A supramolecular colorimetric sensing array for detecting six aniline and phenol pollutants in aqueous solution

Abstract

The present invention discloses a method for detecting six aniline and phenol pollutants in aqueous solution using a supramolecular colorimetric sensing array. The method comprises preparing a supramolecular colorimetric sensing array using supramolecular probes and using the supramolecular colorimetric sensing array to detect six aniline and phenol pollutants, namely p-PD, m-PD, o-PD, m-AP, HQ and RS, in aqueous solution. The supramolecular colorimetric sensing array includes three supramolecular probes MV 2+ @Q[8](P1),VCN 2+ @Q[8](P2) and MVE 2+ @Q[8](P3). This method is simple, rapid, and effective for visual online detection and identification of pollutants. The supramolecular colorimetric sensor array constructed by the present invention can not only distinguish different types of pollutants, but also has a good discrimination effect on different concentration gradients of the same pollutant, pollutant mixtures, and pollutants in actual samples. This array construction has potential application value for the rapid detection of aniline and phenol pollutants in aqueous solutions. The method of the present invention is more intuitive and convenient than traditional detection technologies.

Description

Technical Field

[0001] The invention belongs to the technical field of analytical chemistry, and particularly relates to a method for detecting six aniline and phenol pollutants in an aqueous solution using a supramolecular colorimetric sensor array. Background Art

[0002] With the advancement of industrialization, an increasing number of harmful pollutants are entering the environment upon which humans depend. These substances not only disrupt the balance of ecosystems but also pose a significant threat to human health. Aniline and phenolic compounds, among others, are important organic chemical raw materials and fine chemical intermediates, widely used in industries such as dyes, pharmaceuticals, cosmetics, antioxidants, pesticides, and rubber. As toxic pollutants emitted from various industrial processes, they are difficult to biodegrade in the environment and have become common pollutants. Currently, commonly used methods for detecting aniline and phenolic pollutants include high-performance liquid chromatography (HPLC), gas chromatography (GC), liquid chromatography-mass spectrometry (HPLC-MS), and gas chromatography-mass spectrometry (GC-MS). These methods offer unique advantages such as high sensitivity and selectivity, as well as high accuracy and reliability, and are widely used for the analysis and detection of organic pollutant molecules. However, they also have limitations, such as expensive instrumentation, complex operation, and lack of portability, making them impractical for simple and rapid detection of small organic molecules. Furthermore, aniline and phenolic pollutants often coexist in mixed forms, which can lead to analytical confusion, making detection and differentiation of target analytes a challenge. Therefore, it is of great significance to propose a rapid, timely and convenient analysis and detection method for aniline and phenol pollutants. Summary of the Invention

[0003] The purpose of the present invention is to provide a preparation of a colorimetric supramolecular sensor array and a method for rapid identification and detection of six aniline and phenol pollutants, namely p-phenylenediamine (p-PD), m-phenylenediamine (m-PD), o-phenylenediamine (o-PD), m-aminophenol (m-AP), hydroquinone (HQ) and resorcinol (RS). 2+ 、VCN 2+ and MVE 2+ ( Figure 1 ), respectively, and Q[8] form MV 2+ @Q[8](P1), VCN 2+ @Q[8](P2) and MVE 2+ @Q[8](P3) Three supramolecular probes were used to construct a cucurbitacin-based supramolecular colorimetric sensor array. A certain concentration of aniline and phenol pollutants were added to the colorimetric sensor array to obtain the colorimetric fingerprint of the colorimetric sensor detection array. The colorimetric fingerprint was then distinguished and identified using a classical pattern recognition method, which is simple, sensitive, rapid and effective.

[0004] The technical solution of the present invention is a method for detecting six aniline and phenol pollutants in an aqueous solution using a supramolecular colorimetric sensing array. The method is to prepare a supramolecular colorimetric sensing array using supramolecular probes, and use the supramolecular colorimetric sensing array to detect the six aniline and phenol pollutants, p-PD, m-PD, o-PD, m-AP, HQ and RS, in an aqueous solution.

[0005] The above-mentioned method for detecting six aniline and phenol pollutants in aqueous solution using the supramolecular colorimetric sensor array is carried out according to the following steps:

[0006] (1) Preparation of supramolecular colorimetric sensing array;

[0007] (2) Prepare standard solutions of p-PD, m-PD, o-PD, m-AP, HQ, and RS for aniline and phenol pollutants;

[0008] (3) adding each pollutant standard solution in step (2) to the supramolecular colorimetric sensing array in step (1) to obtain a mixed sample solution, monitoring the color change of the mixed sample solution, reacting for three hours, and obtaining a colorimetric fingerprint of the colorimetric sensing detection array;

[0009] (4) Extracting the image data matrix of the colorimetric fingerprint of step (3), and using classical pattern recognition methods to distinguish and identify the components in the analyte.

[0010] Specifically, in the above-mentioned method for detecting six aniline and phenol pollutants in aqueous solution using a supramolecular colorimetric sensing array, in step (1), the supramolecular colorimetric sensing array includes the following three supramolecular probes: MV 2+ @Q[8] Supramolecular probe, VCN 2+ @Q[8] Supramolecular probes and MVE 2+ @Q[8] Supramolecular probes; the concentrations of the three supramolecular probes P1, P2 and P3 are all 500 μM.

[0011] More specifically, the method for detecting six aniline and phenol pollutants in aqueous solution using the supramolecular colorimetric sensor array is as follows: 2+ The preparation method of @Q[8] supramolecular probe is as follows: 132.8 mg of eight-membered cucurbitacin Q[8], methyl viologen MV 2+ 25.7 mg, the volume ratio of the two is 1:1, that is, the molar ratio is 1:1, dissolved in ultrapure water, ultrasonicated, and transferred to a 100 mL volumetric flask to obtain a concentration of 1×10 -3 mol / L probe solution, and then dilute it to 5×10 -4mol / L, and the P1 supramolecular probe was obtained.

[0012] More specifically, the method for detecting six aniline and phenol pollutants in aqueous solution using the supramolecular colorimetric sensor array is as follows: 2+ Preparation method of @Q[8] supramolecular probe: 132.8 mg of eight-membered cucurbit ring Q[8] and VCN 2+ 43.1 mg, the volume ratio of the two is 1:1, that is, the molar ratio is 1:1, dissolved in ultrapure water, ultrasonicated, and transferred to a 100 mL volumetric flask to obtain a concentration of 1×10 -3 mol / L probe solution, and then dilute it to 5×10 -4 mol / L, and the P2 supramolecular probe was obtained.

[0013] More specifically, the method for detecting six aniline and phenol pollutants in aqueous solution using the supramolecular colorimetric sensor array is as follows: 2+ @Q[8] Preparation method of supramolecular probe: 132.8 mg of eight-membered cucurbit ring Q[8] and MVE 2+ 46.6 mg, the volume ratio of the two is 1:1, that is, the molar ratio is 1:1, dissolved in ultrapure water, ultrasonicated, and transferred to a 100 mL volumetric flask to obtain a concentration of 1×10 -3 mol / L probe solution, and then dilute it to 5×10 -4 mol / L, and the P3 supramolecular probe was obtained.

[0014] Specifically, in the above-mentioned method for detecting six aniline and phenol pollutants in aqueous solution using the supramolecular colorimetric sensor array, in step (3), the concentration of the added pollutant solution is the same as the concentration of the supramolecular probe (500 μM).

[0015] Specifically, in the above-mentioned method for detecting six aniline and phenol pollutants in aqueous solution using a supramolecular colorimetric sensor array, in step (2), the pollutant standard solution is prepared by accurately weighing the required pollutants p-PD, m-PD, o-PD, m-AP, HQ and RS, dissolving them in ultrapure water, and preparing a molar concentration of 1×10 -1 mol / L pollutant standard solution; the pollutants p-PD, m-PD, o-PD, m-AP, HQ and RS are analytical grade standards.

[0016] Specifically, in the above-mentioned method for detecting six aniline and phenol pollutants in an aqueous solution using a supramolecular colorimetric sensor array, in step (3), the method for obtaining the colorimetric fingerprint of the colorimetric sensor array includes: placing the colorimetric sensor array under white light, taking a photo to obtain an image, and using image processing software to extract the RGB value of each sensor unit, and using the difference ΔRGB between the RGB value of each sensor unit and the control value as the colorimetric fingerprint of different pollutant samples based on this detection array.

[0017] Specifically, in the above-mentioned method for detecting six aniline and phenol pollutants in aqueous solution using the supramolecular colorimetric sensor array, in step (4), linear discriminant analysis is performed on the data matrix using SPSS software to obtain a standard model; the standard model is a linear discriminant analysis LDA model. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 :Guest molecule MV 2+ , VCN 2+ , MVE 2+ Chemical structure;

[0019] Figure 2 : Changes in UV-visible absorption spectra of P1(a), P2(b) and P3(c) in the presence of six pollutants (500 μM);

[0020] Figure 3 : Color changes and color difference diagrams before and after the addition of six pollutants to P1 (a), P2 (b) and P3 (c);

[0021] Figure 4 : Linear discriminant analysis diagram of the colorimetric response pattern of the colorimetric array to different pollutants;

[0022] Figure 5 :Linear discriminant analysis of the colorimetric response patterns of o-PD at different concentrations using a colorimetric array;

[0023] Figure 6 :Linear discriminant analysis of the colorimetric response patterns of o-PD / m-PD binary mixed pollutants at different concentration ratios using colorimetric arrays;

[0024] Figure 7 : In the MV 2+ UV absorption spectra (a) when increasing the concentration of Q[8] (20μM); N MV 2+ / N Q[8] UV absorbance relationship curve (b), insert: by continuously changing MV 2+ and the Job diagram obtained with the mole fraction of Q[8];

[0025] Figure 8 :In VCN2+ UV absorption spectra (a) when increasing the concentration of Q[8] (20μM); N VCN 2+ / N Q[8] UV absorbance relationship curve (b), insert: by continuously changing VCN 2+ and the Job diagram obtained with the mole fraction of Q[8];

[0026] Figure 9 :In MVE 2+ UV absorption spectra (a) when increasing the concentration of Q[8] (20μM); N MVE 2+ / N Q[8] UV absorbance relationship curve (b), insert: by continuously changing MVE 2+ Job diagram obtained with the mole fraction of and Q[8]. DETAILED DESCRIPTION

[0027] Example 1:

[0028] 1. Preparation of supramolecular probe standard solution

[0029] 1) Take Q[8]132.8mg, MV 2+ 25.7mg (MV 2+ The volume ratio of the two is 1:1 (i.e. the molar ratio is 1:1), dissolved in ultrapure water, ultrasonicated, and transferred to a 100 mL volumetric flask to obtain a concentration of 1×10 -3 mol / L probe solution, for later use;

[0030] 2) Take the above concentration as 1×10 -3 mol / L probe solution, diluted with water to 5×10 -4 mol / L, and the P1 supramolecular probe is obtained. The probe P1 is colorless.

[0031] 2. Preparation of standard solutions of aniline and phenol pollutants:

[0032] Accurately weigh the analytically pure standards of the required pollutants p-PD, m-PD, o-PD, m-AP, HQ and RS, respectively, dissolve them in ultrapure water, and prepare a molar concentration of 1×10 -1 mol / L pollutant standard solution.

[0033] 3. Detection methods:

[0034] The obtained different pollutant standard solutions were added to the P1 supramolecular probe solution (the molar ratio of P1 supramolecular probe to each pollutant was 1:1), and the solution was allowed to stand for 3 hours. The ultraviolet absorption spectrum of the solution was measured and the color change under natural light was observed.

[0035] 4. Test results:

[0036] The P1 supramolecular probe itself has no color. When p-PD is added, a charge transfer peak is generated at 454nm, and the color of the solution changes to gray under natural light; when m-PD is added, a charge transfer peak is generated at 432nm, and the color of the solution changes to light yellow-brown under natural light; when o-PD is added, a charge transfer peak is generated at 572nm, and the color of the solution changes to blue-gray under natural light; when m-AP is added, a charge transfer peak is generated at 510nm, and the color of the solution changes to light pink under natural light; when HQ is added, a charge transfer peak is generated at 465nm, and the color of the solution changes to pink under natural light; when RS is added, a charge transfer peak is generated at 404nm, and the color of the solution changes to yellow under natural light;

[0037] Example 2

[0038] 1. Preparation of supramolecular probe standard solution

[0039] 1) Take Q[8]132.8mg, VCN 2+ 43.1mg (VCN 2+ The volume ratio of the two is 1:1 (i.e. the molar ratio is 1:1), dissolved in ultrapure water, ultrasonicated, and transferred to a 100 mL volumetric flask to obtain a concentration of 1×10 -3 mol / L probe solution, for later use;

[0040] 2) Take the above concentration as 1×10 -3 mol / L probe solution, diluted with water to 5×10 -4 mol / L, and the P2 supramolecular probe is obtained. The probe P2 is yellow.

[0041] 2. Preparation of standard solutions of aniline and phenol pollutants:

[0042] Accurately weigh the analytically pure standards of the required pollutants p-PD, m-PD, o-PD, m-AP, HQ and RS, dissolve them in ultrapure water, and prepare a molar concentration of 1×10 -1 mol / L standard solutions of each pollutant.

[0043] 3. Determination method:

[0044] Different pollutant standard solutions were added to the P2 supramolecular probe solution (the molar ratio of P2 supramolecular probe to each pollutant was 1:1), and the solution was allowed to stand for 3 hours. The ultraviolet absorption spectrum of the solution was measured and the color change under natural light was observed.

[0045] 4. Measurement results:

[0046] The P2 supramolecular probe itself is yellow. When p-PD is added, a charge transfer peak is generated at 650nm, and the color changes from yellow to grass-green under natural light. When o-PD is added, a charge transfer peak is generated at 670nm, and the color changes from yellow to dark green under natural light. When m-PD is added, there is no obvious charge transfer band, and the color changes from yellow to yellow-green under natural light. When m-AP is added, there is no obvious charge transfer band, and the color changes from yellow to bean green under natural light. When HQ is added, there is no obvious charge transfer band, and the color changes from yellow to yellow-brown under natural light. When RS is added, there is no obvious charge transfer band, and the color changes from yellow to orange under natural light.

[0047] Example 3:

[0048] 1 Preparation of P3 supramolecular probe standard solution

[0049] 1) Take Q[8]132.8mg, MVE 2+ 46.6mg (MVE 2+ The volume ratio of the two is 1:1 (i.e. the molar ratio is 1:1), dissolved in ultrapure water, ultrasonicated, and transferred to a 100 mL volumetric flask to obtain a concentration of 1×10 -3 mol / L probe solution, for later use;

[0050] 2) Take the above concentration as 1×10 -3 mol / L probe solution, diluted with water to 5×10 -4 mol / L, and the P3 supramolecular probe was obtained. The probe P3 was light orange.

[0051] 2. Preparation of standard solutions of aniline and phenol pollutants:

[0052] Accurately weigh the analytically pure standards of the required pollutants p-PD, m-PD, o-PD, m-AP, HQ and RS, dissolve them in ultrapure water, and prepare a molar concentration of 1×10 -1 mol / L standard solutions of each pollutant.

[0053] 3. Determination method:

[0054] Different pollutant standard solutions were added to the P3 supramolecular probe solution (the molar ratio of supramolecular probe to each pollutant was 1:1), and the solution was allowed to stand for 3 hours. The solutions were then subjected to UV absorption spectrum measurement and the color changes under natural light were observed.

[0055] 4. Measurement results:

[0056] The P3 supramolecular probe itself is light orange. When p-PD is added, charge transfer peaks are generated at 422nm and 594nm, and the color changes from light orange to gray-brown under natural light. When HQ is added, a charge transfer peak is generated at 426nm, and the color changes from light orange to light orange-yellow under natural light. When m-PD is added, there is no obvious charge transfer band, and the color changes from light orange to nude under natural light. When o-PD is added, there is no obvious charge transfer band, and the color changes from light orange to pink-brown under natural light. When m-AP is added, there is no obvious charge transfer band, and the color changes from light orange to light pink-orange under natural light. When RS is added, there is no obvious charge transfer band, and the color changes from light orange to ginger under natural light.

[0057] Example 4:

[0058] The color changes of P1, P2 and P3 in Examples 1-3 were photographed respectively to design a colorimetric array of 3 sensor elements × 6 pollutants. The above 6 pollutants were distinguished by comparing the color signals of the matrix under natural light.

[0059] Example 5:

[0060] 1) Three supramolecular probes, P1 (500 μM), P2 (500 μM), and P3 (500 μM), were prepared in ultrapure water. A 96-well white titration plate was used to add 300 μL of a mixed sample solution of each of the three probes (all at 500 μM) and six pollutants (p-PD, m-PD, o-PD, m-AP, HQ, and RS) (500 μM) to each well. Five replicates were generated for each mixed sample. The reaction was allowed to proceed for three hours. The 96-well plate was then exposed to white light, and an image was captured. The RGB values ​​of each well were extracted using image processing software. The difference (ΔRGB) between the RGB value of each well and the control value was used as the colorimetric fingerprint of each pollutant sample based on this detection array. The resulting data matrix consisted of three sensing systems × six pollutants × five replicates. This data matrix was subjected to linear discriminant analysis (LDA) using SPSS version 22.0. In the LDA model, five replicates of the same pollutant clustered together and were well separated from the points of other pollutants.

[0061] Results: From the data results, it can be seen that the sensor array can detect and identify six different pollutants: p-PD, m-PD, o-PD, m-AP, HQ, and RS.

[0062] 2) Using the method described in 1), o-PD was selected as the model analyte, and colorimetric fingerprints of 7 different o-PD concentrations (0 μM, 10 μM, 50 μM, 100 μM, 200 μM, 300 μM, 400 μM, and 500 μM) were obtained. A data matrix consisting of 3 sensor elements × 8 o-PD concentrations × 5 parallel experiments was obtained, and the data were analyzed using LDA.

[0063] Results: In the LDA model, the o-PD concentration distribution gradually transitions from positive factors to negative factors along the X-axis. From these data results, it can be seen that the sensor array can, to a certain extent, realize the identification of pollutants of different concentrations.

[0064] 3) Using the method described in 1), a binary mixture of p-PD and m-PD was selected as a model analyte. Colorimetric fingerprints were obtained for five different concentration ratios of the o-PD / m-PD binary mixture (0 μM:500 μM, 150 μM:350 μM, 250 μM:250 μM, 150 μM:350 μM, and 500 μM:0 μM). This yielded a data matrix consisting of three sensor elements, five different concentration ratios of the o-PD / m-PD binary mixture, and five replicates. LDA was used for data analysis. In the LDA model, five replicate points of the binary mixture of pollutants at the same concentration ratio clustered together and were well separated from points of other binary mixtures of pollutants at different concentration ratios.

[0065] Results: From the data results, it can be seen that the sensor array can identify mixed pollutants to a certain extent.

[0066] Advantageous Effects of the Invention

[0067] With the increasing demands for environmental protection, monitoring and detecting environmental pollutants with complex components is particularly important for environmental protection and human health. The optical sensor array is composed of a wide spectrum of cross-responsive sensing units and has the ability to detect and monitor complex mixtures. Cucurbitacin has a hydrophobic cavity and a negatively charged carbonyl port, which can react with some guest molecules to form a probe with optical response. Therefore, three electron-deficient guest MVs were selected in the present invention. 2+ 、VCN 2+ and MVE 2+ , respectively, together with Q[8] to form MV 2+ @Q[8](P1), VCN 2+ @Q[8](P2) and MVE 2+@Q[8](P3) three supramolecular probes, and then designed and constructed a cucurbitacin-based supercolorimetric supramolecular sensor array system. The sensor array uses the different responses of each sensor element to different aniline and phenol pollutants to identify and detect six pollutants (p-PD, m-PD, o-PD, m-AP, HQ, RS) in aqueous solution.

[0068] Compared with the prior art, the present invention has obvious beneficial effects. From the above technical scheme, it can be seen that the present invention is based on a supramolecular probe formed by three guest molecules and a cucurbit ring. Under natural light, the colors of the three probes are different, P1 is colorless, P2 is yellow, and P3 is light orange. When six aniline and phenol pollutants, p-PD, m-PD, o-PD, m-AP, HQ and RS, are added to the probe, the response mode and response degree of different probes to the above six pollutants are quite different. The three probes are placed in a 96-well plate under white light and designed into a colorimetric array of 3 sensor elements × 6 pollutants. The image is taken and the RGB value of each well is extracted using image processing software. The difference ΔRGB between the RGB value of each well and the control value is used as the colorimetric fingerprint of different pollutant samples based on this detection array. Finally, linear discriminant analysis (LDA) was used to perform pattern recognition on the colorimetric fingerprints of the six pollutants on the sensor array and evaluate the response of the sensor array to the test samples, thereby realizing the detection of the six pollutants p-PD, m-PD, o-PD, m-AP, HQ and RS in aqueous solution.

[0069] The detection method of six aniline and phenol pollutants p-PD, m-PD, o-PD, m-AP, HQ and RS provided by the present invention is more intuitive and convenient than traditional detection technology.

[0070] The inventors conducted the following experiments to verify the effects of the present invention:

[0071] Experimental example:

[0072] 1. Test reagents and reagent instruments

[0073] 1.1 Test materials and reagents

[0074] Q[8] is made in the laboratory, MV 2+ 、VCN 2+ and MVE 2+ All were purchased from Chemsoon, and six aromatic pollutants (p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, m-aminophenol, hydroquinone, and resorcinol) were purchased from Inokane. All reagents were of analytical reagent grade and used without further purification. Ultrapure water was used to prepare experimental samples.

[0075] 1.2 Test instruments

[0076] Shimadzu UV-2700 UV-visible spectrophotometer (Shimadzu, China), Sarteorius-BS110S electronic balance, and ultrasonic cleaner were used.

[0077] 2 Test methods

[0078] 2.1 Preparation of P1 supramolecular probe standard solution

[0079] 1) Take Q[8]132.8mg, MV 2+ 25.7mg (MV 2+ The volume ratio of the two is 1:1 (i.e. the molar ratio is 1:1), dissolved in ultrapure water, ultrasonicated, and transferred to a 100 mL volumetric flask to obtain a concentration of 1×10 -3 mol / L probe solution, for later use;

[0080] 2) Take the above concentration as 1×10 -3 mol / L probe solution, diluted with water to 5×10 -4 mol / L, and the P1 supramolecular probe was obtained.

[0081] 2.2 Preparation of P2 supramolecular probe standard solution

[0082] 1) Take Q[8]132.8mg, VCN 2+ 43.1mg (VCN 2+ The volume ratio of the two is 1:1 (i.e. the molar ratio is 1:1), dissolved in ultrapure water, ultrasonicated, and transferred to a 100 mL volumetric flask to obtain a concentration of 1×10 -3 mol / L probe solution, for later use;

[0083] 2) Take the above concentration as 1×10 -3 mol / L probe solution, diluted with water to 5×10 -4 mol / L, and the P2 supramolecular probe was obtained.

[0084] 2.3 Preparation of P3 supramolecular probe standard solution

[0085] 1) Take Q[8]132.8mg, MVE 2+ 46.6mg (MVE 2+ The volume ratio of the two is 1:1 (i.e. the molar ratio is 1:1), dissolved in ultrapure water, ultrasonicated, and transferred to a 100 mL volumetric flask to obtain a concentration of 1×10 -3 mol / L probe solution, for later use;

[0086] 2) Take the above concentration as 1×10 -3mol / L probe solution, diluted with water to 5×10 -4 mol / L, and the P3 supramolecular probe was obtained.

[0087] 2.4 Preparation of standard solutions of aniline and phenol pollutants:

[0088] Accurately weigh the analytically pure standards of the required pollutants p-PD, m-PD, o-PD, m-AP, HQ and RS, dissolve them in ultrapure water, and prepare a molar concentration of 1×10 -1 mol / L standard solutions of each pollutant.

[0089] 2.5 Qualitative analysis:

[0090] 1) Add different pollutant standard solutions obtained in step 4 to the P1 supramolecular probe solution obtained in step 1 (the molar ratio of supramolecular probe to each pollutant is 1:1), let it stand for 3 hours, and perform UV absorption spectrum measurement on the solutions ( Figure 2 (a)) and observe the color changes under natural light ( Figure 3 (a)):

[0091] The P1 supramolecular probe itself is colorless. If charge transfer peaks are generated at 454 nm, 432 nm, 572 nm, 510 nm, 465 nm, and 404 nm, and the solution changes color from colorless to gray, light yellow-brown, bluish-gray, light pink, pink, and yellow under natural light, respectively, these pollutants are p-PD, m-PD, o-PD, m-AP, HQ, and RS, respectively.

[0092] 2) Add different pollutant standard solutions obtained in step 4 to the P2 supramolecular probe solution obtained in step 2 (the molar ratio of supramolecular probe to each pollutant is 1:1), let it stand for 3 hours, and perform UV absorption spectrum measurement on the solutions ( Figure 2 (b)) and observe the color changes under natural light ( Figure 3 (b)):

[0093] The P2 supramolecular probe itself is yellow. If charge transfer peaks are observed at 650nm and 670nm, and the solution changes from yellow to grass green and dark green under natural light, respectively, these pollutants are p-PD and o-PD, respectively. If there are no obvious charge transfer bands, but the solution changes from yellow to yellow-green, pea green, yellow-brown, and orange under natural light, respectively, these pollutants are m-PD, m-AP, HQ, and RS, respectively.

[0094] 3) Add different pollutant standard solutions obtained in step 4 to the P3 supramolecular probe solution obtained in step 3 (the molar ratio of supramolecular probe to each pollutant is 1:1), let it stand for 3 hours, and perform UV absorption spectrum measurement on the solutions ( Figure 2 (c)) and observe the color changes under natural light ( Figure 3 (c)):

[0095] The P3 supramolecular probe itself is light orange. If two charge transfer peaks are generated at 422nm and 594nm, and the solution changes from light orange to gray-brown under natural light, the pollutant is p-PD. If a single charge transfer peak is generated at 426nm, and the solution changes from light orange to light orange-yellow, the pollutant is HQ. If there is no obvious charge transfer band, but the solution changes color from light orange to nude, pink-brown, light pink-orange, and ginger-yellow under natural light, the pollutants are m-PD, o-PD, m-AP, and RS, respectively.

[0096] 4) The color changes of P1, P2 and P3 obtained in 1), 2) and 3) were photographed and designed into a colorimetric array of 3 sensor elements × 6 pollutants. It can be clearly found that the above array has significant differences in response to the 6 pollutants of p-PD, m-PD, o-PD, m-AP, HQ and RS. By comparing the color signals of the matrix under natural light, the purpose of distinguishing the above 6 pollutants can be achieved. Figure 3 .

[0097] 2.6 Obtaining colorimetric fingerprints for linear discriminant analysis

[0098] 1) Three supramolecular probes, P1 (500 μM), P2 (500 μM), and P3 (500 μM), were prepared in ultrapure water. A 96-well white titration plate was used to add 300 μL of a mixed sample solution of each of the three probes (all at 500 μM) and six pollutants (p-PD, m-PD, o-PD, m-AP, HQ, and RS) (500 μM) to each well. Five replicates were generated for each mixed sample. The reaction was allowed to proceed for three hours. The 96-well plate was then exposed to white light, and an image was captured. Image processing software was used to extract the RGB values ​​for each well. The difference (ΔRGB) between the RGB value of each well and the control value was used as the colorimetric fingerprint of each pollutant sample based on this detection array. This generated a data matrix consisting of 3 sensing systems × 6 pollutants × 5 replicates. This data matrix was subjected to linear discriminant analysis (LDA) using SPSS version 22.0. In the LDA model, five replicates of the same pollutant clustered together and were well separated from the points of other pollutants. From the data results, it can be seen that the sensor array can detect and identify six different pollutants: p-PD, m-PD, o-PD, m-AP, HQ, and RS ( Figure 4 ).

[0099] 2) Using the method described in 1), o-PD was selected as the model analyte and colorimetric fingerprints were obtained for seven different o-PD concentrations (0 μM, 10 μM, 50 μM, 100 μM, 200 μM, 300 μM, 400 μM, and 500 μM). This yielded a data matrix consisting of three sensor elements, eight o-PD concentrations, and five parallel experiments, which was then analyzed using LDA. In the LDA model, the o-PD concentration distribution gradually transitions from positive factors to negative factors along the X-axis. These data indicate that the sensor array can, to a certain extent, identify pollutants of varying concentrations ( Figure 5 ).

[0100] 3) Using the method described in 1), a binary mixture of p-PD and m-PD was selected as a model analyte, and colorimetric fingerprints of 5 different concentration ratios of o-PD / m-PD binary mixtures (0μM: 500μM, 150μM: 350μM, 250μM: 250μM, 150μM: 350μM, 500μM: 0μM) were obtained. A data matrix consisting of 3 sensor elements × 5 different concentration ratios of o-PD / m-PD binary mixtures × 5 parallel experiments was obtained and data analysis was performed using LDA. In the LDA model diagram, five parallel points of binary mixed pollutants with the same concentration ratio are clustered together, which can be well separated from points of other binary mixed pollutants with different concentration ratios. From this data result, it can be seen that the sensor array can realize the identification of mixed pollutants to a certain extent ( Figure 6 ).

[0101] Experimental Case 1: Preparation method of each reagent in the analytical method of the present invention.

[0102] 1) Q[8]、MV 2+ 、VCN 2+ 、MVE 2+ Preparation of standard solutions

[0103] Q[8]: Dissolve 13.3 mg of Q[8] in ultrapure water, sonicate, and dilute to volume with a 100 mL volumetric flask to obtain solution A with a concentration of 100 μM. Set aside.

[0104] MV 2+ :Get MV 2+ Dissolve 25.7 mg of the product in ultrapure water and dilute to volume with a 100 mL volumetric flask to obtain solution B with a concentration of 1000 μM.

[0105] VCN 2+ : Get VCN 2+ Dissolve 43.1 mg of the product in ultrapure water and dilute to volume in a 100 mL volumetric flask to obtain solution C with a concentration of 1000 μM. Set aside.

[0106] MVE 2+ : Get MVE 2+ Dissolve 46.6 mg of the product in ultrapure water and dilute to volume in a 100 mL volumetric flask to obtain solution D with a concentration of 1000 μM. Set aside.

[0107] 2) Preparation of pollutant standard solution:

[0108] Accurately weigh the analytically pure standards of the required pollutants p-PD, m-PD, o-PD, m-AP, HQ and RS, dissolve them in ultrapure water, and prepare a molar concentration of 1×10 -1 mol / L standard solutions of each pollutant.

[0109] Experimental case: 2: Prepare three supramolecular probe solutions P1, P2 and P3.

[0110] 1) To determine Q[8] and MV 2+ 、VCN 2+ and MVE 2+ The inventors used UV-visible absorption to analyze the effect of Q[8] and MV 2+ 、VCN 2+ or MVE 2+ The interactions between them were studied.

[0111] For example: Solution B (MV 2+ ) was diluted to 20 μM with ultrapure water, and the concentration of Q[8] was gradually increased by the molar ratio method, and its UV-visible absorption spectrum was measured; as the concentration of Q[8] (0-40 μM) in the system gradually increased, the UV absorbance of the system continued to decrease ( Figure 7 a); UV absorbance at 257 nm and Q[8] and MV 2+ The amount of substance I 257nm -N Q[8] / N MV 2+ Relationship curve ( Figure 7 b) and Job diagram ( Figure 7 b illustration) It can be seen that MV 2+ The action ratio with Q[8] is 1:1. Therefore, take Q[8] 66.4mg, MV 2+ 12.86mg (MV 2+ The volume ratio of the two is 1:1 (i.e. the molar ratio is 1:1), dissolved in ultrapure water, ultrasonicated, and transferred to a 100 mL volumetric flask to obtain a concentration of 5×10 -4 mol / L probe solution P1.

[0112] Q[8] and VCN 2+ 、MVE 2+The interaction between the two refers to Q[8] and MV 2+ The experimental method of Q[8] and VCN 2+ The action ratio is 1:1( Figure 8 ), Q[8] and MVE 2+ The action mode between them is 1:1( Figure 9 ). Then we can get the concentration of 5×10 -4 mol / L P2 supramolecular probe solution and a concentration of 5×10 -4 mol / L P3 supramolecular probe solution.

[0113] Experimental Case 3: Qualitative Analysis of 6 Pollutants by Probes P1, P2, and P3

[0114] To the three supramolecular probe solutions (P1, P2, and P3) prepared in Experimental Example 2 (all at 500 μM), different pollutant standard solutions (at a molar ratio of 1:1) obtained in Step 2 of Experimental Example 1 were added. The solutions were allowed to stand for 3 hours. UV absorption spectra of the solutions were then measured and the color changes observed under natural light. The absorption peaks and colors of the P1, P2, and P3 probes all changed. For the P1 supramolecular probe, the addition of p-PD, m-PD, o-PD, m-AP, HQ, and RS produced charge transfer peaks at 454 nm, 432 nm, 572 nm, 510 nm, 465 nm, and 404 nm, respectively. The color of the solution under natural light changed from colorless to gray, light yellow-brown, blue-gray, light pink, pink, and yellow, respectively. In contrast, for the P2 supramolecular probe, the addition of the six electron-rich aromatic pollutants resulted in different changes in the UV-visible absorption spectrum than that of P1. For example, when p-PD and o-PD were added to the P2 supramolecular probe, charge transfer peaks were generated at 650 nm and 670 nm, and the solution changed from yellow to grass green and dark green, respectively. When o-PD, m-AP, HQ, and RS were added to the P2 probe, although there were no obvious charge transfer peaks, changes occurred compared to the UV-visible absorption spectrum of the P2 probe itself, and under natural light, the colors changed from yellow to yellow-green, bean green, yellow-brown, and orange, respectively. Similarly, after the six electron-rich aromatic pollutants were added to the P3 supramolecular probe, its UV-visible absorption spectrum changed to varying degrees. When p-PD was added, two charge transfer peaks were generated at 422 nm and 594 nm, and the solution changed from light orange to gray-brown. When HQ was added, a charge transfer peak was generated at 426 nm, and the solution changed from light orange to light orange-yellow. After adding m-PD, o-PD, m-AP, and RS, their UV-visible absorption spectra were enhanced to varying degrees, with the colors changing from light orange to nude, pink-brown, light pink-orange, and turmeric, respectively. The results showed that the three supramolecular probes responded differently to the six aromatic pollutants.

[0115] Experimental Case 4: Constructing fingerprints for six phenol and aniline pollutants and conducting qualitative and quantitative determinations

[0116] 1) The array experiment was carried out on a 96-well white titration plate. 300 μL of a mixed sample solution of P1 (500 μM), P2 (500 μM), P3 (500 μM) and pollutants (500 μM) was added to each well, and each mixed sample was repeated in parallel for five sets of data. After three hours of reaction, the 96-well plate was placed on white light, the image was taken and the RGB value of each well was extracted using image processing software. The difference ΔRGB between the RGB value of each well and the control value was used as the colorimetric fingerprint of the detection array based on this different pollutant samples. It generated a data matrix consisting of 3 sensing systems × 6 pollutants × 5 repetitions. The data matrix was subjected to linear discriminant analysis (LDA) using SPSS22.0 version, as shown in Figure 2. Figure 4 The results showed that the sensor array correctly classified 100% of the pollutants. The LDA discriminant model, built using the Fisher function, clearly distinguished the six pollutants: p-PD, m-PD, o-PD, m-AP, HQ, and RS. Therefore, the sensor array was able to qualitatively identify and distinguish the six pollutants.

[0117] 2) Add 300 μL of o-PD with different concentration gradients (0 μM, 50 μm, 100 μM, 200 μM, 300 μM, 400 μM, 500 μM + an unknown concentration (actually 400 μM)) to the 96-well plate, respectively, and mix them with P1 (500 μM), P2 (500 μM) and P3 (500 μM), and each mixed sample has five parallel data sets. After three hours of reaction, place the 96-well plate on white light, take pictures to obtain images, and use image processing software to extract the RGB value of each well. The difference ΔRGB between the RGB value of each well and the control value is used as the colorimetric fingerprint of different pollutant samples based on this detection array. A data matrix consisting of 3 sensor elements × 8 o-PD concentrations × 5 parallel experiments was generated. The data matrix was subjected to linear discriminant analysis (LDA) using SPSS 22.0 version, as shown in the following figure: Figure 5 The results showed that the array was able to correctly classify 100% of the o-PD concentration data. Different o-PD concentrations had very clear discrimination under the LDA discriminant model established using the Fisher function. Through cross-validation, the grouped cases were correctly classified 100%. We gave the array an "unknown" sample of 400μMo-PD for classification. The results showed that the five parallel data of the unknown sample were all discriminated into the 400μM concentration range. These results further demonstrate the versatility of the sensor array and its ability to quantitatively detect and identify pollutants.

[0118] 3) 300 μL of a mixture of o-PD / m-PD at varying concentrations (0 μM:500 μM, 150 μM:350 μM, 250 μM:250 μM, 150 μM:350 μM, and 500 μM:0 μM) and P1 (500 μM), P2 (500 μM), and P3 (500 μM) were added to a 96-well plate. Five replicates were generated for each sample. The reaction was allowed to proceed for three hours. The 96-well plate was then exposed to white light, and an image was captured. Image processing software was used to extract the RGB values ​​for each well. The difference (ΔRGB) between the RGB value of each well and the control value was used as the colorimetric fingerprint of each contaminant sample based on this detection array. A data matrix consisting of three sensor elements, five different concentrations of the o-PD / m-PD binary mixture, and five replicates was generated, and the data were analyzed using LDA. In the LDA model diagram, five parallel points of binary mixed pollutants with the same concentration ratio are clustered together, which can be well separated from the points of other binary mixed pollutants with different concentration ratios. From this data result, it can be seen that the sensor array can realize the identification of mixed pollutants to a certain extent ( Figure 6 ).

[0119] The above description is merely a preferred experimental example of the present invention and does not constitute any form of limitation to the present invention. Any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention without departing from the content of the technical solution of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A method for detecting six aniline and phenol pollutants in aqueous solution using a supramolecular colorimetric sensor array, characterized by: The method is a method for preparing a supramolecular colorimetric sensing array using supramolecular probes, and using the supramolecular colorimetric sensing array to detect six aniline and phenol pollutants, namely p-PD, m-PD, o-PD, m-AP, HQ and RS, in aqueous solution; The method for detecting six aniline and phenol pollutants in aqueous solution using the supramolecular colorimetric sensor array is carried out according to the following steps: (1) Prepare supramolecular colorimetric sensing array; the supramolecular colorimetric sensing array includes the following three supramolecular probes: MV 2+ @Q[8] Supramolecular probe, VCN 2+ @Q[8] Supramolecular probes and MVE 2+ @Q[8] Supramolecular probe; The MV 2+ @Q[8] Supramolecular probe, VCN 2+ @Q[8] Supramolecular probes and MVE 2+ @Q[8] The concentration of supramolecular probes was 500 μM; (2) Prepare standard solutions of p-PD, m-PD, o-PD, m-AP, HQ and RS of aniline and phenol pollutants; (3) adding each pollutant standard solution in step (2) to the supramolecular colorimetric sensing array in step (1) to obtain a mixed sample solution, monitoring the color change of the mixed sample solution, reacting for three hours, and obtaining a colorimetric fingerprint of the colorimetric sensing detection array; (4) Extracting the image data matrix of the colorimetric fingerprint of step (3), and using the classical pattern recognition method to distinguish and identify the components in the test object.

2. The method for detecting six aniline and phenol pollutants in aqueous solution using a supramolecular colorimetric sensor array according to claim 1, characterized in that: In step (1), MV 2+ The preparation method of @Q[8] supramolecular probe is as follows: 132.8 mg of eight-membered cucurbitacin Q[8], methyl viologen MV 2+ 25.7 mg, the volume ratio of the two is 1:1, that is, the molar ratio is 1:1, dissolved in ultrapure water, ultrasonicated, and transferred to a 100 mL volumetric flask to obtain a concentration of 1×10 -3 mol / L probe solution, and then dilute it to 5×10 -4 mol / L, and the P1 supramolecular probe was obtained.

3. The method for detecting six aniline and phenol pollutants in aqueous solution using a supramolecular colorimetric sensor array according to claim 1, characterized in that: VCN in step (1) 2+ Preparation method of @Q[8] supramolecular probe: 132.8 mg of eight-membered cucurbit ring Q[8] and VCN 2+ 43.1 mg, the volume ratio of the two is 1:1, that is, the molar ratio is 1:1, dissolved in ultrapure water, ultrasonicated, and transferred to a 100 mL volumetric flask to obtain a concentration of 1×10 -3 mol / L probe solution, and then dilute it to 5×10 -4 mol / L, and the P2 supramolecular probe was obtained.

4. The method for detecting six aniline and phenol pollutants in aqueous solution using a supramolecular colorimetric sensor array according to claim 1, characterized in that: In step (1), MVE 2+ @Q[8] Preparation method of supramolecular probe: 132.8 mg of eight-membered cucurbit ring Q[8] and MVE 2+ 46.6 mg, the volume ratio of the two is 1:1, that is, the molar ratio is 1:1, dissolved in ultrapure water, ultrasonicated, and transferred to a 100 mL volumetric flask to obtain a concentration of 1×10 -3 mol / L probe solution, and then dilute it to 5×10 -4 mol / L, and the P3 supramolecular probe was obtained.

5. The method for detecting six aniline and phenol pollutants in aqueous solution using a supramolecular colorimetric sensor array according to claim 1, characterized in that: In the step (3), the concentration of the added pollutant solution is the same as the concentration of the supramolecular probe, which is 500 μM.

6. The method for detecting six aniline and phenol pollutants in aqueous solution using a supramolecular colorimetric sensor array according to claim 1, characterized in that: In step (2), the preparation method of the pollutant standard solution is to accurately weigh the required pollutants p-PD, m-PD, o-PD, m-AP, HQ and RS respectively, dissolve them in ultrapure water, and prepare a molar concentration of 1×10 -1 mol / L pollutant standard solution; The pollutants p-PD, m-PD, o-PD, m-AP, HQ and RS were analytically pure standards.

7. The method for detecting six aniline and phenol pollutants in aqueous solution using a supramolecular colorimetric sensor array according to claim 1, characterized in that: In the step (3), the method for obtaining the colorimetric fingerprint of the colorimetric sensor array includes: placing the colorimetric sensor array on white light, taking a photo to obtain an image and extracting the RGB value of each sensor unit using image processing software, and using the difference ΔRGB between the RGB value of each sensor unit and the control value as the colorimetric fingerprint of different pollutant samples based on this detection array.

8. The method for detecting six aniline and phenol pollutants in aqueous solution using a supramolecular colorimetric sensor array according to claim 1, characterized in that: In the step (4), SPSS software is used to perform linear discriminant analysis on the data matrix to obtain a standard model; the standard model is a linear discriminant analysis LDA model.

Images