Multichannel fluorescence array sensor based on dendritic porphyrin and preparation method and use thereof

Abstract

The application discloses a kind of based on tree porphyrin multi-channel fluorescence array sensor and its preparation method and purposes, the fluorescence array sensor includes any one of two kinds of fluorescence array sensing units, the two kinds of fluorescence array sensing units are tree porphyrin with symmetrical structure and the repeating unit molecule with different generations in four directions, and the tree porphyrin structure general formula is as shown in formula I or formula II.The application utilizes the excitation spectrum of tree porphyrin and the absorption spectrum of the to-be-measured substance polycyclic aromatic hydrocarbon overlap, IFE effect occurs, is used for the differentiation and detection of different polycyclic aromatic hydrocarbon, and the fluorescence array sensor of the application is simple to prepare, easy to operate, and raw materials are easy to obtain, and various polycyclic aromatic hydrocarbons can be tested in time quickly.

Description

Technical Field

[0001] This invention belongs to the field of fluorescence sensors, and particularly relates to a multichannel fluorescence array sensor based on dendritic porphyrin, its preparation method and application. Background Technology

[0002] Polycyclic aromatic hydrocarbons (PAHs) are hazardous, persistent organic compounds composed of multiple benzene rings linked in linear, clustered, or angular arrangements. These compounds typically exist as white or pale yellow solids. Currently, over 100 PAHs have been identified, with 16 classified as priority pollutants due to their high toxicity. PAH pollution primarily originates from anthropogenic and natural sources. If PAH exposure reaches an appropriate threshold, there is a 45% risk of carcinogenesis. The high lipophilicity of PAHs leads to their significant deposition in organs with dense fat cells, such as the skin, lungs, pancreas, esophagus, bladder, colon, and female breasts, after exposure. PAH exposure may increase the risk of lung cancer, as well as cardiovascular diseases (CVD) such as atherosclerosis, hypertension, thrombosis, and myocardial infarction.

[0003] Traditional methods for detecting polycyclic aromatic hydrocarbons (PAHs) mainly include high-performance liquid chromatography (HPLC), gas chromatography-mass spectrometry (GC-MS), and atmospheric pressure gas chromatography (APGC). These methods are sensitive and accurate, but expensive and time-consuming, requiring experienced analysts to perform the data analysis, thus limiting their application. On the other hand, nanomaterial-based sensors, such as silver nanoparticles / graphene hybrids, quantum dots, graphene, and carbon nanotubes, offer alternatives for PAH monitoring. However, they exhibit poor resolution in multiplex analysis.

[0004] Fluorescent array sensors are broadly defined as those that use synthetic molecules and / or materials to mimic the olfactory or gustatory systems of mammals. Due to their high sensitivity, strong discrimination ability, and real-time detection, they are widely used in various fields such as analyte detection and anti-counterfeiting technologies. Traditional fluorescent sensors often employ a "lock-and-key" combination mode, achieving high selectivity and specificity for specific analytes, but not for identifying a class or multiple similar analytes. Therefore, sensing technology based on cross-responsive fluorescent arrays generates multiple sets of detection signals based on the differential interaction between the analyte and the sensing element. These signals are used to generate fingerprint features for each analyte, enabling the identification of various analytes with similar structures and properties. Compared to traditional methods, fluorescent sensor arrays are simpler to design, easier to operate, have shorter detection times, and can identify a wider range and greater number of analytes.

[0005] However, existing array sensors are often complex in design, expensive to produce, have narrow detection ranges, low sensitivity, and poor reproducibility. Therefore, there is still a need to develop a fluorescent array sensor that is simple to operate, highly sensitive, and has a wide detection range for the detection of polycyclic aromatic hydrocarbons.

[0006] In recent years, fluorescence-based chemical sensing systems have attracted widespread attention due to their excellent sensitivity and selectivity, as well as their simplicity, real-time detection capability, and portability. Various fluorescence sensing methods based on fluorescence quenching have been designed and applied. The inner filter effect (IFE) is an important non-radiative energy conversion model in fluorescence spectroscopy. Establishing an IFE-based sensing system requires two optical units: an absorber and a luminescent emitter. IFE is a fluorescence quenching phenomenon caused by the absorber absorbing excitation or emission light from the luminescent emitter; it does not require any chemical response and is ideal for analytes lacking active recognition sites.

[0007] To understand the extent of polycyclic aromatic hydrocarbon (PAH) exposure, sensitive, selective, and reliable detection methods are needed. Current methods for PAH detection rely on separation techniques, such as liquid chromatography or gas chromatography, followed by detection via mass spectrometry or fluorescence spectroscopy. While these methods are highly sensitive, they are time-consuming and expensive, thus limiting their practical applicability. There is an urgent need to find new detection methods. Summary of the Invention

[0008] Purpose of the invention: To address the aforementioned technical problems, this invention aims to provide a multi-channel fluorescence array sensor based on dendritic porphyrins. This sensor solves the problems of complex and time-consuming operation in traditional polycyclic aromatic hydrocarbon (PAH) analysis and is expected to be extended to detect more similar aromatic hydrocarbons lacking active recognition sites. This multi-channel fluorescence array sensor has high sensitivity, simple operation, and good reproducibility. It solves the problem that there is still a lack of rapid identification of uncharged, nonpolar, similar, and relatively uncharacteristic PAH compounds, as well as compounds lacking heteroatoms or substituents.

[0009] The present invention also provides a method for preparing and using a multichannel fluorescence array sensor based on dendritic porphyrin.

[0010] Technical Solution: To achieve the above objectives, this invention provides a multichannel fluorescence array sensor based on dendritic porphyrin, comprising any one of two types of fluorescence array sensing units. The two types of fluorescence array sensing units are dendritic porphyrins with symmetrical structures and molecules surrounded by repeating units of several generations. The general formula of the dendritic porphyrin structure is shown in Formula I or Formula II:

[0011]

[0012] Where R represents repeating units, each independently selected from C. 1-6Alkyl, substituted, or unsubstituted benzyl ethers, wherein the substituents include C 1-6 Alkyl groups or benzyloxy groups having 1-15 aromatic rings.

[0013] Furthermore, R is selected from either Formula III or Formula IV:

[0014]

[0015] In the above formula IV, n is an integer from 1 to 4.

[0016] Furthermore, the R is preferably selected from any of the following structural segments:

[0017]

[0018] The multichannel fluorescence array sensor based on dendritic porphyrin described in this invention includes any one of ten fluorescence array sensing units, the structural formulas of which are shown in D1-D10:

[0019]

[0020] Among them, G1-G5 are selected from any one of the structural segments of Formula III and V-VIII.

[0021] The method for preparing a multichannel fluorescence array sensor based on dendritic porphyrin according to the present invention includes the following steps:

[0022] (1) Using p-methoxybenzaldehyde and pyrrole as raw materials, intermediates of the I series of compounds were obtained by Alder-Longo method;

[0023] (2) Using 3,5-dimethoxybenzaldehyde and pyrrole as raw materials, intermediates of the II series of compounds were obtained by Alder-Longo method;

[0024] (3) Using methyl 3,5-dihydroxybenzoate as a raw material, benzyl ethers V-VIII of different generations were obtained through nucleophilic substitution, reduction and bromination reactions;

[0025] (4) Using the intermediates of the I / II series compounds as the core and different benzyl ethers as peripheral substitution units, different fluorescent array sensing units D1-D10 are obtained through nucleophilic substitution reactions.

[0026] Preferably, the preparation method of the multichannel fluorescence array sensor based on dendritic porphyrin according to the present invention includes the following steps:

[0027] (1) Using p-methoxybenzaldehyde and pyrrole as raw materials, intermediate 3 of the I series compounds was obtained by Alder-Longo method;

[0028] (2) Using 3,5-dimethoxybenzaldehyde and pyrrole as raw materials, intermediate 6 of the II series compounds was obtained by Alder-Longo method;

[0029] (3) Using methyl 3,5-dihydroxybenzoate as a raw material, benzyl ethers of different generations were obtained through nucleophilic substitution, reduction and bromination reactions;

[0030] (4) Using intermediate 3 of the I series compounds as the core and benzyl ethers of different generations as peripheral substitution units, different fluorescent array sensing units D1-D5 are obtained through nucleophilic substitution reaction. Using intermediate 6 of the II series compounds as the core and benzyl ethers of different generations as peripheral substitution units, different fluorescent array sensing units D6-D10 are obtained through nucleophilic substitution reaction.

[0031] Further, in step (1), para-methoxy-substituted porphyrins are synthesized using p-methoxybenzaldehyde and pyrrole as raw materials and propionic acid as solvent via the Adler-Longo method, and then subjected to boron tribromide demethylation reaction to obtain 3.

[0032]

[0033] Further, in step (2), 3,5-dimethoxybenzaldehyde and pyrrole are used as raw materials and propionic acid is used as solvent to synthesize 3,5-dimethoxy-substituted porphyrin by the Adler-Longo method, and then undergoes demethylation reaction with boron tribromide to obtain 6.

[0034]

[0035] The present invention relates to the application of a dendritic porphyrin-based multichannel fluorescence array sensor in the detection of polycyclic aromatic hydrocarbons.

[0036] Furthermore, the multichannel fluorescence array sensor based on dendritic porphyrin described in this invention is applied to the detection of polycyclic aromatic hydrocarbons in soil or sediment.

[0037] Furthermore, the application specifically includes the following steps:

[0038] (1) Mix the diluted fluorescence sensing unit solution and the polycyclic aromatic hydrocarbon solution to be tested, shake, and then measure the fluorescence intensity data. Repeat the above detection steps for different sensing units.

[0039] (2) Use statistical analysis software to process and analyze fluorescence data, use linear discriminant analysis to convert fluorescence response mode into normal mode, classify data matrix, and obtain two-dimensional array fingerprint spectrum of polycyclic aromatic hydrocarbons contained in the test solution to achieve visual identification.

[0040] (3) The obtained two-dimensional array fingerprint spectrum is used as a model to detect unknown samples and the accuracy of the prediction of unknown samples is calculated, so as to realize the differentiation and detection of polycyclic aromatic hydrocarbons.

[0041] Further, in step (1), the fluorescence array sensing unit is diluted to a final concentration of 1-10 μmol / ml, and the polycyclic aromatic hydrocarbon is diluted to a final concentration of 1-100 μmol / ml.

[0042] Preferably, in step (1), the fluorescence array sensing unit is diluted to a final concentration of 5 μmol / ml, and the polycyclic aromatic hydrocarbon is diluted to a final concentration of 50 μmol / ml.

[0043] Furthermore, in step (1), the excitation wavelength for measuring fluorescence intensity is 280 nm, and the emission wavelengths are 660 nm and 720 nm.

[0044] Further, the polycyclic aromatic hydrocarbons include any one or more combinations of naphthalene, fluorene, acenaphthene, acenaphthene, phenanthrene, anthracene, 1,2-benzophenanthrene, benzo(α)anthracene (BaA), pyrene, fluoranthracene (Fla), benzo[K]fluoranthracene (BkF), dibenzo[a,h]anthracene (DahA), 3,4-benzopyrene (BaP), and benzo(G,H,I)perylene (BghiP).

[0045] The present invention also provides a method for detecting polycyclic aromatic hydrocarbons using the above-mentioned dendritic porphyrin fluorescence array sensor. By using different sensing units of the dendritic porphyrin fluorescence array sensor to mix with different polycyclic aromatic hydrocarbons, the fluorescence intensity of each sensing unit is measured, the fluorescence data is processed, and the data matrix is ​​classified to achieve the differentiation and detection of multiple polycyclic aromatic hydrocarbons.

[0046] Fluorescence data is processed using various algorithms, including linear discriminant analysis, and the data matrix is ​​classified to obtain a two-dimensional array distinguishing fingerprint spectrum of polycyclic aromatic hydrocarbons (PAHs), enabling visual identification. The obtained two-dimensional array distinguishing fingerprint spectrum is used as a model to detect unknown samples, and the accuracy of predicting unknown samples is calculated, thus achieving the differentiation and detection of PAHs from unknown sources.

[0047] The method for detecting polycyclic aromatic hydrocarbons using a dendritic porphyrin fluorescence array sensor of the present invention specifically includes the following steps:

[0048] (1) Dissolve and dilute D1-D10 with DMSO to a final concentration of 5 μM as the sensing unit; dissolve and dilute the polycyclic aromatic hydrocarbon with DMSO to a final concentration of 50 μM as the analyte; take 100 μL of the sensing unit and the analyte respectively and add them to a 96-well plate. After shaking and mixing, detect the fluorescence intensity data. Repeat the above steps for different sensing units.

[0049] (2) The fluorescence data were processed and analyzed using the statistical analysis software SYSTAT 13. The fluorescence response mode was converted into a normalized mode using linear discriminant analysis. The data matrix was classified to obtain a two-dimensional array fingerprint spectrum of polycyclic aromatic hydrocarbons contained in the test solution, so as to achieve visual identification.

[0050] (3) The obtained two-dimensional array fingerprint spectrum is used as a model to detect unknown samples and the accuracy of the prediction of unknown samples is calculated, so as to realize the differentiation and detection of different polycyclic aromatic hydrocarbons.

[0051] Internal fluorescence filtering (IFE) is the phenomenon where the absorption of excitation or emission light (or both) by an absorber by a luminescent source leads to a decrease in the fluorescence intensity of the luminescent source. IFE results from the effective overlap of the absorbance spectrum of the absorber with the excitation or emission spectrum of the luminescent source. Since changes in the absorbance of the absorber can be converted into an exponential change in the fluorescence signal of the luminescent source, the sensitivity of the analytical detection is improved. IFE does not require consideration of the specific interaction distance and covalent bonding between the luminescent and absorber, avoiding many cumbersome surface modification or labeling processes.

[0052] The ten sensing units of this invention are centered around porphyrin, whose dual emission peaks are located in the near-infrared region, avoiding interference from the emission peaks of polycyclic aromatic hydrocarbons (PAHs) themselves during detection and increasing the reliability of the results. Different generations of benzyl ethers serve as peripheral repeating units. This structure allows the sensing units to have dual excitation, which can overlap with the absorption spectra of PAHs. PAHs, as absorbers exhibiting the IFE effect, have absorption spectra between 250 nm and 400 nm. The fluorescence array sensing units D1-D10, acting as emitting sources, have excitation peaks at 280 nm that overlap with the absorption peaks of the 14 PAHs, respectively. Under this excitation, the IFE effect occurs, leading to a decrease in emission intensity. Because the excitation peak areas of D1-D10 differ, and their overlap areas with the absorption peaks of the 14 PAHs also differ, the degree of emission intensity reduction of D1-D10 also varies. D1-D10 have dual emission peaks, and each detection can collect changes in both emission peaks, achieving dual signals from a single aperture. The above structural features mean that the array sensor of the present invention has a richer fluorescence response.

[0053] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:

[0054] The dendritic porphyrin multichannel fluorescence array sensor of this invention utilizes the IFE effect to achieve dual signals per hole, meaning that one detection hole yields two signals at 660 nm and 720 nm. Multiple signal channels output the signal, and data processing is performed using linear discriminant analysis, enabling the identification and differentiation of 14 structurally analogous polycyclic aromatic hydrocarbons (PAHs). Based on the cross-reactivity of the array sensor, a "fingerprint spectrum" is formed by combining the detection results of different PAHs, thereby achieving the identification and differentiation of unknown PAHs.

[0055] The dendritic porphyrin multichannel fluorescence array sensor of the present invention acquires multiple detection signals in a single measurement, which not only effectively reduces the number of sensing elements, but also eliminates the negative impact caused by factors such as sensor concentration and instrument parameter settings, and reduces background noise, compared with sensing units that rely on the signal intensity change of a single wavelength to identify the analyte, thus reducing the negative impact caused by factors such as sensor concentration and instrument parameter settings, and is of great significance for improving the practical application capability of the sensor.

[0056] The array sensor of this invention is simple to prepare, requires no professional technicians, is low in cost, has high sensitivity, and a short detection time. It can accurately distinguish 14 kinds of polycyclic aromatic hydrocarbons and can assist in the monitoring of environmental pollution, thus having high practical value. Attached Figure Description

[0057] Figure 1 The excitation spectra of the ten sensing units D1-D10 selected in Example 13;

[0058] Figure 2 The ultraviolet absorption spectrum of the polycyclic aromatic hydrocarbon selected as the analyte in Example 13;

[0059] Figure 3 The quenching curves of the analyte Phe selected in Example 13 on sensing units D1-D10;

[0060] Figure 4 This is a visualization (LDA) of the rapid identification of polycyclic aromatic hydrocarbons by the array sensor in Example 14;

[0061] Figure 5 This is a visualization (LDA) of the rapid quantification of different concentrations of polycyclic aromatic hydrocarbons (Phe) by the array sensor in Example 16;

[0062] Figure 6 This is a visualization (LDA) of the rapid identification of soil containing different types of polycyclic aromatic hydrocarbons by the array sensor in Example 17. Detailed Implementation

[0063] The technical solution of the present invention will be further described below with reference to the accompanying drawings.

[0064] Unless otherwise specified, all materials and reagents used in the following examples are commercially available. Experimental methods not specifically described in the examples are generally performed under standard conditions or as recommended by the manufacturer.

[0065] Example 1

[0066] (1) Synthesis of porphyrin 4,4',4”,4”′-(porphyrin-5,10,15,20-tetramethyl)tetraphenol (intermediate 3), the synthetic route is as follows:

[0067]

[0068] 2.2 mmol, 1 eq of p-methoxybenzaldehyde was placed in a three-necked flask and added to 25 mL of propionic acid. The mixture was heated to 140 °C, and at this temperature, a 25 mL propionic acid solution of pyrrole (2.2 mmol, 1 eq) was slowly added dropwise. The reaction was continued for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was distilled under reduced pressure until half was obtained. 200 mL of methanol was added, and the mixture was placed in a refrigerator at -4 °C and cooled overnight. The solution was filtered and washed several times with 100 mL of methanol until the filtrate was colorless. The filter cake was subjected to column chromatography (eluent: petroleum ether: dichloromethane = 2:1 → 1:5) to give a purple solid, i.e., intermediate 2, with a yield of 37%.

[0069] Intermediate 2 (0.75 mmol, 1 eq) was placed in a single-necked flask and dissolved in anhydrous dichloromethane (10 mL). Boron tribromide (4.5 mmol, 6 eq) was added dropwise under ice bath conditions. After the addition was complete, the reaction mixture was allowed to react at this temperature and then slowly heated to room temperature overnight. Once the reaction was complete, the reaction mixture was filtered and washed several times in portions with dichloromethane (200 mL) until the filtrate was colorless. The filter cake was then subjected to column chromatography (eluent: petroleum ether: ethyl acetate = 1:1 → 1:5) to give a purple solid, which was intermediate 3, with a yield of 56%.

[0070] (2) Synthesis of porphyrin 5,5',5”,5”′-(porphyrin-5,10,15,20-tetramethyl)tetra(phenyl-1,3-diol) (intermediate 6), the synthetic route is as follows:

[0071]

[0072] 3,5-Dimethoxybenzaldehyde,4 (2 mmol, 1 eq) was dissolved in a three-necked flask and added to 25 mL of propionic acid. The mixture was heated to 140 °C, and at this temperature, a 25 mL propionic acid solution of pyrrole (2 mmol, 1 eq) was slowly added dropwise. The reaction was continued for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was distilled under reduced pressure until half was obtained. 200 mL of methanol was added, and the mixture was placed in a refrigerator at -4 °C and cooled overnight. The solution was filtered and washed several times with methanol (100 mL) in batches until the filtrate was colorless. The filter cake was subjected to column chromatography (eluent: petroleum ether: dichloromethane = 2:1 → 1:5) to give a purple solid, i.e., intermediate 5, with a yield of 21%.

[0073] Intermediate 5 (1.6 mmol / eq) was placed in a single-necked flask and dissolved in anhydrous dichloromethane (20 mL). Boron tribromide (24 mmol / eq) was added dropwise under ice bath conditions. After the addition was complete, the reaction was allowed to proceed at this temperature, and then slowly heated to room temperature overnight. Once the reaction was complete, the reaction solution was filtered and washed several times in portions with dichloromethane (100 mL) until the filtrate was colorless. The filter cake was then subjected to column chromatography (eluent: petroleum ether: ethyl acetate = 1:1 → 1:5) to give a purple solid, namely intermediate 6, with a yield of 40%.

[0074] Example 2

[0075] The synthesis routes for intermediates G1-G4 are shown below:

[0076]

[0077] Methyl 3,5-dihydroxybenzoate, 7 (3 mmol, 1 eq), and potassium carbonate (12 mmol, 4 eq) were dissolved in 20 mL of acetone. Iodomethane (6.6 mmol, 2.2 eq) was added, and the mixture was reacted overnight at 55 °C. After the reaction was complete, the reaction solution was concentrated under reduced pressure, extracted three times with ethyl acetate (20 mL × 3), and washed with saturated sodium chloride (60 mL). After concentration under reduced pressure, column chromatography (petroleum ether:ethyl acetate = 10:1) was performed to give a white solid 8, in 87% yield.

[0078] Lithium aluminum hydride (12 mmol, 1.2 eq) was placed in a three-necked flask, and 25 mL of anhydrous tetrahydrofuran was added. Under nitrogen protection in an ice bath, 10 mL of a tetrahydrofuran solution of intermediate 8 (10 mmol, 1 eq) was added dropwise. After the addition was complete, the mixture was stirred at this temperature for 20 minutes, then heated to 70 °C and reacted for 2 hours. After the reaction was complete, 20 mL of ice water was added to quench the reaction. The reaction solution was concentrated under reduced pressure, extracted three times with ethyl acetate (30 mL × 3), washed with saturated sodium chloride (60 mL), concentrated under reduced pressure, and then subjected to column chromatography (petroleum ether: ethyl acetate = 3:1) to give white solid 9, with a yield of 92%.

[0079] 9 (6 mmol, 1 eq) was placed in a double-necked flask, and triphenylphosphine (7.5 mmol, 1.25 eq) and anhydrous tetrahydrofuran (20 mL) were added. Carbon tetrabromide (7.5 mmol, 1.25 eq) was added in three portions under ice bath. The mixture was slowly heated to room temperature under nitrogen protection and reacted for 5 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted three times with ethyl acetate (30 mL × 3), washed with saturated sodium chloride (60 mL), and the solid obtained after concentration was recrystallized from methanol to give G1, a white solid with a yield of 86%.

[0080] G1 (2.5 mmol, 2.1 eq) was placed in a single-necked flask, and potassium carbonate (4.8 mmol, 4 eq) and 7 (1.2 mmol, 1 eq) were added. 20 mL of acetone was added, and the mixture was heated to 55 °C and refluxed for 8 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted three times with ethyl acetate (50 mL × 3), washed with saturated sodium chloride (100 mL), concentrated under reduced pressure, and then subjected to column chromatography (petroleum ether: ethyl acetate = 3:1) to give intermediate 10, which was a white solid with a yield of 76%.

[0081] Lithium aluminum hydride (18 mmol, 1.5 eq) was placed in a three-necked flask, and 20 mL of anhydrous tetrahydrofuran was added. Under nitrogen protection in an ice bath, 20 mL of a tetrahydrofuran solution of intermediate 10 (12 mmol, 1 eq) was added dropwise. After the addition was complete, the mixture was stirred at this temperature for 20 minutes, then heated to 70 °C and reacted for 2 hours. After the reaction was complete, ice water (30 mL) was added to quench the reaction. The reaction solution was concentrated under reduced pressure, extracted three times with ethyl acetate (40 mL × 3), washed with saturated sodium chloride (60 mL), concentrated under reduced pressure, and then subjected to column chromatography (petroleum ether: ethyl acetate = 1:1) to give intermediate 11 as a white solid with a yield of 93%.

[0082] Intermediate 11 (6 mmol, 1 eq) was placed in a double-necked flask, and triphenylphosphine (7.5 mmol, 1.25 eq) and anhydrous tetrahydrofuran (50 ml) were added. Carbon tetrabromide (7.5 mmol, 1.25 eq) was added in three batches under ice bath. Under nitrogen protection, the mixture was slowly heated to room temperature and reacted for 5 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted three times with ethyl acetate (40 ml × 3), washed with saturated sodium chloride (60 ml), and the solid obtained after concentration was recrystallized from methanol to give G2, a white solid with a yield of 75%.

[0083] G2 (1.68 mmol, 2.1 eq) was placed in a single-necked flask, and potassium carbonate (3.5 mmol, 4 eq) and 7 (0.8 mmol, 1 eq) were added. 20 mL of acetone was added, and the mixture was heated to 55 °C and refluxed for 8 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted three times with ethyl acetate (50 mL × 3), washed with saturated sodium chloride (100 mL), concentrated under reduced pressure, and then subjected to column chromatography (petroleum ether: ethyl acetate = 1:1) to give intermediate 12, which was a white solid with a yield of 64%.

[0084] Lithium aluminum hydride (2.4 mmol, 1.2 eq) was placed in a three-necked flask, and 20 mL of anhydrous tetrahydrofuran was added. Under nitrogen protection in an ice bath, 20 mL of a tetrahydrofuran solution containing intermediate 12 (2 mmol, 1 eq) was added dropwise. After the addition was complete, the mixture was stirred at this temperature for 20 minutes, then the temperature was raised to 70 °C and the reaction was allowed to proceed for 2 hours. After the reaction was complete, ice water was added to quench the reaction, and the reaction solution was concentrated under reduced pressure. The solution was extracted three times with ethyl acetate (40 mL × 3), washed with saturated sodium chloride (100 mL), concentrated under reduced pressure, and then subjected to column chromatography (petroleum ether: ethyl acetate = 1:1) to give intermediate 13 as a white solid with a yield of 91%.

[0085] Intermediate 13 (2 mmol, 1 eq) was placed in a double-necked flask, and triphenylphosphine (2.5 mmol, 1.25 eq) and anhydrous tetrahydrofuran (20 mL) were added. Carbon tetrabromide (2.5 mmol, 1.25 eq) was added in three portions under ice bath. The mixture was slowly heated to room temperature under nitrogen protection and reacted for 5 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted three times with ethyl acetate (50 mL × 3), washed with saturated sodium chloride (100 mL), and the solid obtained after concentration was recrystallized from methanol to give G3, a white solid with a yield of 66%.

[0086] G3 (4.2 mmol, 2.1 eq) was placed in a single-necked flask, and potassium carbonate (8 mmol, 4 eq) and 7 (2 mmol, 1 eq) were added. 40 mL of acetone was added, and the mixture was heated to 55 °C and refluxed for 8 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and extracted three times with ethyl acetate (50 mL × 3). The mixture was washed with saturated sodium chloride (100 mL), concentrated under reduced pressure, and then subjected to column chromatography (petroleum ether: ethyl acetate = 1:2) to give intermediate 14, a white solid with a yield of 43%.

[0087] Lithium aluminum hydride (1.2 mmol, 1.5 eq) was placed in a three-necked flask, and 10 mL of anhydrous tetrahydrofuran was added. Under nitrogen protection in an ice bath, 10 mL of a tetrahydrofuran solution of intermediate 14 (0.8 mmol, 1 eq) was added dropwise. After the addition was complete, the mixture was stirred at this temperature for 20 minutes, then heated to 70 °C and reacted for 2 hours. After the reaction was complete, ice water was added to quench the reaction, and the reaction solution was concentrated under reduced pressure. The mixture was extracted three times with ethyl acetate (40 mL × 3), washed with saturated sodium chloride (100 mL), concentrated under reduced pressure, and then subjected to column chromatography (petroleum ether: ethyl acetate = 1:1) to give intermediate 15 as a white solid with a yield of 84%.

[0088] Intermediate 15 (8 mmol, 1 eq) was placed in a double-necked flask, and triphenylphosphine (20 mmol, 2.5 eq) and anhydrous tetrahydrofuran (20 mL) were added. Carbon tetrabromide (20 mmol, 2.5 eq) was added in three portions under ice bath. The mixture was slowly heated to room temperature under nitrogen protection and reacted for 5 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted three times with ethyl acetate (40 mL × 3), washed with saturated sodium chloride (100 mL), and the solid obtained after concentration was recrystallized from methanol to give G4, a white solid with a yield of 61%.

[0089] Example 3

[0090] Synthesis of D1

[0091] Following the method of Example 1, p-methoxybenzaldehyde, 1 (2.2 mmol, 1 eq) was placed in a three-necked flask, and 25 ml of propionic acid was added. The mixture was heated to 140°C, and at this temperature, a 25 ml propionic acid solution of pyrrole (2.2 mmol, eq) was slowly added dropwise, and the reaction was continued for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was distilled under reduced pressure until half was obtained. 200 ml of methanol was added, and the mixture was placed in a refrigerator at -4°C and cooled overnight. The mixture was filtered, and washed several times in batches with methanol (100 ml) until the filtrate was colorless. The filter cake was subjected to column chromatography (eluent: petroleum ether: dichloromethane = 2:1 → 1:5) to obtain a purple solid, namely D1, with a yield of 37%. 1 H NMR (300MHz, Chloroform-d) δ8.89 (s, 8H), 8.15 (s, 8H), 7.33 (d, J = 2.2Hz, 8H), 4.03 (s, 12H), -2.73 (s, 2H).

[0092] Example 4

[0093] The synthesis route for D2 is as follows:

[0094]

[0095] Intermediate 3 (0.14 mmol, 1 eq) prepared in Example 1, potassium carbonate (1.4 mmol, 10 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and intermediate G1 (1.4 mmol, 10 eq) prepared in Example 2 were dissolved in THF:DMF = 9 ml: 3 ml. The mixture was heated to 70 °C and refluxed for 24 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and extracted three times with dichloromethane (20 ml × 3). The solution was washed with saturated sodium chloride (60 ml), concentrated, and then subjected to column chromatography (petroleum ether: dichloromethane = 1:3) to obtain purple solid D2 in 87% yield. 1 H NMR(300MHz,Chloroform-d)δ8.90(s,8H),8.15(d,J=8.2Hz,8H),7.37(d,J=8.2Hz,8H) ,6.82(d,J=2.3Hz,8H),6.55(t,J=2.3Hz,4H),5.31(s,8H),3.92(s,24H),-2.72(s,2H).

[0096] Example 5

[0097] Synthesis of D3

[0098] Intermediate 3 (0.14 mmol, 1 eq) prepared in Example 1, potassium carbonate (1.4 mmol, 10 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and intermediate G2 (1.4 mmol, 10 eq) prepared in Example 2 were dissolved in THF:DMF = 9 ml: 3 ml. The mixture was heated to 70 °C and refluxed for 24 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and extracted three times with dichloromethane (20 ml × 3). The solution was washed with saturated sodium chloride (60 ml), concentrated, and then subjected to column chromatography (petroleum ether; dichloromethane = 1:3) to obtain purple solid D3 in 85% yield. 1 H NMR(300MHz,Chloroform-d)δ8.90(s,8H),8.15(d,J=8.5Hz,8H),7.43–7.33(m,8H),6.91(d,J=2.2Hz,8H), 6.68(dd,J=4.4,2.3Hz,20H),6.46(t,J=2.3Hz,8H),5.31(s,8H),5.10(s,16H),3.84(s,54H),-2.72(s,2H).

[0099] Example 6

[0100] D4 Synthesis

[0101] Intermediate 3 (0.14 mmol, 1 eq) prepared in Example 1, potassium carbonate (1.4 mmol, 10 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and intermediate G3 (1.4 mmol, 10 eq) prepared in Example 2 were dissolved in THF:DMF = 9 ml: 3 ml. The mixture was heated to 70 °C and refluxed for 24 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and extracted three times with dichloromethane (20 ml × 3). The solution was washed with saturated sodium chloride (60 ml), concentrated, and then subjected to column chromatography (petroleum ether; dichloromethane = 1:3) to obtain purple solid D4 in 70% yield. 1 H NMR(400MHz,Chloroform-d)δ8.90(s,8H),8.16(d,J=8.4Hz,8H),7.39(d,J=8.0Hz,8H),6.92(s,8H),6.77(t,J=2.4Hz,18 H), 6.60 (d, J = 3.6Hz, 42H), 6.42 (t, J = 2.3Hz, 16H), 5.31 (s, 8H), 5.10 (s, 16H), 5.03 (s, 32H), 3.80 (s, 96H), -2.72 (s, 2H).

[0102] Example 7

[0103] D5 Synthesis

[0104] Intermediate 3 (0.14 mmol, 1 eq) prepared in Example 1, potassium carbonate (1.4 mmol, 10 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and intermediate G4 (1.4 mmol, 10 eq) prepared in Example 2 were dissolved in THF:DMF = 9 ml: 3 ml. The mixture was heated to 70 °C and refluxed for 24 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and extracted three times with dichloromethane (20 ml × 3). The solution was washed with saturated sodium chloride (60 ml), concentrated, and then subjected to column chromatography (petroleum ether; dichloromethane = 1:3) to obtain purple solid D5 in 63% yield. 1 H NMR(300MHz,Chloroform-d)δ8.92(s,8H),8.17(d,J=8.0Hz,8H),7.40(d,J=8.1Hz,8H),6.95(s,8H),6.78(s,16H),6.74–6.69( m,36H),6.60–6.54(m,84H),6.41(s,36H),5.30(s,8H),5.10(s,16H),5.02(s,32H),4.96(s,64H),3.77(s,192H),-2.73(s,2H).

[0105] Example 8

[0106] Synthesis of D6

[0107] 3,5-Dimethoxybenzaldehyde,4 (2 mmol, 1 eq) was dissolved in a three-necked flask and added to 25 mL of propionic acid. The mixture was heated to 140 °C, and at this temperature, a 25 mL propionic acid solution of pyrrole (2 mmol, 1 eq) was slowly added dropwise. The reaction was continued for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was distilled under reduced pressure until half was obtained. 200 mL of methanol was added, and the mixture was placed in a refrigerator at -4 °C and cooled overnight. The solution was filtered and washed several times with methanol (100 mL) in batches until the filtrate was colorless. The filter cake was subjected to column chromatography (eluent: petroleum ether: dichloromethane = 2:1 → 1:5) to give a purple solid D6, with a yield of 21%. 1 H NMR (400MHz, Chloroform-d) δ8.97 (s, 8H), 7.43 (d, J = 2.3Hz, 8H), 6.93 (t, J = 2.3Hz, 4H), 3.99 (s, 24H), -2.80 (s, 2H).

[0108] Example 9

[0109] D7 Synthesis

[0110] Following the method of Example 4, intermediate 6 (0.13 mmol, 1 eq), potassium carbonate (2.6 mmol, 20 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and intermediate G1 prepared in Example 2 were dissolved in THF:DMF = 9 ml: 3 ml. The mixture was heated to 70 °C and refluxed for 24 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted three times with dichloromethane, washed with saturated sodium chloride, concentrated, and then subjected to column chromatography (petroleum ether:dichloromethane = 1:3) to obtain purple solid D7, with a yield of 81%. 1 H NMR(300MHz,Chloroform-d)δ8.91(s,8H),7.55(d,J=2.3Hz,8H),7.11(t,J=2.3Hz,4H), 6.71(d,J=2.3Hz,16H),6.48(t,J=2.3Hz,8H),5.22(s,16H),3.82(s,52H),-2.84(s,2H).

[0111] Example 10

[0112] D8 Synthesis

[0113] Following the method of Example 4, intermediate 6 (0.13 mmol, 1 eq), potassium carbonate (2.6 mmol, 20 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and intermediate G2 prepared in Example 2 were dissolved in THF:DMF = 9 ml: 3 ml. The mixture was heated to 70 °C and refluxed for 24 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted three times with dichloromethane, washed with saturated sodium chloride, concentrated, and then subjected to column chromatography (petroleum ether:dichloromethane = 1:3) to obtain purple solid D8, with a yield of 73%. 1 H NMR(300MHz,Chloroform-d)δ8.94(s,8H),7.52(d,J=2.2Hz,8H),7.08(t,J=2.2Hz,4H),6.77(d,J=2.2Hz,16H),6.60(d,J=2.3Hz,1 0H), 6.53 (d, J = 2.3Hz, 24H), 6.44 (t, J = 2.3Hz, 6H), 6.36 (t, J = 2.3Hz, 16H), 5.16 (s, 16H), 4.96 (s, 32H), 3.70 (s, 96H), -2.83 (s, 2H).

[0114] Example 11

[0115] D9 Synthesis

[0116] Following the method of Example 4, intermediate 6 (0.13 mmol, 1 eq), potassium carbonate (2.6 mmol, 20 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and intermediate G3 prepared in Example 2 were dissolved in THF:DMF = 9 ml: 3 ml. The mixture was heated to 70 °C and refluxed for 24 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted three times with dichloromethane, washed with saturated sodium chloride, concentrated, and then subjected to column chromatography (petroleum ether: dichloromethane = 1:3) to obtain purple solid D9, with a yield of 69%. 1 H NMR(300MHz,Chloroform-d)δ8.96(s,8H),7.55(s,8H),7.09(d,J=3.4Hz,4H),6.77(d,J=2.3Hz,8H),6.71(d,J=2.0Hz,8H),6.61(q,J=2.9,2.4Hz, 64H),6.49(p,J=3.8,3.0Hz,54H),6.38–6.32(m,34H),5.11(d,J=13.1Hz, 16H), 5.01 (d, J = 2.9Hz, 32H), 4.85 (s, 64H), 3.68 (s, 192H), -2.85 (s, 2H).

[0117] Example 12

[0118] Synthesis of D10

[0119] Following the method of Example 4, intermediate 6 (0.13 mmol, 1 eq), potassium carbonate (2.6 mmol, 20 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and intermediate G4 prepared in Example 2 were dissolved in THF:DMF = 9 ml: 3 ml. The mixture was heated to 70 °C and refluxed for 24 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted three times with dichloromethane, washed with saturated sodium chloride, concentrated, and then subjected to column chromatography (petroleum ether:dichloromethane = 1:3) to obtain purple solid D10, with a yield of 56%. 1 H NMR(400MHz,Chloroform-d)δ8.99(s,8H),7.57(d,J=3.3Hz,8H),7.05(s,4H),6.75(s,16H),6.58(d,J=12.1Hz,114H),6.52–6 .42(m,166H),6.31(d,J=2.4Hz,64H),5.07(s,16H),4.97(s,32H),4.83(s,64H),4.78(s,128H),3.64(s,384H),-2.90(s,2H).

[0120] Example 13

[0121] System construction and application of fluorescence array sensors

[0122] The dendritic molecules D1-D10 synthesized in Examples 3-12 were dissolved in dimethyl sulfoxide to prepare 1 mM stock solutions, thus obtaining 10 fluorescent array sensing units D1-D10 for later use. Their excitation spectra are shown below. Figure 1 As shown.

[0123] Fourteen commercially purchased polycyclic aromatic hydrocarbons (product information shown in Table 1) were dissolved in dimethyl sulfoxide to prepare 100 mM stock solutions, which were then used to prepare the test samples. Their absorption spectra are shown in the figure below. Figure 2 As shown, the absorption peak of each PAH overlaps differently with the excitation peak of the sensing unit. Figure 3 As shown, taking Phe as an example, the quenching effect of polycyclic aromatic hydrocarbons on sensors was explored. The selected molecules have a certain quenching effect on the sensing element.

[0124] Table 1. 14 commercially purchased polycyclic aromatic hydrocarbons

[0125]

[0126] The method for distinguishing different types of polycyclic aromatic hydrocarbons (PAHs) is as follows: 100 μL of each of the 10 prepared sensing units (D1, D2, D3, D4, D5, D6, D7, D8, D9, D10) (final concentration 5 μM) is mixed with 100 μL of each of the 14 different types of PAH solutions (final concentration 50 μM), and the mixture is shaken for 10 seconds. The PAH types include naphthalene (Nap), fluorene (Flu), acenaphthene (Ace), acenaphthene (Acy), phenanthrene (Phe), anthracene (Ant), 1,2-benzophenanthrene (Chr), benzo(α)anthracene (BaA), pyrene (Pry), fluoranthene (Fla), benzo[K]fluoranthene (BkF), dibenzo[a,h]anthracene (DahA), 3,4-benzopyrene (BaP), and benzo(G,HI)perylene (BghiP). The fluorescence intensity of the array sensing units interacting with polycyclic aromatic hydrocarbons (PAHs) during the IFE effect was measured at an excitation wavelength of 280 nm and emission wavelengths of 660 nm and 720 nm. Two sets of signals were obtained each time, resulting in 20 signal channels generated by the 10 sensing units (Table 2). The fluorescence intensity was measured using a multi-functional microplate reader, and the relative fluorescence intensity change was used as the detection signal (I-I0) / I0. Each PAH was detected in 6 replicates using 10 sensing units, resulting in 1680 fluorescence signals (10 sensing units × 14 PAHs × 2 sets of signals × 6 replicates). These 1680 fluorescence signals were then used to form a data matrix, showing that the 10 sensor units exhibited different fluorescence responses to different PAHs.

[0127] Table 220: Sensing Units and Wavelengths Corresponding to Different Channels

[0128]

[0129] Example 14

[0130] Analysis and processing of fluorescence array sensor data

[0131] The fluorescence response data were processed and analyzed using the statistical analysis software SYSTAT (version 13.0), and the fluorescence response pattern was converted into a canonical pattern using linear discriminant analysis (LDA).

[0132] All variables were used in the model (full model), with a tolerance of 0.001. Mahalanobis distances from each individual model to each group centroid were calculated in the multidimensional space, and all class assignments were based on the shortest Mahalanobis distance. This was then analyzed using LDA plots (…). Figure 4 As can be seen, even with a large number of different polycyclic aromatic hydrocarbons (PAHs) at low concentrations, it is still possible to distinguish between different categories of PAHs. The Jackknifed Classification Matrix shows that the array sensor has a detection accuracy of 100% for 14 PAHs (Tables 3 and 4).

[0133] Table 3. Fluorescence response data matrix and LDA results of fluorescence array sensor for different polycyclic aromatic hydrocarbons.

[0134]

[0135]

[0136]

[0137] Continued from Table 3

[0138]

[0139]

[0140]

[0141] Note: CH1~CH20 represent channels 1~20

[0142] Table 4. Verification results of the accuracy of the array sensor for classifying different polycyclic aromatic hydrocarbon samples.

[0143]

[0144] Fluorescence data were processed and analyzed using statistical analysis software. Linear discriminant analysis (LDA) was used to convert fluorescence response patterns into canonical patterns. The Mahalanobis distance from each individual pattern to each group centroid was calculated in multidimensional space, and all class assignments were based on the shortest Mahalanobis distance. Figure 4 As shown in the figure, the LDA plot shows that even with low concentrations and a wide variety of polycyclic aromatic hydrocarbons (PAHs), it is still possible to distinguish between different PAHs. Using LDA data as a model, the Jackknifed Classification Matrix demonstrates that the accuracy of distinguishing PAHs reaches 100%.

[0145] Example 15

[0146] Differentiation of unknown polycyclic aromatic hydrocarbon samples by a fluorescence array sensor

[0147] Following the method described in Example 13 for distinguishing 14 different types of polycyclic aromatic hydrocarbons (PAHs), the only difference was that the 14 PAH solutions were replaced with 56 unknown sample solutions. Data analysis and processing were performed using the method described in Example 14, and changes in relative fluorescence intensity were recorded. Linear discriminant analysis (LDA) was then used to verify the model's ability to test unknown samples and distinguish the types of PAHs. The 56 unknown samples were tested, and the fluorescence response patterns were converted to canonical patterns using LDA to obtain the LDA maps of the unknown samples. The LDA maps of the unknown samples were then overlaid with those of the known samples, as shown in the image. Figure 4As shown in the figure, the cross-shaped symbols represent unknown samples. The 95% confidence intervals of the 14 unknown samples intersect or overlap with the 95% confidence intervals of the known samples, indicating that they are the same polycyclic aromatic hydrocarbon (PAH). The Jackknifed Classification Matrix shows that the array sensor has a 100% accuracy rate in distinguishing unknown PAH samples (Table 5).

[0148] Table 5. Fluorescence response data matrix of array sensor in unknown polycyclic aromatic hydrocarbon samples.

[0149]

[0150]

[0151]

[0152] Continued from Table 5

[0153]

[0154]

[0155] Example 16

[0156] Distinguishing between polycyclic aromatic hydrocarbon samples of different concentrations using a fluorescence array sensor

[0157] Taking Phe as an example, the mother liquor was diluted to 12 concentrations: 100 μM, 10 μM, 5 μM, 2.5 μM, 1.5 μM, 1 μM, 0.75 μM, 0.5 μM, 0.25 μM, 0.1 μM, 0.05 μM, and 0 μM. Following the method for distinguishing different types of polycyclic aromatic hydrocarbons (PAHs) in Example 13, the only difference was that the 14 PAH solutions were replaced with different concentrations of Phe solutions. Data analysis and processing were performed using the method in Example 14. Fluorescence intensity was measured after each sensing element was mixed with different concentrations of Phe. LDA analysis showed that even low concentrations of Phe could be completely distinguished. Figure 5 (and Table 6).

[0158] Table 6. Fluorescence response data matrix and LDA results of the array sensor for different concentrations of polycyclic aromatic hydrocarbons.

[0159]

[0160]

[0161]

[0162] Continued from Table 6

[0163]

[0164]

[0165] Example 17

[0166] Distinguishing polycyclic aromatic hydrocarbon samples in soil using a fluorescence array sensor

[0167] Two actual samples, named Sample 1 and Sample 2, were prepared by randomly adding two unknown polycyclic aromatic hydrocarbons (PAHs) at 100 μM to silt collected from the riverbank within the campus of China Pharmaceutical University. Following the method for distinguishing different types of PAHs in Example 13, the only difference was that the 14 PAH solutions were replaced with Sample 1 and Sample 2. Data analysis and processing were performed using the method in Example 14. Fluorescence intensity was measured after each sensing element was mixed with two samples. LDA converts the response signal acquired from the training matrix into a typical score based on its Mahalanobis distance, such as... Figure 6 As shown, circles of different radii are drawn with the unknown sample cluster as the center. The unknown samples are assigned to the known sample clusters closest to the center, indicating that they belong to this type of polycyclic aromatic hydrocarbon. The two unknown samples are assigned to Chr and Flu, respectively. It was later proven that the identification of the unknown samples was entirely correct.

Claims

1. A multichannel fluorescence array sensor based on dendritic porphyrin, characterized in that, It includes ten fluorescence array sensing units, the structural formulas of which are shown in D1-D10: ； Wherein, G1 is selected from structural segment III, G2 is selected from structural segment V, G3 is selected from structural segment VI, G4 is selected from structural segment VII, and G5 is selected from structural segment VIII. The structural fragments of Formulas III and V-VIII are shown below: 。 2. The application of the dendritic porphyrin-based multichannel fluorescence array sensor of claim 1 in the detection of polycyclic aromatic hydrocarbons.

3. The application according to claim 2, characterized in that, The application specifically includes the following steps: (1) Mix the diluted fluorescence sensor solution and the test sample solution, shake, and measure the fluorescence intensity data. Repeat the above detection steps for different sensing units. (2) Use statistical analysis software to process and analyze fluorescence data, use linear discriminant analysis to convert fluorescence response mode into normal mode, classify data matrix, and obtain two-dimensional array fingerprint spectrum of polycyclic aromatic hydrocarbons contained in the test solution to achieve visual identification; (3) The obtained two-dimensional array fingerprint spectrum is used as a model to detect unknown samples and the accuracy of the prediction of unknown samples is calculated, so as to realize the differentiation and detection of polycyclic aromatic hydrocarbons.

4. The application according to claim 3, characterized in that, In step (1), the fluorescence array sensor is diluted to a final concentration of 1-10 μmol / ml, and the polycyclic aromatic hydrocarbon is diluted to a final concentration of 1-100 μmol / ml.

5. The application according to claim 3, characterized in that, In step (1), the excitation wavelength for measuring fluorescence intensity is 280 nm, and the emission wavelengths are 660 nm and 720 nm.

6. The application according to claim 3, characterized in that, The polycyclic aromatic hydrocarbons include any one or more combinations of naphthalene, fluorene, acenaphthene, acenaphthene, phenanthrene, anthracene, 1,2-benzophenanthrene, benzo(α)anthracene, pyrene, fluoranthracene, benzo[K]fluoranthracene, dibenzo[a,h]anthracene, 3,4-benzopyrene, and benzo(G,H,I)perylene.

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