samples;
T4) irradiating the two control samples and each test sample with a fluorescence spectrometer, and obtaining a corresponding fluorescence spectrum.
The technical scheme has the beneficial effects that the fluorescent probe molecule for detecting the perfluorooctanoic acid has a ring structure, and the ring structure can provide a space for the tetraphenyl group of the luminous color group to combine with the detected perfluorooctanoic acid molecule, so that the combined tetraphenyl group becomes the luminous color group and has obvious fluorescent response in an effective detection concentration range.
Furthermore, the preparation method of the fluorescent probe molecule provided by the invention obtains tetraphenyl ethylene monopyridine through a coupling reaction, prepares the fluorescent probe molecule through dehalogenation reaction and anion replacement, and provides a new process path for synthesizing a fluorescent probe for detecting PFOA.
Furthermore, the method for detecting the perfluorooctanoic acid by using the fluorescent probe molecules provided by the invention has the advantages of low using amount of the fluorescent probe molecules, obvious fluorescent response phenomenon and good sensitivity.
Drawings
FIG. 1 is a 1 H NMR characterization of the fluorescent probe molecule for detecting perfluorooctanoic acid according to the present invention;
FIG. 2 is a 1 H NMR spectrum of the prepared organic ligand of the present invention;
FIG. 3 is a graph showing fluorescence spectra of test samples for detecting perfluorooctanoic acid at different molar concentrations at a concentration of 10 -5 M, wherein #1 is a control sample of perfluorooctanoic acid at a concentration of 10 -4 M, #2 is a control sample of fluorescent molecular probe at a concentration of 10 -5 M, and the fluorescence spectra of #1 is a horizontal baseline in the graph;
FIG. 4 is a fluorescence photograph of a sample of perfluorooctanoic acid detected at a concentration of 10 -5 M by using a fluorescent molecular probe prepared according to an example of the present invention;
FIG. 5 is an ESI-MS spectrum of a fluorescent molecular probe prepared according to an embodiment of the present invention;
FIG. 6 is an ESI-MS spectrum of an organic ligand prepared in accordance with an embodiment of the present invention;
wherein, C1 is fluorescent molecular probe, PFOA is perfluorooctanoic acid, 1# is 1# reference sample, and 2# is 2# reference sample.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
In the description herein, reference to the term "embodiment," "example," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
A fluorescent probe molecule for detecting perfluorooctanoic acid, the fluorescent probe molecule comprising a tetrastyryl group and a linked benzyl biphenyl group;
The fluorescent probe molecules are in a hexagonal annular structure, and tetraphenyl groups distributed on the annular structure of the fluorescent probe molecules can be combined with perfluorooctanoic acid to generate fluorescence, wherein the tetraphenyl groups are luminous color groups;
The molecular general formula of the fluorescent probe molecule is C 100H76F24N4P4;
the fluorescent probe molecule for detecting the perfluorooctanoic acid provided by the invention contains the benzyl biphenyl group which is connected with the tetrastyrene group and forms a ring structure, and the ring structure provides a space for the tetrastyrene group to combine with the detected perfluorooctanoic acid molecule, so that the combined tetrastyrene group becomes a luminescent color group and has obvious fluorescent response in an effective detection concentration range. The molecular structural formula of the fluorescent probe molecule is as follows:
preferably, the plurality of luminescent clusters are distributed in the annular structure in a central symmetry manner.
The distribution structure of the plurality of luminescent clusters is centrosymmetric, so that the fluorescent probe molecules are more easily aggregated in acetonitrile aqueous solution containing perfluoro caprylic acid, thereby enhancing the fluorescence effect and improving the detection sensitivity.
Furthermore, the invention provides a preparation method of a fluorescent probe molecule, which is used for preparing the fluorescent probe molecule for detecting perfluorooctanoic acid, and comprises the following steps of:
S1) respectively adding 4,4' - (2, 2-diphenylethylene-1, 1-diyl) bis (bromobenzene) and 4-pyridineboronic acid into a stirred reaction vessel, adding an N, N-dimethylformamide solution, and uniformly dissolving the N, N-dimethylformamide to prepare a mixed solution;
S2) adding an alkaline agent into the mixed solution, adding a magneton, adding a catalyst, repeatedly vacuumizing and filling nitrogen three times to prepare a reaction solution;
S3) under the protection of nitrogen, controlling the reaction temperature of the reaction liquid, stirring until the coupling reaction is stopped, cooling to room temperature, filtering the reaction liquid, taking filtrate, and removing the residual N, N-dimethylformamide by rotary evaporation to obtain a crude product;
S4) using neutral Al 2O3 as a stationary phase, using a mixed solution of dichloromethane and petroleum ether as an eluent, purifying a crude product through column chromatography, removing an organic solvent through rotary evaporation, and removing residual organic solvent from an obtained solid through vacuum drying to prepare the organic ligand of tetraphenyl ethylene monopyridine;
S5) dissolving an organic ligand in acetonitrile to prepare an organic ligand solution;
S6) dissolving 4, 4-dibromo methyl biphenyl in acetonitrile, slowly dropwise adding the acetonitrile into an organic ligand solution, controlling the reaction temperature, stirring until dehalogenation reaction is stopped, cooling to room temperature, filtering, adding excessive first anion displacer into the obtained filtrate to enable the solution to completely separate out first precipitate, filtering to obtain a filter cake, dissolving the filter cake in deionized water, filtering and obtaining the filtrate, adding excessive second anion displacer into the filtrate to enable the filtrate to completely separate out second precipitate, and purifying the second precipitate to obtain the fluorescent probe molecule.
The preparation method of the fluorescent probe molecule comprises the steps of preparing tetraphenyl ethylene monopyridine through a coupling reaction of 4,4' - (2, 2-diphenyl ethylene-1, 1-diyl) bis (bromobenzene) and 4-pyridine boric acid, taking the tetraphenyl ethylene monopyridine as an organic ligand, carrying out dehalogenation reaction on the organic ligand and 4, 4-dibromo methyl biphenyl, and carrying out anion replacement and purification to obtain the fluorescent probe molecule with a ring structure.
Preferably, in step S2), the catalyst is palladium tetraphenylphosphine.
The yield of the organic ligand of the tetraphenylphosphine monopyridine is improved through the catalytic coupling reaction of the tetraphenylphosphine palladium.
Preferably, in step S2), the alkaline agent is potassium carbonate dissolved in deionized water, and the molar ratio of the alkaline agent to the 4,4' - (2, 2-diphenylethylene-1, 1-diyl) bis (bromobenzene) is (4-8): 1.
The alkaline environment is provided for the reaction liquid by adding the potassium carbonate, and the volume ratio of the N, N-dimethylformamide solution to the deionized water for dissolving the potassium carbonate is controlled to be 7:1, so that the use amount of the deionized water in the reaction liquid is reduced, and the influence on the reaction efficiency is avoided.
Preferably, in steps S1) to S2), the molar ratio of 4,4' - (2, 2-diphenylethylene-1, 1-diyl) bis (bromobenzene) to 4-pyridineboronic acid is 1 (2-3).
Preferably, the reaction temperature of step S3) is 90-110℃and the reaction temperature of step S6) is 70-90 ℃;
In step S4), the eluent contains methylene dichloride and petroleum ether in a volume ratio of 3:1.
The chemical reaction formula of the tetraphenyl ethylene monopyridine organic ligand of steps S1) to S4) is as follows:
the chemical reaction formulas of steps S5) to S6) are as follows:
preferably, in step S6), the first anionic displacer is tetrabutylammonium chloride or tetrabutylammonium iodide and the second anionic displacer is ammonium hexafluorophosphate.
The first anion displacer is used for displacing chloride ions introduced in the reaction process, and the second anion displacer is used for separating out the fluorescent molecular probe from filtrate, so that the purity and yield of the prepared fluorescent molecular probe can be improved.
Furthermore, the invention also provides a method for detecting perfluorooctanoic acid by using the fluorescent probe molecules, and the fluorescent probe molecules prepared by the preparation method of the fluorescent probe molecules comprise the following steps:
t1) respectively adding acetonitrile and deionized water into a container according to the volume ratio of 1:9, and preparing to obtain a detection solvent;
T2) adding 5mL of detection solvent into a cuvette, and then adding perfluorooctanoic acid with the concentration of 10 -4 mol/L to prepare a first control sample;
T3) adding 5mL of detection solvent into a second cuvette, and then adding fluorescent molecular probe with the concentration of 10 -5 mol/L to prepare a second control sample;
T3) taking five cuvettes, respectively adding 5mL of detection solvent, respectively adding 10 -5 mol/L of fluorescent molecular probe, and then respectively adding perfluorooctanoic acid with corresponding molar concentration into the five cuvettes according to the molar concentration ratio of the fluorescent molecular probe to the perfluorooctanoic acid of 100:1, 10:1, 1:1, 1:10 and 1:100 to prepare five detection samples;
T4) irradiating the two control samples and each test sample with a fluorescence spectrometer, and obtaining a corresponding fluorescence spectrum.
The fluorescence spectrum detection is carried out at room temperature, as shown in fig. 3, C1 in the graph represents the fluorescent probe molecule, PFOA represents perfluorooctanoic acid in the detection sample, the fluorescence intensity of the first control sample (1#) and the second control sample (2#) is close to the baseline, when the molar concentration ratio of the fluorescent molecular probe C1 to the perfluorooctanoic acid is 1:1, fluorescence starts to be obvious, with the increase of the molar concentration of PFOA, the fluorescence emission peak is shifted, the emission peak wavelength is shifted from 580nm to 560nm, with the rapid increase of fluorescence, the interaction between the PFOA with the fluorescent molecular probe C1 with the increased content is continuously enhanced, the obvious fluorescence response phenomenon is realized, and as shown in fig. 4, when the molar concentration ratio of the fluorescent molecular probe C1 to the perfluorooctanoic acid is 1:100, the fluorescence emission color is changed from orange yellow to yellow green, so that the concentration of PFOA with the concentration of more than 10 -5 mol/L can be detected by using the fluorescent probe molecule with the concentration of the invention with good detection sensitivity.
Examples
1. The fluorescent probe molecules of the examples were prepared according to the following procedure:
S1) adding 4,4' - (2, 2-diphenylethylene-1, 1-diyl) bis (bromobenzene) (1.020 mmol) and 4-pyridineboronic acid (0.326 g,2.652 mmol) to a stirred reaction vessel, respectively, adding 42mL of an N, N-dimethylformamide solution, and allowing N, N-dimethylformamide to dissolve uniformly to prepare a mixed solution;
s2) adding an alkaline agent into the mixed solution, putting a magneton, adding catalyst tetra-triphenylphosphine palladium (0.141 g,0.122 mmol), repeatedly vacuumizing and filling nitrogen three times to prepare a reaction solution;
S3) stirring the reaction liquid at 110 ℃ under the protection of nitrogen until the reaction is stopped, cooling to room temperature, filtering the reaction liquid, taking filtrate, and removing N, N-dimethylformamide by rotary evaporation to obtain a crude product;
S4) taking neutral Al 2O3 as a stationary phase, taking a mixed solution of dichloromethane and petroleum ether with the volume ratio of 3:1 as an eluent, purifying a crude product through column chromatography, removing an organic solvent through rotary evaporation, and removing the residual organic solvent from the obtained solid through vacuum drying to prepare an organic ligand (400 mg, 80%) which is a white solid;
s5) dissolving the organic ligand (0.100 g,0.21 mmol) in 50mL of acetonitrile to prepare an organic ligand solution as tetraphenyl ethylene monopyridine;
s6) dissolving 4, 4-dibromomethylbiphenyl (0.077 g,0.23 mmol) in 30mL of acetonitrile, slowly dropwise adding the solution into an organic ligand solution, stirring at 90 ℃ until the reaction is stopped, cooling to room temperature, filtering, adding excessive tetrabutylammonium chloride into the obtained filtrate to enable the solution to completely separate out a first precipitate, filtering to obtain a filter cake, dissolving the filter cake into deionized water, filtering and obtaining the filtrate, adding excessive ammonium hexafluorophosphate into the filtrate to enable the filtrate to completely separate out a second precipitate, and purifying the second precipitate to obtain the fluorescent probe molecule.
2. Test of the example article, hereinafter C1 represents a fluorescent molecular probe:
2.1 characterization of fluorescent molecular probes Using Mass Spectrometry
2.1.1 Detecting the 1 H NMR spectrum of the fluorescent molecular probe C1 prepared in the example by using a nuclear magnetic resonance apparatus, wherein the 1 H NMR spectrum of the obtained nuclear magnetic resonance is shown in FIG. 1;
1H NMR(500MHz,CD3CN)δ8.69–8.66(d,J＝15Hz,8H,Hi),8.18–8.15(d,J＝15Hz,8H,Hh),7.74–7.70(dd,J＝20Hz,16H,Hg,f),7.53–7.51(d,J＝10Hz,8H,Hj),7.30–7.27(d,J＝15Hz,8H,Hk),7.20–7.17(m,12H,Ha,d,e),7.11–7.09(dd,J＝10Hz,8H,Hb,c),5.70(s,8H,Hm).ESI-MS(m/z):1769.0518[M-PF6ˉˉ
]+(calcd m/z:1768.4995),811.9007[M-2PF6]2+(calcd m/z:811.7676),492.8546
ˉˉ
[M-3PF6]3+(calcd m/z:492.8545),333.0748[M-4PF6]4+(calcd m/z:333.4017).
2.1.2 measuring the molecular weight and composition of the fluorescent molecular probe C1 obtained in the example by using an electrospray mass spectrometer (ESI-MS), wherein a mass spectrum of the fluorescent molecular probe C1 is shown in FIG. 5, four signal peaks of M/z=1769.0518, M/z=811.9007, M/z= 492.8546 and M/z= 333.0748 are observed in the graph, the four signal peaks correspond to signals of [ M-PF 6ˉ]+,[M-2PF6ˉ]2+,[M-3PF6ˉ]3+ and [ M-4PF 6ˉ]4+ ] respectively, and the molecular weight of the fluorescent molecular probe C1 is 1913Da according to the calculation of charge and mass-to-charge ratio values and is consistent with a theoretical calculation value of molecular weight of a molecular formula C 100H76F24N4P4.
2.1.3 Detection of the 1 H NMR spectrum of the organic ligand prepared in the examples by means of a nuclear magnetic resonance spectrometer, the 1 H NMR spectrum of the nuclear magnetic resonance obtained being shown in FIG. 2;
1H NMR(500MHz,CDCl3)δ8.64–8.59(d,J＝25Hz,4H,Hi),7.50–7.46(d,J＝30Hz,4H,Hh),7.46–7.41(d,J＝25Hz,4H,Hf),7.18–7.10(m,10H,Ha,b,d,e,g),7.10–7.05(m,4H,Hc).ESI-MS(486.62calcd.For C36H26N2):m/z 487.2178[M+H+]+(calcd m/z:487.2174).
2.1.4 detection of organic ligands prepared in the examples using electrospray mass spectrometer (ESI-MS) the mass spectrum of the obtained organic ligands is shown in FIG. 6.
2.2 Fluorescence Spectrum testing of the fluorescent molecular Probe C1 for detecting perfluorooctanoic acid (PFOA), the steps are as follows:
t1) respectively adding acetonitrile and deionized water into a container according to the volume ratio of 1:9, and preparing to obtain a detection solvent;
T2) adding 5mL of detection solvent into the first cuvette, and then adding perfluorooctanoic acid with the concentration of 10 -4 mol/L to prepare a No.1 control sample;
T3) adding 5mL of detection solvent into a second cuvette, and then adding fluorescent molecular probe C1 with the concentration of 10 -5 mol/L to prepare a No. 2 control sample;
T3) taking five cuvettes, respectively adding 5mL of detection solvent, respectively adding 10 -5 mol/L of fluorescent molecular probe C1, and then respectively adding perfluorooctanoic acid with corresponding molar concentration into the five cuvettes according to the molar concentration ratio of the fluorescent molecular probe C1 to the perfluorooctanoic acid of 100:1, 10:1, 1:1, 1:10 and 1:100 to prepare five detection samples;
T4) irradiating the two control samples and the five detection samples with a fluorescence spectrometer, and obtaining corresponding fluorescence spectrograms.
The obtained fluorescence spectra of the two control samples and the five test samples were collected as shown in fig. 3.
The fluorescence photographs of the two control samples and the five test samples are shown in FIG. 4.
The above fluorescence spectrum detection was performed at room temperature, and as shown in fig. 3, the fluorescence intensities of the 1# control sample and the 2# control sample were close to the baseline, the fluorescence started to be significant when the molar concentration ratio of the fluorescent molecular probe C1 to the perfluorooctanoic acid was 1:1, the fluorescence emission peak was shifted with the increase of the molar concentration of PFOA, the emission peak wavelength was shifted from 580nm to 560nm, and the interaction of PFOA with the fluorescent molecular probe C1 with the increase of the content was continuously enhanced with the rapid increase of fluorescence.
As shown in FIG. 4, when the molar concentration ratio of the photo molecular probe C1 to the perfluorooctanoic acid is 1:100, the color of fluorescence emission is changed from orange yellow to yellow-green, and the fluorescence response phenomenon is obvious.
In summary, the fluorescent probe molecule for detecting perfluorooctanoic acid of the present invention has a ring structure, and the ring structure can provide a space for the tetrastyrene group of the luminescent color group to combine with the detected perfluorooctanoic acid molecule, so that the combined tetrastyrene group becomes the luminescent color group and has obvious fluorescent response in an effective detection concentration range.
Furthermore, the preparation method of the fluorescent probe molecule provided by the invention obtains tetraphenyl ethylene monopyridine through a coupling reaction, prepares the fluorescent probe molecule through dehalogenation reaction and anion replacement, and provides a new process path for synthesizing a fluorescent probe for detecting PFOA.
Furthermore, the method for detecting the perfluorooctanoic acid by using the fluorescent probe molecules provided by the invention has the advantages of low using amount of the fluorescent probe molecules, obvious fluorescent response phenomenon and good sensitivity.
The technical principle of the present invention is described above in connection with the specific embodiments. The description is made for the purpose of illustrating the general principles of the invention and should not be taken in any way as limiting the scope of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of this specification without undue burden.
Claims (9)
1. A fluorescent probe molecule for detecting perfluorooctanoic acid, characterized in that the fluorescent probe molecule comprises a benzyl biphenyl group connected with a tetrastyrene group;
The fluorescent probe molecules are in a hexagonal annular structure, and tetraphenyl groups distributed on the annular structure of the fluorescent probe molecules can be combined with perfluorooctanoic acid to generate fluorescence, wherein the tetraphenyl groups are luminous color groups;
The molecular general formula of the fluorescent probe molecule is C 100H76F24N4P4.
2. The fluorescent probe molecule for detecting perfluorooctanoic acid according to claim 1, wherein a plurality of luminescent clusters are centrally and symmetrically distributed in said ring structure.
3. A method for preparing a fluorescent probe molecule for detecting perfluorooctanoic acid according to claim 1 or 2, comprising the steps of:
S1) respectively adding 4,4' - (2, 2-diphenylethylene-1, 1-diyl) bis (bromobenzene) and 4-pyridineboronic acid into a stirred reaction vessel, adding an N, N-dimethylformamide solution, and uniformly dissolving the N, N-dimethylformamide to prepare a mixed solution;
S2) adding an alkaline agent into the mixed solution, adding a magneton, adding a catalyst, repeatedly vacuumizing and filling nitrogen three times to prepare a reaction solution;
S3) under the protection of nitrogen, controlling the reaction temperature of the reaction liquid, stirring until the coupling reaction is stopped, cooling to room temperature, filtering the reaction liquid, taking filtrate, and removing the residual N, N-dimethylformamide by rotary evaporation to obtain a crude product;
S4) using neutral Al 2O3 as a stationary phase, using a mixed solution of dichloromethane and petroleum ether as an eluent, purifying a crude product through column chromatography, removing an organic solvent through rotary evaporation, and removing residual organic solvent from an obtained solid through vacuum drying to prepare the organic ligand of tetraphenyl ethylene monopyridine;
S5) dissolving an organic ligand in acetonitrile to prepare an organic ligand solution;
S6) dissolving 4, 4-dibromo methyl biphenyl in acetonitrile, slowly dropwise adding the acetonitrile into an organic ligand solution, controlling the reaction temperature, stirring until dehalogenation reaction is stopped, cooling to room temperature, filtering, adding excessive first anion displacer into the obtained filtrate to enable the solution to completely separate out first precipitate, filtering to obtain a filter cake, dissolving the filter cake in deionized water, filtering and obtaining the filtrate, adding excessive second anion displacer into the filtrate to enable the filtrate to completely separate out second precipitate, and purifying the second precipitate to obtain the fluorescent probe molecule.
4. The method of preparing a fluorescent probe molecule according to claim 3, wherein in the step S2), the catalyst is tetraphenylphosphine palladium.
5. The method of preparing a fluorescent probe according to claim 3, wherein in the step S2), the alkaline agent is potassium carbonate dissolved in deionized water, and the molar ratio of the alkaline agent to 4,4' - (2, 2-diphenylethylene-1, 1-diyl) bis (bromobenzene) is (4-8): 1.
6. The method of preparing a fluorescent probe molecule according to claim 3, wherein in steps S1) to S2), the molar ratio of 4,4' - (2, 2-diphenylethylene-1, 1-diyl) bis (bromobenzene) to 4-pyridineboronic acid is 1 (2-3).
7. The method for preparing a fluorescent probe molecule according to claim 3, wherein the reaction temperature of step S3) is 90 to 110 ℃, and the reaction temperature of step S6) is 70 to 90 ℃;
In step S4), the eluent contains methylene dichloride and petroleum ether in a volume ratio of 3:1.
8. The method of preparing a fluorescent probe molecule according to claim 3, wherein in the step S6), the first anionic displacer is tetrabutylammonium chloride or tetrabutylammonium iodide and the second anionic displacer is ammonium hexafluorophosphate.
9. A method for detecting perfluorooctanoic acid using a fluorescent probe molecule, characterized by using the fluorescent probe molecule produced by the method for producing a fluorescent probe molecule according to any one of claims 4 to 7, comprising the steps of:
t1) respectively adding acetonitrile and deionized water into a container according to the volume ratio of 1:9, and preparing to obtain a detection solvent;
T2) adding 5mL of detection solvent into a cuvette, and then adding perfluorooctanoic acid with the concentration of 10 -4 mol/L to prepare a first control sample;
T3) adding 5mL of detection solvent into a second cuvette, and then adding fluorescent molecular probe with the concentration of 10 -5 mol/L to prepare a second control sample;
T3) taking five cuvettes, respectively adding 5mL of detection solvent, respectively adding 10 -5 mol/L of fluorescent molecular probe, and then respectively adding perfluorooctanoic acid with corresponding molar concentration into the five cuvettes according to the molar concentration ratio of the fluorescent molecular probe to the perfluorooctanoic acid of 100:1, 10:1, 1:1, 1:10 and 1:100 to prepare five detection samples;
T4) irradiating the two control samples and each test sample with a fluorescence spectrometer, and obtaining a corresponding fluorescence spectrum.
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