Multi-channel fluorescent array sensor based on dendritic porphyrin as well as preparation method and application of multi-channel fluorescent array sensor

Abstract

The invention discloses a multi-channel fluorescent array sensor based on dendritic porphyrin as well as a preparation method and application of the multi-channel fluorescent array sensor. The fluorescent array sensor comprises any one of two types of fluorescent array sensing units, the two types of fluorescent array sensing units are dendritic porphyrin with a symmetrical structure and repeated unit molecules with different generations on the periphery, and the structural general formula of the dendritic porphyrin is shown as a formula I or a formula II. According to the invention, the excitation spectrum of the dendritic porphyrin and the absorption spectrum of the polycyclic aromatic hydrocarbon to be detected are overlapped to generate an IFE effect, the fluorescent array sensor is used for distinguishing and detecting different polycyclic aromatic hydrocarbons, and the fluorescent array sensor is simple to prepare, simple to operate, easily available in raw materials and capable of rapidly testing various polycyclic aromatic hydrocarbons in time. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the field of fluorescence sensors, and in particular relates to a multi-channel fluorescence array sensor based on dendritic porphyrin and a preparation method and application thereof. Background Art

[0002] Polycyclic aromatic hydrocarbons (PAHs) are harmful persistent organic compounds composed of multiple benzene rings combined in a linear, clustered or angular form. The compound usually exists in the form of white or light yellow solids. At present, more than 100 PAHs have been identified, of which 16 are listed as priority pollutants due to their high toxicity. The sources of PAH pollution are mainly man-made pollution sources and natural pollution sources. If the exposure to PAHs reaches the appropriate threshold, there is a 45% carcinogenic risk. The high lipophilicity of PAHs leads to large-scale deposition in multiple fat cell-dense organs such as the skin, lungs, pancreas, esophagus, bladder, colon and female breast after human exposure. Exposure to PAHs may increase the risk of lung cancer and cardiovascular diseases (CVD) such as atherosclerosis, hypertension, thrombosis and myocardial infarction.

[0003] Traditional PAH detection methods are mainly high performance liquid chromatography, gas chromatography-mass spectrometry, atmospheric pressure gas chromatography, etc. These methods are sensitive and accurate, but expensive and plagued by long analysis times. The data analysis process needs to be completed by experienced analysts, which limits their scope of application. On the other hand, sensors based on nanomaterials, such as silver nanoparticles / graphene hybrids, quantum dots, graphene, and carbon nanotubes are alternatives for PAH monitoring. However, they have poor resolution in multiple analytical detection.

[0004] Fluorescence array sensors are broadly defined as the use of synthetic molecules and / or materials to simulate the mammalian olfactory or taste system. Due to their high sensitivity, strong discrimination ability and real-time detection, they are widely used in the detection of various analytes and anti-counterfeiting technology. Traditional fluorescence sensors mostly use a "lock-key" binding mode, which can achieve high selectivity and specific recognition of specific analytes, but cannot achieve recognition of one or more similar analytes. Therefore, based on the sensing technology of cross-responsive fluorescence arrays, multiple groups of detection signals are generated according to the differential interaction between the analyte and the sensing element, and fingerprint features for each analyte are generated according to different signals, so as to realize the recognition of various analytes with similar structures and properties. Compared with traditional methods, the design of fluorescence sensing arrays is simpler, the operation is easier, the detection time is shorter, and the range and number of recognition are larger.

[0005] However, existing array sensors are often complex in design, high in production cost, narrow in detection range, low in sensitivity, and poor in reproducibility. Therefore, there is still a need to develop a fluorescent array sensor with simple operation, high sensitivity, and wide detection range for the detection of PAHs.

[0006] In recent years, fluorescence-based chemical sensing systems have attracted widespread attention due to their good sensitivity, selectivity, simple operation, real-time detection 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 measurement. The establishment of an IFE-based sensing system requires two optical units, namely the absorber and the luminophore. IFE is a fluorescence quenching phenomenon caused by the absorber absorbing the excitation light or emission light of the luminophore. It does not require any chemical response and is an ideal choice for analytes that lack active recognition sites.

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

[0008] Purpose of the invention: In order to solve the above technical problems, the present invention aims to provide a multi-channel fluorescence array sensor based on dendritic porphyrin, which solves the problems of complex and time-consuming operation of traditional polycyclic aromatic hydrocarbon analysis, and is expected to be expanded to detect more similar aromatic hydrocarbons that lack active recognition sites. The multi-channel fluorescence array sensor has high sensitivity, simple operation, and good reproducibility, and solves the problem that uncharged, non-polar, similar and relatively featureless polycyclic aromatic hydrocarbon compounds and compounds lacking heteroatoms or substituents still lack rapid identification of species.

[0009] The invention also provides a preparation method and application of a multi-channel fluorescence array sensor based on dendritic porphyrin.

[0010] Technical solution: In order to achieve the above-mentioned purpose, the present invention provides a multi-channel fluorescence array sensor based on dendritic porphyrin, comprising any one of two types of fluorescence array sensor units, wherein the two types of fluorescence array sensor units are dendritic porphyrins with symmetrical structures and repeating unit molecules with different generations around them, and the general structure of the dendritic porphyrin is shown in Formula I or Formula II:

[0011]

[0012] Wherein, R is a repeating unit, each independently selected from C 1-6Alkyl, substituted or unsubstituted benzyl ether, the substituents include C 1-6 An alkyl group or a benzyloxy group having 1 to 15 aromatic rings.

[0013] Furthermore, the R is selected from any one of Formula III or Formula IV:

[0014]

[0015] Wherein, n in the formula IV is an integer of 1-4.

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

[0017]

[0018] The multi-channel fluorescence array sensor based on dendritic porphyrin described in the present invention includes any one of ten fluorescence array sensor units, and the structural formulas of the ten fluorescence array sensor units are shown in D1-D10:

[0019]

[0020] Wherein, G1-G5 are selected from any one of the structural fragments of formula III, V-VIII respectively.

[0021] The method for preparing the multi-channel fluorescence array sensor based on dendritic porphyrin of the present invention comprises the following steps:

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

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

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

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

[0026] Preferably, the method for preparing the multi-channel fluorescence array sensor based on dendritic porphyrin of the present invention comprises the following steps:

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

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

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

[0030] (4) With the intermediate 3 of the series I compound 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 reactions. With the intermediate 6 of the series II compound 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 reactions.

[0031] Furthermore, in step (1), p-methoxybenzaldehyde and pyrrole are used as raw materials, propionic acid is used as solvent, and the p-methoxy substituted porphyrin is synthesized by the Adler-Longo method, and then subjected to a boron tribromide demethylation reaction to obtain 3.

[0032]

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

[0034]

[0035] The invention discloses an application of the multi-channel fluorescence array sensor based on dendritic porphyrin in detecting polycyclic aromatic hydrocarbons.

[0036] Furthermore, the multi-channel fluorescence array sensor based on dendritic porphyrin described in the present invention is used to detect polycyclic aromatic hydrocarbons in soil or sediment.

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

[0038] (1) Mixing and shaking the diluted fluorescent sensor unit solution and the polycyclic aromatic hydrocarbon solution to be tested, and measuring the fluorescence intensity data. Repeat the above detection steps for different sensor units;

[0039] (2) using statistical analysis software to process and analyze the fluorescence data, using linear discriminant analysis to convert the fluorescence response pattern into a standard pattern, classifying the data matrix, and obtaining a two-dimensional array fingerprint of the polycyclic aromatic hydrocarbons contained in the test solution to achieve visual identification;

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

[0041] Furthermore, in step (1), the fluorescent array sensor unit is diluted to a final concentration of 1-10 μmol / ml, and the polycyclic aromatic hydrocarbons are diluted to a final concentration of 1-100 μmol / ml.

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

[0043] Furthermore, in step (1), the excitation wavelength for measuring the 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 (Nap), fluorene (Flu), acenaphthene (Ace), acenaphthylene (Acy), phenanthrene (Phe), anthracene (Ant), 1,2-triphenylene (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,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, using different sensing units of the dendritic porphyrin fluorescence array sensor to mix with different polycyclic aromatic hydrocarbons, measuring the fluorescence intensity of each sensing unit, processing the fluorescence data, and classifying the data matrix to achieve the distinction and detection of multiple polycyclic aromatic hydrocarbons.

[0046] The fluorescence data is processed using multiple algorithms such as linear discriminant analysis, and the data matrix is ​​classified to obtain a two-dimensional array distinguishing fingerprint of PAHs, which can be visually identified. The obtained two-dimensional array distinguishing fingerprint is used as a model to detect unknown samples, and the accuracy of the unknown sample prediction is calculated to achieve the unknown distinction and detection of PAHs.

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

[0048] (1) D1-D10 was dissolved in DMSO and diluted to a final concentration of 5 μM as a sensing unit; polycyclic aromatic hydrocarbons were dissolved in DMSO and diluted to a final concentration of 50 μM as the analyte; 100 μL of each sensing unit and analyte were taken and added to a 96-well plate, and the fluorescence intensity data was detected after shaking and mixing. The above steps were repeated for different sensing units.

[0049] (2) The fluorescence data were processed and analyzed using the statistical analysis software SYSTAT 13, and the fluorescence response pattern was converted into a standard pattern using linear discriminant analysis. The data matrix was classified to obtain a two-dimensional array fingerprint of the PAHs contained in the test solution, and visual identification was achieved;

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

[0051] Internal fluorescence filtering effect (IFE) is a phenomenon in which the absorption of the excitation light or emission light (or both) of the luminophore by the absorber leads to a decrease in the fluorescence intensity of the luminophore. IFE is caused by the effective overlap of the absorption spectrum of the absorber with the excitation or emission spectrum of the luminophore. Since the change in the absorbance of the absorber can be converted into an exponential change in the fluorescence signal of the luminophore, the sensitivity of analytical detection is improved. IFE does not need to consider the specific interaction distance and covalent connection between the luminophore and the absorber, avoiding many tedious surface modification or labeling processes.

[0052] The ten sensing units of the present invention are centered on porphyrin, and the double emission peak of porphyrin is located in the near-infrared region, which avoids the interference of the emission peak of polycyclic aromatic hydrocarbons themselves during detection and increases the reliability of the results; benzyl ethers of different generations are peripheral repeating units, and such a structure enables the sensing unit to have double excitation, which can overlap with the absorption spectrum of polycyclic aromatic hydrocarbons. As an absorber for the IFE effect, the absorption spectrum of polycyclic aromatic hydrocarbons is between 250nm-400nm. The excitation peaks of the fluorescent array sensing units D1-D10 at 280nm as luminophores overlap with the absorption peaks of 14 polycyclic aromatic hydrocarbons respectively. Under this excitation, the IFE effect occurs, resulting in a decrease in emission intensity. Since the excitation peak areas of D1-D10 are different, the overlapping areas with the absorption peaks of the 14 polycyclic aromatic hydrocarbons are also different, which further leads to different degrees of reduction in the emission intensity of D1-D10. D1-D10 has double emission peaks, and the changes of two emission peaks can be collected each time detection to achieve single-hole dual signals. The above structural features mean that the array sensor of the present invention has richer fluorescence response.

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

[0054] The dendritic porphyrin multi-channel fluorescence array sensor of the present invention uses the IFE effect to achieve single-hole dual signals, that is, one detection hole obtains two signals at 660nm and 720nm, and multiple signal channels are output, and then linear discriminant analysis is used for data processing, which can realize the identification and differentiation of 14 structural analogs of polycyclic aromatic hydrocarbons. According to the cross-reactivity of the array sensor, the detection results of different polycyclic aromatic hydrocarbons are combined to form a "fingerprint spectrum", thereby realizing the identification and differentiation of unknown polycyclic aromatic hydrocarbons.

[0055] The dendritic porphyrin multi-channel fluorescence array sensor of the present invention obtains multiple detection signals through a single measurement, which not only effectively reduces the number of sensor elements, but also eliminates the negative effects caused by factors such as sensor concentration and instrument parameter settings, and reduces background noise, compared with the sensor unit that relies on the signal intensity change of a single wavelength to identify the object to be detected, which is of great significance to improving the practical application ability of the sensor;

[0056] The array sensor of the present invention has a simple preparation method, does not require professional technicians to operate, has low cost, high sensitivity, and short detection time, can accurately distinguish 14 types of polycyclic aromatic hydrocarbons, and can assist in monitoring environmental pollution, and has high practical value. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0058] Figure 2 The ultraviolet absorption spectrum of the polycyclic aromatic hydrocarbons selected as the test object in Example 13;

[0059] Figure 3 This is the quenching curve of the analyte Phe selected in Example 13 for the sensing units D1-D10;

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

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

[0062] Figure 6 This is a visualization diagram (LDA) of the rapid identification of soil containing different types of PAHs by the array sensor in Example 17. DETAILED DESCRIPTION

[0063] The technical solution of the present invention is further described below in conjunction with the accompanying drawings.

[0064] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources. Experimental methods without specific conditions specified in the examples are usually carried out under conventional conditions or under conditions recommended by the manufacturer.

[0065] Example 1

[0066] (1) Synthesis of porphyrin 4,4',4",4"'-(porphyrin-5,10,15,20-tetrayl)tetraphenol (intermediate 3), the synthetic route is:

[0067]

[0068] Place p-methoxybenzaldehyde, 1 (2.2mmol, 1eq) in a three-necked flask, add 25ml of propionic acid, heat to 140°C, slowly drop pyrrole (2.2mmol, 1eq) in 25ml of propionic acid solution at this temperature, and continue to react for 2 hours. After the reaction is completed, cool to room temperature, distill the reaction solution under reduced pressure to half, add 200ml of methanol, put it in a refrigerator at -4°C, and cool overnight. Filter and wash with methanol (100ml) several times in batches until the filtrate is colorless, filter cake column chromatography (eluent is petroleum ether: dichloromethane = 2:1→1:5) to obtain a purple solid, namely intermediate 2, with a yield of 37%.

[0069] Intermediate 2 (0.75 mmol, 1 eq) was placed in a single-necked bottle, anhydrous dichloromethane (10 ml) was added to dissolve, and boron tribromide (4.5 mmol, 6 eq) was added dropwise under an ice bath. After the addition was complete, the reaction was allowed to proceed at this temperature and the temperature was slowly raised to room temperature for overnight reaction. After the reaction was completed, the reaction solution was filtered and washed several times in batches with dichloromethane (200 ml) until the filtrate was colorless. The filter cake was subjected to column chromatography (eluent was petroleum ether: ethyl acetate = 1:1→1:5) to obtain a purple solid, namely intermediate 3, with a yield of 56%.

[0070] (2) Synthesis of porphyrin 5,5',5",5"'-(porphyrin-5,10,15,20-tetrayl)tetra(benzene-1,3-diol) (Intermediate 6), the synthetic route is:

[0071]

[0072] Dissolve 3,5-dimethoxybenzaldehyde, 4 (2mmol, 1eq) in a three-necked flask, add 25ml of propionic acid, heat to 140°C, slowly drop 25ml of propionic acid solution of pyrrole (2mmol, 1eq) at this temperature, and continue to react for 2 hours. After the reaction is completed, cool to room temperature, distill the reaction solution under reduced pressure to half, add 200ml of methanol, put it in a refrigerator at -4°C, and cool overnight. Filter by suction, and wash with methanol (100ml) several times in batches until the filtrate is colorless, and filter the cake by column chromatography (eluent is petroleum ether: dichloromethane = 2:1→1:5) to obtain a purple solid, namely intermediate 5, with a yield of 21%.

[0073] Intermediate 5 (1.6 mmol. 1 eq) was placed in a single-necked bottle, anhydrous dichloromethane (20 ml) was added to dissolve, and boron tribromide (24 mmol, 15 eq) was added dropwise under an ice bath. After the addition was complete, the reaction was allowed to proceed at this temperature and the temperature was slowly raised to room temperature for overnight reaction. After the reaction was completed, the reaction solution was filtered and washed several times in batches with dichloromethane (100 ml) until the filtrate was colorless. The filter cake was subjected to column chromatography (eluent was petroleum ether: ethyl acetate = 1:1→1:5) to obtain a purple solid, namely intermediate 6, with a yield of 40%.

[0074] Example 2

[0075] The synthesis route of intermediates G1-G4 is as follows:

[0076]

[0077] Dissolve 3,5-dihydroxybenzoic acid methyl ester, 7 (3 mmol, 1 eq) and potassium carbonate (12 mmol, 4 eq) in 20 ml of acetone, add iodomethane (6.6 mmol, 2.2 eq), and react at 55°C overnight. After the reaction is completed, concentrate the reaction solution under reduced pressure, extract with ethyl acetate (20 ml×3) 3 times, and wash with saturated sodium chloride (60 ml). After concentration under reduced pressure, column chromatography (petroleum ether: ethyl acetate = 10:1) was performed to obtain a white solid 8 with a yield of 87%.

[0078] Lithium aluminum hydride (12 mmol, 1.2 eq) was placed in a three-necked flask, and 25 ml of anhydrous tetrahydrofuran was added. In an ice bath, 10 ml of a tetrahydrofuran solution of intermediate 8 (10 mmol, 1 eq) was added dropwise under nitrogen protection. After the addition was complete, the mixture was stirred at this temperature for 20 minutes, and 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 (20 ml) was added to quench the reaction, and the reaction solution was concentrated under reduced pressure, extracted 3 times with ethyl acetate (30 ml×3), washed with saturated sodium chloride (60 ml), concentrated under reduced pressure, and subjected to column chromatography (petroleum ether:ethyl acetate=3:1) to obtain a 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 batches under an ice bath. Under nitrogen protection, the temperature was slowly raised to room temperature and the reaction was carried out for 5 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted with ethyl acetate (30 ml×3) for 3 times, washed with saturated sodium chloride (60 ml), and the solid obtained after concentration was recrystallized from methanol to obtain G1 as a white solid with a yield of 86%.

[0080] G1 (2.5 mmol, 2.1 eq) was placed in a single-necked bottle, potassium carbonate (4.8 mmol, 4 eq), 7 (1.2 mmol, 1 eq), and 20 ml of acetone were added, and the temperature was raised to 55°C and refluxed for reaction for 8 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted with ethyl acetate (50 ml×3) for 3 times, washed with saturated sodium chloride (100 ml), concentrated under reduced pressure, and then column chromatography (petroleum ether: ethyl acetate = 3:1) was performed to obtain intermediate 10 as 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. The mixture was placed in an ice bath and under nitrogen protection, 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, and then the temperature was raised to 70°C and the reaction was carried out for 2 hours. After the reaction was completed, ice water (30 ml) was added to quench the reaction, and the reaction solution was concentrated under reduced pressure. The reaction solution was extracted 3 times with ethyl acetate (40 ml×3), washed with saturated sodium chloride (60 ml), concentrated under reduced pressure, and then column chromatography (petroleum ether:ethyl acetate=1:1) was performed to obtain intermediate 11 as a white solid with a yield of 93%.

[0082] The 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 an ice bath. Under nitrogen protection, the temperature was slowly raised to room temperature and the reaction was carried out for 5 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted with ethyl acetate (40 ml×3) 3 times, washed with saturated sodium chloride (60 ml), and the solid obtained after concentration was recrystallized from methanol to obtain G2 as a white solid with a yield of 75%.

[0083] G2 (1.68 mmol, 2.1 eq) was placed in a single-necked bottle, potassium carbonate (3.5 mmol, 4 eq), 7 (0.8 mmol, 1 eq), and 20 ml of acetone were added, and the temperature was raised to 55°C and refluxed for reaction for 8 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted with ethyl acetate (50 ml×3) for 3 times, washed with saturated sodium chloride (100 ml), concentrated under reduced pressure, and then column chromatography (petroleum ether: ethyl acetate = 1:1) was performed to obtain intermediate 12 as 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. The mixture was placed in an ice bath and under nitrogen protection, 20 ml of a tetrahydrofuran solution of intermediate 12 (2 mmol, 1 eq) was added dropwise. After the addition was complete, the mixture was stirred at this temperature for 20 minutes, and then the temperature was raised to 70°C and the reaction was carried out for 2 hours. After the reaction was completed, ice water was added to quench the reaction, and the reaction solution was concentrated under reduced pressure. The reaction solution was extracted with ethyl acetate (40 ml×3) for 3 times, washed with saturated sodium chloride (100 ml), concentrated under reduced pressure, and subjected to column chromatography (petroleum ether:ethyl acetate=1:1) to obtain intermediate 13 as a white solid with a yield of 91%.

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

[0086] G3 (4.2 mmol, 2.1 eq) was placed in a single-necked bottle, potassium carbonate (8 mmol, 4 eq), 7 (2 mmol, 1 eq), and 40 ml of acetone were added, and the temperature was raised to 55°C and refluxed for reaction for 8 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and ethyl acetate (50 ml×3) was added to extract 3 times, washed with saturated sodium chloride (100 ml), concentrated under reduced pressure, and then column chromatography (petroleum ether: ethyl acetate = 1:2) was performed to obtain intermediate 14 as 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, 10 ml of anhydrous tetrahydrofuran was added, and an ice bath was placed under nitrogen protection. 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, and then the temperature was raised to 70°C and reacted for 2 hours. After the reaction was complete, ice water was added to quench the reaction, the reaction solution was concentrated under reduced pressure, and ethyl acetate (40 ml×3) was added to extract 3 times, washed with saturated sodium chloride (100 ml), concentrated under reduced pressure, and then column chromatography (petroleum ether:ethyl acetate=1:1) was performed to obtain intermediate 15 as a white solid with a yield of 84%.

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

[0089] Example 3

[0090] Synthesis of D1

[0091] Referring to the method of Example 1, p-methoxybenzaldehyde, 1 (2.2mmol, 1eq) was placed in a three-necked flask, added to 25ml of propionic acid, heated to 140°C, and 25ml of propionic acid solution of pyrrole (2.2mmol, eq) was slowly added dropwise at this temperature, and the reaction was continued for 2 hours. After the reaction was completed, it was cooled to room temperature, the reaction solution was distilled under reduced pressure to half, 200ml of methanol was added, and it was placed in a refrigerator at -4°C and cooled overnight. Filtered by suction, and washed with methanol (100ml) in batches several times until the filtrate was colorless, and the filter cake was subjected to column chromatography (eluent was 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 of D2, the synthetic route is:

[0094]

[0095] The intermediate 3 prepared in Example 1 (0.14 mmol, 1 eq), potassium carbonate (1.4 mmol, 10 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and the intermediate G1 prepared in Example 2 (1.4 mmol, 10 eq) were dissolved in THF:DMF=9 ml:3 ml, and the temperature was raised to 70°C and refluxed for reaction for 24 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and dichloromethane (20 ml×3) was added to extract three times, washed with saturated sodium chloride (60 ml), concentrated, and then column chromatography (petroleum ether:dichloromethane=1:3) was performed to obtain a purple solid D2 with a yield of 87%. 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] The intermediate 3 prepared in Example 1 (0.14 mmol, 1 eq), potassium carbonate (1.4 mmol, 10 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and the intermediate G2 prepared in Example 2 (1.4 mmol, 10 eq) were dissolved in THF:DMF=9 ml:3 ml, and the temperature was raised to 70°C and refluxed for reaction for 24 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and dichloromethane (20 ml×3) was added for extraction three times, washed with saturated sodium chloride (60 ml), concentrated, and then column chromatography (petroleum ether; dichloromethane=1:3) was performed to obtain a purple solid D3 with a yield of 85%. 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] Synthesis of D4

[0101] The intermediate 3 prepared in Example 1 (0.14 mmol, 1 eq), potassium carbonate (1.4 mmol, 10 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and the intermediate G3 prepared in Example 2 (1.4 mmol, 10 eq) were dissolved in THF:DMF=9 ml:3 ml, and the temperature was raised to 70°C and refluxed for reaction for 24 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and dichloromethane (20 ml×3) was added to extract three times, washed with saturated sodium chloride (60 ml), concentrated, and then column chromatography (petroleum ether; dichloromethane=1:3) was performed to obtain a purple solid D4 with a yield of 70%. 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] Synthesis of D5

[0104] The 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 the intermediate G4 (1.4 mmol, 10 eq) prepared in Example 2 were dissolved in THF:DMF=9 ml:3 ml, and the temperature was raised to 70°C and refluxed for reaction for 24 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and dichloromethane (20 ml×3) was added for extraction three times, washed with saturated sodium chloride (60 ml), concentrated, and then column chromatography (petroleum ether; dichloromethane=1:3) was performed to obtain a purple solid D5 with a yield of 63%. 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 (2mmol, 1eq) was dissolved in a three-necked flask, added to 25ml of propionic acid, heated to 140°C, and slowly added 25ml of propionic acid solution of pyrrole (2mmol, 1eq) at this temperature, and continued to react for 2 hours. After the reaction was completed, it was cooled to room temperature, and the reaction solution was distilled under reduced pressure to half, and 200ml of methanol was added. It was placed in a refrigerator at -4°C and cooled overnight. Filtered and washed with methanol (100ml) in batches several times until the filtrate was colorless, and the filter cake was subjected to column chromatography (eluent was petroleum ether: dichloromethane = 2:1→1:5) to obtain 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] Synthesis of D7

[0110] Referring to the method of Example 4, the intermediate 6 prepared in Example 1 (0.13 mmol, 1 eq), potassium carbonate (2.6 mmol, 20 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and the intermediate G1 prepared in Example 2 were dissolved in THF:DMF=9 ml:3 ml, and the temperature was raised 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 column chromatography (petroleum ether: dichloromethane=1:3) was performed to obtain a 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] Synthesis of D8

[0113] Referring to the method of Example 4, the intermediate 6 prepared in Example 1 (0.13 mmol, 1 eq), potassium carbonate (2.6 mmol, 20 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and the intermediate G2 prepared in Example 2 were dissolved in THF:DMF=9 ml:3 ml, and the temperature was raised 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 subjected to column chromatography (petroleum ether: dichloromethane=1:3) to obtain a 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] Embodiment 11

[0115] Synthesis of D9

[0116] Referring to the method of Example 4, the intermediate 6 prepared in Example 1 (0.13 mmol, 1 eq), potassium carbonate (2.6 mmol, 20 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and the intermediate G3 prepared in Example 2 were dissolved in THF:DMF=9 ml:3 ml, and the temperature was raised 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 subjected to column chromatography (petroleum ether: dichloromethane=1:3) to obtain a 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] Referring to the method of Example 4, the intermediate 6 prepared in Example 1 (0.13 mmol, 1 eq), potassium carbonate (2.6 mmol, 20 eq), 18-crown ether-6 (0.014 mmol, 0.1 eq), and the intermediate G4 prepared in Example 2 were dissolved in THF:DMF=9 ml:3 ml, and the temperature was raised to 70°C and refluxed for 24 hours. After the reaction was completed, the reaction solution was concentrated under reduced pressure, extracted with dichloromethane three times, washed with saturated sodium chloride, concentrated, and subjected to column chromatography (petroleum ether: dichloromethane=1:3) to obtain a 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 sensor

[0122] The dendrimer molecules D1-D10 synthesized in Examples 3-12 were dissolved in dimethyl sulfoxide to prepare a mother solution with a concentration of 1 mM, thereby obtaining 10 fluorescent array sensor units D1-D10 for use. The excitation spectra thereof are shown in FIG. Figure 1 shown.

[0123] Fourteen commercially available PAHs (product information is shown in Table 1) were dissolved in dimethyl sulfoxide to prepare a mother solution with a concentration of 100 mM to obtain the sample to be tested. The absorption spectrum is shown in Figure 2 As shown in Figure 2, the absorption peak of each PAH overlaps with the excitation peak of the sensing unit in different ways. Figure 3 As shown, taking Phe as an example, the quenching effect of polycyclic aromatic hydrocarbons on the sensor is explored, and the selected molecules have a certain quenching effect on the sensing element.

[0124] Table 1 14 PAHs purchased commercially

[0125]

[0126] The method for distinguishing different types of PAHs is as follows: 100 μL (final concentration 5 μM) of the prepared 10 sensor units (D1, D2, D3, D4, D5, D6, D7, D8, D9, D10) are mixed with 100 μL of 14 different types of PAH solutions (final concentration 50 μM) and shaken for 10 seconds. PAHs include naphthalene (Nap), fluorene (Flu), acenaphthene (Ace), acenaphthylene (Acy), phenanthrene (Phe), anthracene (Ant), 1,2-triphenylene (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,HIperylene) (BghiP). The fluorescence intensity of the IFE effect between the array sensor unit and PAHs was measured at an excitation wavelength of 280 nm and an emission wavelength of 660 nm and 720 nm. Two groups of signals were obtained each time. Ten sensor units generated a total of 20 signal channels (Table 2). The fluorescence intensity was measured using a multifunctional microplate reader, and the relative fluorescence intensity change was the detection signal (I-I0) / I0. Each PAH was detected in 6 replicates using 10 sensor units, and 10 sensor units × 14 PAHs × 2 groups of signals × 6 repetitions = 1680 fluorescence signals were obtained. These 1680 fluorescence signals were then used to form a data matrix. The 10 sensor units had different fluorescence responses to different PAHs.

[0127] Table 220 Sensing units and wavelengths corresponding to the 20 channels

[0128]

[0129] Embodiment 14

[0130] Analysis and processing of fluorescence array sensor data

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

[0132] All variables were used in the model (full mode) and the tolerance was set to 0.001. The Mahalanobis distance from each individual mode to each group centroid in multidimensional space was calculated, and all species were assigned based on the shortest Mahalanobis distance. Figure 4 ) It can be seen that even if there are many types of PAHs and the concentration is low, PAHs of different categories can be distinguished in the end. The Jackknifed Classification Matrix shows that the detection accuracy of the array sensor for 14 PAHs is 100% (Table 3 and Table 4).

[0133] Table 3 Fluorescence response data matrix and LDA results of fluorescence array sensor to different PAHs

[0134]

[0135]

[0136]

[0137] Table 3

[0138]

[0139]

[0140]

[0141] Note: CH1~CH20 means channel 1~channel 20

[0142] Table 4 Verification results of the accuracy of the array sensor classification matrix for different PAH samples

[0143]

[0144] The fluorescence data were processed and analyzed using statistical analysis software. The fluorescence response patterns were converted into canonical patterns using linear discriminant analysis (LDA). The Mahalanobis distance from each single pattern to each group centroid in the multidimensional space was calculated, and all categories were assigned based on the shortest Mahalanobis distance. Figure 4 As shown, the LDA graph shows that even if the concentration of PAHs is low and there are many types, different PAHs can be distinguished in the end. Using the LDA data as a model, the Jackknifed Classification Matrix shows that the accuracy of distinguishing PAHs reaches 100%.

[0145] Embodiment 15

[0146] Differentiation of unknown polycyclic aromatic hydrocarbon samples using fluorescence array sensors

[0147] According to the method of Example 13 for distinguishing 14 different types of PAHs, the only difference is that the 14 PAH solutions are replaced with 56 unknown sample solutions. The method in Example 14 is used to analyze and process the data and record the relative fluorescence intensity changes. Then, linear discriminant analysis is used to verify the ability of the model to test unknown samples and distinguish the types of PAHs. 56 unknown samples are tested, and the fluorescence response pattern is converted into a standard pattern using the linear discriminant analysis method to obtain the LDA graph of the unknown sample. The LDA graph of the unknown sample is overlapped with the LDA graph of the known sample, as shown in FIG. Figure 4As shown in the figure, the symbol type is a cross for unknown samples, and 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 type of PAHs. The Jackknifed Classification Matrix shows that the accuracy of the array sensor in distinguishing unknown samples of PAHs is 100% (Table 5).

[0148] Table 5 Fluorescence response data matrix of array sensor in unknown PAH samples

[0149]

[0150]

[0151]

[0152] Table 5

[0153]

[0154]

[0155] Example 16

[0156] Differentiation of PAH samples with different concentrations using fluorescence array sensors

[0157] Taking Phe as an example, the mother solution was diluted to 100μM, 10μM, 5μM, 2.5μM, 1.5μM, 1μM, 0.75μM, 0.5μM, 0.25μM, 0.1μM, 0.05μM, and 0μM, a total of 12 concentrations. According to the method of distinguishing different types of PAHs in Example 13, the only difference is that the 14 PAH solutions are replaced with Phe solutions of different concentrations. The method in Example 14 is used to analyze and process the data, and each sensor element is mixed with Phe of different concentrations and the fluorescence intensity is measured. After LDA analysis, it can be seen that even Phe with lower concentrations can be completely distinguished ( Figure 5 and Table 6).

[0158] Table 6 Fluorescence response data matrix and LDA results of array sensors to different concentrations of PAHs

[0159]

[0160]

[0161]

[0162] Table 6

[0163]

[0164]

[0165] Embodiment 17

[0166] Differentiation of polycyclic aromatic hydrocarbons in soil samples using fluorescence array sensors

[0167] The silt collected from the riverside of China Pharmaceutical University was randomly added with two unknown PAHs at 100 μM to prepare two actual samples, named Sample 1 and Sample 2. The method for distinguishing different types of PAHs in Example 13 was followed, except that the 14 PAH solutions were replaced with Sample 1 and Sample 2. The data were analyzed and processed using the method in Example 14. Each sensor element was mixed with the two samples and the fluorescence intensity was measured. LDA converted the response signals collected by the training matrix into typical scores according to their Mahalanobis distances, such as Figure 6 As shown, with the unknown sample cluster as the center, circles of different radii are drawn to classify the unknown samples into the known sample cluster closest to the center, indicating that they belong to this type of PAHs, and the two unknown samples are classified into Chr and Flu respectively. It was later proved that the identification of the unknown samples was all correct.

Claims

1. A multi-channel fluorescence array sensor based on dendritic porphyrin, characterized in that: It includes any one of two types of fluorescent array sensor units, wherein the two types of fluorescent array sensor units are dendritic porphyrins with symmetrical structures and molecules with different generations of repeating units around them, and the general structure of the dendritic porphyrin is shown in Formula I or Formula II: Wherein, R is a repeating unit, each independently selected from C 1-6 Alkyl, substituted or unsubstituted benzyl ether, the substituents include C 1-6 An alkyl group or a benzyloxy group having 1 to 15 aromatic rings.

2. The multi-channel fluorescence array sensor based on dendritic porphyrin according to claim 1, characterized in that: The R is selected from any one of Formula III or Formula IV: Wherein, n in the formula IV is an integer of 1-4.

3. The multi-channel fluorescence array sensor based on dendritic porphyrin according to claim 2, characterized in that: The R is preferably selected from any one of the following structural fragments:

4. A multi-channel fluorescence array sensor based on dendritic porphyrin, characterized in that: It includes any one of ten fluorescent array sensor units, and the structural formulas of the ten fluorescent array sensor units are shown in D1-D10: Wherein, G1-G5 are selected from any one of the structural fragments of formula III, V-VIII described in claim 3.

5. A method for preparing the multi-channel fluorescence array sensor based on dendritic porphyrin according to claim 4, characterized in that: The steps include: (1) using p-methoxybenzaldehyde and pyrrole as raw materials, and obtaining the intermediate of the series compound of formula I of claim 1 by the Alder-Longo method; (2) Using 3,5-dimethoxybenzaldehyde and pyrrole as raw materials, the intermediate of the compound of formula II series according to claim 1 is obtained by the Alder-Longo method; (3) Using methyl 3,5-dihydroxybenzoate as the raw material, benzyl ethers V-VIII of different generations were obtained through nucleophilic substitution, reduction, and bromination reactions; (4) With the intermediate of the series of compounds of formula I / II as the core and benzyl ethers of different generations as the peripheral substitution units, different fluorescent array sensing units D1-D10 are obtained through nucleophilic substitution reaction.

6. Use of the multi-channel fluorescence array sensor based on dendritic porphyrin according to claim 1 or claim 4 in detecting polycyclic aromatic hydrocarbons.

7. The use according to claim 6, characterized in that: The application specifically comprises the following steps: (1) Mixing and shaking the diluted fluorescent sensor solution and the test product solution, measuring the fluorescence intensity data, and repeating the above detection steps for different sensor units; (2) using statistical analysis software to process and analyze the fluorescence data, using linear discriminant analysis to convert the fluorescence response pattern into a standard pattern, classifying the data matrix, and obtaining a two-dimensional array fingerprint of the polycyclic aromatic hydrocarbons contained in the test solution to achieve visual identification; (3) The obtained two-dimensional array distinguishing fingerprint map is used as a model to detect unknown samples, and the accuracy of the prediction of unknown samples is calculated to achieve the distinction and detection of polycyclic aromatic hydrocarbons.

8. The use according to claim 7, characterized in that: In the step (1), the fluorescent array sensor is diluted to a final concentration of 1-10 μmol / ml, and the polycyclic aromatic hydrocarbons are diluted to a final concentration of 1-100 μmol / ml.

9. The use according to claim 7, characterized in that: The excitation wavelength for measuring the fluorescence intensity in step (1) is 280 nm, and the emission wavelengths are 660 nm and 720 nm.

10. The use according to claim 7, characterized in that: The polycyclic aromatic hydrocarbons include any one or more combinations of naphthalene (Nap), fluorene (Flu), acenaphthene (Ace), acenaphthylene (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,H,I)perylene (BghiP).

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