Supramolecular fluorescent sensing array and use thereof

Abstract

This invention provides a supramolecular fluorescence sensing array and its application, belonging to the field of analytical chemistry detection technology. The supramolecular fluorescence sensing array is composed of three supramolecular fluorescent probes: 2PAL@Q[8], ThT@Q[8], and 2C30@3Q[8]. This invention can detect five anions: F, Cl, and C. ‑ ,Br ‑ I ‑ and ClO ‑ It can perform rapid identification and detection, and has the advantages of simple preparation, high sensitivity and speed of detection and strong anti-interference ability.

Description

Technical Field

[0001] This invention belongs to the field of analytical chemistry detection technology, specifically a supramolecular fluorescence sensing array and its applications. Background Technology

[0002] Anions play a vital role in many biological, chemical, and environmental processes, and some anions are crucial to our lives. For example, appropriate amounts of fluoride help prevent tooth decay and osteoporosis, while high doses of fluoride anions can lead to fluorosis of teeth and bones, nephrotoxic changes, and urolithiasis in humans. The World Health Organization (WHO) ranks dental caries as the third leading cause of harm to human health, after cardiovascular disease and cancer. Chloride ions participate in various physiological processes, are distributed in almost all types of cells, and participate in many physiological processes such as regulating cell volume, controlling membrane potential, and maintaining stable vesicle pH. Iodine is one of the essential trace elements for the human body and is an essential raw material for the synthesis of thyroid hormones. It plays an important role in maintaining health, including intellectual development, regulating metabolism, and influencing the function of other organ systems.

[0003] Anions typically have a low charge-to-radius ratio due to their large size, making their electrostatic binding to acceptors less efficient compared to isoelectric cations. Furthermore, anions possess relatively high solvation free energies, leading to effective competition between the acceptor and the surrounding medium. Therefore, the determination and identification of anions are not as straightforward as those of cations. This places higher demands on the design complexity of the acceptors and sensors required for successful anion sensing. Traditional ion chromatography and inductively coupled plasma mass spectrometry (ICP-MS) are commonly used methods for anion analysis in this field. While these methods offer high sensitivity and selectivity, they typically require complex instrumentation, high cost, time-consuming experiments, and a high level of operational skill. Therefore, developing a simple, rapid, sensitive, and low-cost method for the simultaneous analysis and identification of multiple anions is of great significance. Summary of the Invention

[0004] This invention provides a supramolecular fluorescence sensing array and its application, the purpose of which is to enable the detection of five anions F - Cl - ,Br - I - and ClO - It can perform rapid identification and detection, and has the advantages of simple preparation, high sensitivity and speed of detection and strong anti-interference ability.

[0005] The present invention provides the following technical solution to achieve the above objectives: A supramolecular fluorescence sensing array, wherein the supramolecular fluorescence sensing array is composed of three supramolecular fluorescent probes 2PAL@Q[8], ThT@Q[8] and 2C30@3Q[8].

[0006] In the aforementioned supramolecular fluorescence sensing array, 2PAL@Q[8] is a solution with a molar concentration ratio of Q[8] to PAL of 1:2; ThT@Q[8] is a solution with a molar concentration ratio of Q[8] to ThT of 1:1; and 2C30@3Q[8] is a solution with a molar concentration ratio of Q[8] to C30 of 3:2.

[0007] In the aforementioned supramolecular fluorescent sensing array, the concentrations of the supramolecular fluorescent probes 2PAL@Q[8], ThT@Q[8], and 2C30@3Q[8] are all 10 μM.

[0008] In the aforementioned supramolecular fluorescence sensing array, the monitoring wavelength of 2PAL@Q[8] is 538nm; the monitoring wavelengths of ThT@Q[8] are 560nm and 498nm; and the monitoring wavelengths of 2C30@3Q[8] are 535nm and 579nm.

[0009] In the application of the supramolecular fluorescence sensing array, 2PAL@Q[8], ThT@Q[8] and 2C30@3Q[8] are used to detect the anion F. - Cl - ,Br - I - and ClO - .

[0010] In the application of the supramolecular fluorescence sensing array, the detection method includes the following steps: S1: Prepare supramolecular fluorescent probes 2PAL@Q[8], ThT@Q[8] and 2C30@3Q[8] respectively; S2: Prepare anions F at a concentration 5 times that of any supramolecular fluorescent probe in S1. - Cl - ,Br - I - and ClO - Solution; S3: Add any anion solution prepared in S2 to any supramolecular fluorescent probe prepared in S1, and measure its fluorescence emission spectrum at the monitoring wavelength of the supramolecular fluorescent probe for detection. In the application of the supramolecular fluorescence sensing array, 2PAL@Q[8] is green fluorescence. If the fluorescence intensity at 538 nm decreases and the fluorescence distribution remains almost unchanged, it indicates that the anion is Cl. - or ClO - If the fluorescence intensity at 538 nm decreases and the fluorescence color changes to a pale dark green, it indicates that the anion is Br. -If the fluorescence intensity at 538 nm decreases and the fluorescence color changes to a dark green, it indicates that the anion is F. - Or I - ; The ThT@Q[8] is a yellow-green fluorescence. If the fluorescence intensity decreases at 560 nm and the fluorescence distribution remains almost unchanged, it indicates that the anion is ClO. - If the emission peak shifts from 560 nm (blue) to 498 nm, the fluorescence intensity decreases, and the fluorescence color changes to cyan-green, then the anion is F. - or Cl - If the emission peak shifts from 560 nm (blue) to 498 nm, the fluorescence intensity decreases, and the fluorescence color changes to bright green, it indicates that the anion is Br. - Or I - ; The 2C30@3Q[8] exhibits bright yellow fluorescence. If the emission peak at 535 nm shifts to 531 nm, and a shoulder peak appears at 591 nm with the fluorescence color turning pale yellow, it indicates that the anion is F. - If the emission peak at 535 nm shifts to 530 nm, and a shoulder peak appears at 591 nm with the fluorescence color changing to yellow-green, then the anion is Cl. - If the emission peak at 535 nm shifts to blue at 528 nm, and a shoulder peak appears at 698 nm with the fluorescence color turning green, then the anion is Br. - If the emission peak at 535 nm shifts to blue at 502 nm and the emission peak at 535 nm decreases, and the fluorescence color turns green, it indicates that the anion is I. - If the emission peak at 535 nm shifts to 465 nm and the emission peak at 535 nm decreases, and the fluorescence color turns blue, it indicates that the anion is ClO. - .

[0011] In the application of the supramolecular fluorescent sensing array, three supramolecular fluorescent probes, 2PAL@Q[8], ThT@Q[8] and 2C30@3Q[8], are combined with five anions, F - Cl - ,Br - I - and ClO - The solutions were combined one by one to obtain a mixed sample solution. The fluorescence spectrum of the mixed sample solution and the fluorescence intensity at the monitoring wavelength were detected. Ten parallel experiments were performed to obtain a data matrix consisting of three supramolecular fluorescent probes × five anions × ten parallel experiments. The data matrix was analyzed using software to obtain the standard model.

[0012] In the application of the supramolecular fluorescence sensing array, SPSS software is used to perform linear discriminant analysis on the data matrix to obtain the standard model of linear discriminant analysis.

[0013] In the application of the supramolecular fluorescence sensing array, the standard model is used to detect fluoride toothpaste.

[0014] Beneficial effects Compared with the prior art, the present invention has the following beneficial effects: This invention proposes a supramolecular fluorescent sensing array composed of three supramolecular fluorescent probes: 2PAL@Q[8], ThT@Q[8], and 2C30@3Q[8]. By utilizing the different responses of various supramolecular fluorescent probes to anions in this array, five anions, F, can be identified and detected in aqueous solution. - Cl - ,Br - I - and ClO - It features simple preparation and rapid and sensitive detection; furthermore, the supramolecular fluorescence sensing array of this invention has good anti-interference ability when recognizing the aforementioned 5 anions, and can also identify toothpaste brands with different fluoride contents. Attached Figure Description

[0015] Figure 1 The chemical structural formulas are Q[8], PAL, ThT and C30; Figure 2 The fluorescence emission spectra of S1(a), S2(b) and S3(c) in response to five anions (50 μM); Figure 3 This is the CIE matrix diagram of S1(a), S2(b), and S3(C) for five anions (50 μM); Figure 4 This is an LDA diagram of the fluorescence response of a supramolecular fluorescence sensing array to five anions; Figure 5 It is a supramolecular fluorescence sensing array for different concentrations of F - LDA plot of fluorescence response; Figure 6 This is an LDA diagram of the response patterns of the supramolecular fluorescence sensing array to five anions (50 μM) and other interfering substances (50 μM); Figure 7 This is an LDA diagram of five toothpaste brands obtained using a supramolecular fluorescence sensing array. Figure 8 The fluorescence spectrum changes when the concentration of Q[8] is increased in PAL(10μM) (a); fluorescence intensity to molar ratio I 538nm -N Q[8] / N PAL Relationship curve (b), Insert: Fluorescence Job plot obtained by continuously varying the mole fractions of PAL and Q[8]; Figure 9The fluorescence spectrum changes when the concentration of Q[8] is increased by ThT(10μM) (a); fluorescence intensity to molar ratio I 560nm -N Q[8] / N ThT Relationship curve (b), Insert: Fluorescence Job plot obtained by continuously varying the mole fractions of ThT and Q[8]; Figure 10 The fluorescence spectrum changes when the concentration of Q[8] is increased in C30 (10 μM) (a); fluorescence intensity to molar ratio I 535nm -N Q[8] / N C30 Relationship curve (b), Insert: Fluorescence Job plot obtained by continuously varying the mole fractions of C30 and Q[8]. Detailed Implementation

[0016] The present invention will now be described in further detail with reference to the accompanying drawings and embodiments.

[0017] Example 1: A supramolecular fluorescence sensing array.

[0018] Palmatine chloride (PAL), thioflavine T (ThT), and coumarin 30 (C30) are three optically active small molecules. Figure 1 ), respectively, to construct three supramolecular fluorescent probes with Q[8]: 2PAL@Q[8] (abbreviated as S1), 2ThT@2Q[8] (abbreviated as S2) and 2C 30@3Q[8] (abbreviated as S3).

[0019] The steps are as follows: 1. Preparation of S1 standard solution 1) Take 13.3 mg of Q[8], dissolve it in ultrapure water, sonicate it, and dilute it to volume with a 100 mL volumetric flask to obtain solution A with a concentration of 100 μM, and set it aside; 2) Dissolve 38.7 mg of PAL in ultrapure water, and dilute to volume with ultrapure water in a 100 mL volumetric flask to obtain solution B with a concentration of 1000 μM, for later use; 3) Transfer 10 mL of the above solution A and 2 mL of solution B into a 100 mL volumetric flask, mix them, and add water to make up to the final volume to obtain the 10 μM supramolecular fluorescent probe S1.

[0020] 2. Preparation of S2 standard solution 1) Take 13.3 mg of Q[8], dissolve it in ultrapure water, sonicate it, and dilute it to volume with a 100 mL volumetric flask to obtain solution A with a concentration of 100 μM, and set it aside; 2) Take 1.7 mg of ThT3, dissolve it in ultrapure water, and dilute to volume with ultrapure water in a 100 mL volumetric flask to obtain solution C with a concentration of 1000 μM, and set aside for later use; 3) Transfer 10 mL of solution A and 1 mL of solution B to a 100 mL volumetric flask, mix them, and add water to make up to the final volume to obtain the 10 μM supramolecular fluorescent probe S2.

[0021] 3. Preparation of S3 standard solution 1) Take 13.3 mg of Q[8], dissolve it in ultrapure water, sonicate it, and dilute it to volume with a 100 mL volumetric flask to obtain solution A with a concentration of 100 μM, and set it aside; 2) Dissolve 34.7 mg of C30 in ultrapure water, and dilute to volume with ultrapure water in a 100 mL volumetric flask to obtain solution D with a concentration of 1000 μM, for later use; 3) Transfer 10 mL of the above solution A and 666 μL of solution D to a 100 mL volumetric flask, mix them, and add water to make up to the final volume to obtain the 10 μM supramolecular fluorescent probe S3.

[0022] The three supramolecular fluorescent probes S1, S2, and S3 mentioned above are used as a supramolecular fluorescent sensing array.

[0023] To determine the interaction ratio of Q[8] with PAL, ThT and C30 to form probes, the inventors conducted extensive studies on the interaction between Q[8] and PAL, ThT and C30 using fluorescence emission spectroscopy, such as the following studies: (1) The solution B (PAL) obtained in Example 1 was diluted with water to 10 μM. The concentration of Q[8] was gradually increased by the molar ratio method, and its fluorescence emission spectrum was measured. The excitation wavelength was fixed at 341 nm, the voltage at 500 V, and the slit width at 10 nm. PAL has a characteristic emission peak at 538 nm. As the concentration of Q[8] (0-30 μM) in the system gradually increases, the fluorescence intensity of the system decreases, and the characteristic peak gradually blue-shifts until 518 nm ( Figure 6 a); The fluorescence intensity at 538 nm is related to the molar ratio of Q[8] and PAL. 538nm -N Q[8] / N PAL Relationship curve ( Figure 8 b) and Job chart ( Figure 8 (b illustration) It can be seen that the ratio of PAL to Q[8] is 2:1. Therefore, 10 mL of solution A and 2 mL of solution B from Example 1 can be mixed in a 100 mL volumetric flask, and water can be added to make up to the final volume to obtain the 10 μM supramolecular fluorescent probe S1.

[0024] (2) Similarly, the interaction between Q[8] and ThT and C30 was performed using the same experimental method as Q[8] and PAL in (1) above. When testing the fluorescence emission spectrum, the excitation wavelength of ThT was 408 nm, the voltage was 540 V, and the slit width was 10 nm. The excitation wavelength of C30 was 481 nm, the voltage was 550 V, and the slit width was 10 nm. It was found that the interaction ratio of Q[8] to ThT was 1:1 ( Figure 8 The ratio of Q[8] to C30 is 3:2. Figure 10 Then, S2 supramolecular fluorescent probe solution with a concentration of 10 μM and S3 supramolecular fluorescent probe solution with a concentration of 10 mμM can be obtained respectively.

[0025] Example 2. The supramolecular fluorescence sensing array obtained in Example 1 was used to detect five anions F - Cl - ,Br - I - and ClO - Qualitative analysis.

[0026] Accurately weigh the analytical grade standards of the desired anion (tetrabutyl anion salt) and cation (perchloric acid cation salt), dissolve them in ultrapure water, and prepare a molar concentration of 2 × 10⁻⁶. -2 Standard solutions of each ion of M.

[0027] 1) Add the F obtained in step 4 to the probe S1 solution respectively. - Cl - ,Br - I - and ClO - Anion standard solutions (molar ratio of supramolecular fluorescent probe to each anion 1:5) were allowed to stand for 20 min, and their fluorescence emission spectra were measured. Probe S1 was excited at 341 nm with a voltage of 500 V and a slit width of 10 nm; probe S2 was excited at 408 nm with a voltage of 540 V and a slit width of 10 nm; probe S3 was excited at 481 nm with a voltage of 550 V and a slit width of 10 nm. The results showed that probe S1 had an emission peak at 538 nm. The presence of anions caused different changes in the fluorescence emission spectrum of the probe S1 system, such as Cl... - and ClO - The presence of this caused a slight decrease in fluorescence intensity at 538 nm. Figure 2 a): Probe S1 itself is green fluorescent. A slight decrease in fluorescence emission at 538 nm and almost no change in color distribution in CIE indicate that the anion is Cl. - or ClO -If the fluorescence emission at 538 nm decreases significantly and the fluorescence color slightly changes to a pale dark green, it indicates that the anion is Br. - If the fluorescence emission at 538 nm decreases more significantly and the fluorescence color changes from green to a darker, deeper green, then the anion is F. - Or I - , and I - The fluorescence intensity and color change are both better than F - Big.

[0028] 2) Add the F obtained in step 4 to the probe S2 solution obtained in step 2. - Cl - ,Br - I - and ClO - Anion standard solutions (molar ratio of supramolecular fluorescent probe to each anion 1:5) were allowed to stand for 20 min, and their fluorescence emission spectra were measured separately. Probe S2 showed an emission peak at 560 nm. Adding anions to the probe caused different changes in the emission spectrum of the system. For example, adding ClO- did not significantly change the fluorescence intensity of the probe, while adding F... - Cl - This caused the maximum emission peak to shift from 560 nm to 498 nm, with a significant change in fluorescence intensity; the addition of Br - I - This not only caused the maximum emission peak to blue shift from 560nm to 498nm, but also significantly reduced the fluorescence intensity. Figure 2 b): The probe S2 itself exhibits yellow-green fluorescence. If the fluorescence emission peak at 560 nm decreases slightly and the color distribution in the CIE remains almost unchanged, it indicates that the anion is ClO₂. - If the emission peak shifts from 560 nm to 498 nm (blue shift), the fluorescence intensity is quenched less, and the yellow-green color observed in CIE changes to cyan-green, then the anion is F. - Cl - If the emission peak shifts from 560 nm (blue) to 498 nm, the fluorescence intensity is significantly quenched, and the yellow-green color observed in CIE changes to bright green, then the anion is Br. - I - .

[0029] 3) Add the F obtained in step 4 to the probe S3 solution obtained in step 3. - Cl - ,Br - I - and ClO -Anion standard solutions (molar ratio of supramolecular fluorescent probe to each anion is 1:5) were allowed to stand for 20 min, and their fluorescence emission spectra were measured separately. F was then added. - Cl - ,Br - This causes the emission peak of the probe at 535 nm to be blue-shifted to 531 nm, 530 nm, and 528 nm, respectively, with shoulder peaks at 591 nm, 587 nm, and 698 nm, respectively; while the addition of I - and ClO - The emission peak at 535 nm was blue-shifted to 502 nm and 465 nm, respectively, and the emission peak at 535 nm was significantly reduced and completely reduced. Figure 2 c): The probe S3 itself exhibits bright yellow fluorescence. If the emission peak at 535 nm is blue-shifted to 531 nm, 530 nm, and 528 nm, respectively, and shoulder peaks appear at 591 nm, 587 nm, and 698 nm, respectively, and the color distribution in the CIE spectrum is light yellow, yellow-green, and green, respectively, then the anion is F. - Cl - ,Br - If the emission peak at 535 nm is blue-shifted to 502 nm and 465 nm respectively, and the emission peak at 535 nm is significantly reduced and completely reduced, and the color distribution in CIE is green and blue, then it indicates that the anion is I0. - and ClO - .

[0030] 4) The fluorescence colors of probes S1, S2, and S3 obtained in 1), 2), and 3) in CIE were sampled and designed into a fluorescence array of 3 supramolecular fluorescent probes × 5 anions. It can be clearly seen that the above array is effective for F - Cl - ,Br - I - and ClO - The responses of these five anions are significantly different. By comparing the matrix fluorescence colors, it is possible to effectively distinguish these five anions. Figure 3 .

[0031] Example 3. Analysis of the ability of supramolecular fluorescence sensing array to qualitatively and quantitatively identify and resist interference of the five anions in Example 2.

[0032] 1) The array experiments were performed on a 96-well sterile black microtiter plate. 300 μL of a mixed sample solution of probes S1, S2, and S3 (all 10 μM) and anions (50 μM) was added to each well, with 10 replicates for each mixed sample. The fluorescence spectrum and maximum emission fluorescence intensity of each sample were detected using a full-function microplate reader. This generated a data matrix consisting of 3 supramolecular fluorescent probes × 5 anions × 10 replicates. This data matrix was analyzed using SPSS version 22.0 for linear discriminant analysis (LDA), as shown below. Figure 4 The results show that in the LDA discrimination model diagram established using the Fisher function, the 10 parallel points of the same anion cluster together, which can be well separated from the points of other ions. These data indicate that the sensor array can qualitatively identify F... - Cl - ,Br - I - and ClO - These are 5 different anions.

[0033] 2) Add 300 μL of F at different concentration gradients to the well plate respectively. - (0μM, 5μM, 10μM, 15μM, 20μM, 25μM) were used to create mixed samples with probes S1, S2, and S3, respectively, with 10 sets of data for each mixed sample. These samples were then analyzed using a full-function microplate reader to obtain 3 supramolecular fluorescent probes × 6 F... - A data matrix consisting of concentration × 10 replicates was generated, and linear discriminant analysis (LDA) was performed on this data matrix using SPSS version 22.0. Figure 5 The results showed that the array could correctly classify the original grouped cases with 100% accuracy. This result further illustrates the versatility of the sensor array, enabling quantitative detection and identification of anions.

[0034] 3) Add 300 μL of a mixed sample solution of probes S1, S2, and S3 (all 10 μM) and ions (50 μM) to the well plate, respectively. Repeat each mixed sample 10 times. Analyte (F - Cl - ,Br - I - and ClO - Interference K + Na + Ca 2+ Mn 2+ Al 3+ SO4 2- CO3 2- HPO4 2- HCO3- P2O7 2- AcO - and NO3 - These samples were analyzed using a full-function microplate reader, yielding a data matrix consisting of 3 supramolecular fluorescent probes × 17 ions × 10 repeats. This data matrix was then subjected to linear discriminant analysis (LDA) using SPSS version 22.0. Figure 6 The results show that in the LDA model, the five groups of analyte ions each form their own aggregation point, while the other 12 common interfering ions aggregate separately, clearly having no interfering effect on the five analytes. This result further illustrates the versatility of the sensing array and its excellent anti-interference capability.

[0035] Example 4. Recognition of common fluoride toothpaste by a supramolecular fluorescence sensing array.

[0036] Purchase common fluoride toothpastes such as Hawley, Colgate, Crest, and 3M Clinpro (Fluoridex), weigh out 35.0g of each, dissolve them in 10mL of ultrapure water, sonicate for half an hour, centrifuge at 3000r for half an hour, take 1mL of the supernatant and dilute it with ultrapure water to 10mL as the toothpaste sample standard solution.

[0037] Add 300 μL of probe solutions S1, S2, and S3 (all 10 μM) to the toothpaste samples in a well plate. Each mixed sample was replicated 10 times. These samples were analyzed using a full-function microplate reader to obtain a data matrix consisting of 3 supramolecular fluorescent probes × 5 toothpaste samples × 10 replicates. This data matrix was analyzed using SPSS version 22.0 for linear discriminant analysis (LDA). Figure 7 The results showed that the five toothpaste brands each formed five tightly packed clusters, with large gaps between them and no overlap. The experimental results indicate that the sensor array can effectively identify and distinguish the five toothpaste brands.

[0038] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art can understand the specific meaning of the above terms in the present invention according to the specific circumstances. Furthermore, there may be other modifications and variations in the implementation methods. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A supramolecular fluorescence sensing array, characterized in that: The supramolecular fluorescence sensing array is composed of three supramolecular fluorescent probes: 2PAL@Q[8], ThT@Q[8], and 2C30@3Q[8]. Wherein, PAL refers to palmatine hydrochloride, ThT refers to thiosulfate T, C30 refers to coumarin 30, Q[8] refers to octagonal cucurbit ring, 2PAL@Q[8] refers to a supramolecular fluorescent probe constructed from palmatine hydrochloride and octagonal cucurbit ring, ThT@Q[8] refers to a supramolecular fluorescent probe constructed from thiosulfate T and octagonal cucurbit ring, and 2C30@3Q[8] refers to a supramolecular fluorescent probe constructed from coumarin 30 and octagonal cucurbit ring.

2. The supramolecular fluorescence sensing array according to claim 1, characterized in that: The 2PAL@Q[8] is a solution with a molar concentration ratio of 1:2 formed by Q[8] and PAL; the ThT@Q[8] is a solution with a molar concentration ratio of 1:1 formed by Q[8] and ThT; the 2C30@3Q[8] is a solution with a molar concentration ratio of 3:2 formed by Q[8] and C30.

3. The supramolecular fluorescence sensing array according to claim 2, characterized in that: The concentrations of the supramolecular fluorescent probes 2PAL@Q[8], ThT@Q[8] and 2C30@3Q[8] are all 10 μM.

4. The supramolecular fluorescence sensing array according to claim 3, characterized in that: The monitoring wavelength of 2PAL@Q[8] is 538nm; the monitoring wavelengths of ThT@Q[8] are 560nm and 498nm; and the monitoring wavelengths of 2C30@3Q[8] are 535nm and 579nm.

5. The application of the supramolecular fluorescence sensing array according to claim 4, characterized in that: The anion F was detected by 2PAL@Q[8], ThT@Q[8] and 2C30@3Q[8]. - Cl - ,Br - I - and ClO - .

6. The application of the supramolecular fluorescence sensing array according to claim 5, characterized in that: The detection method includes the following steps: S1: Prepare supramolecular fluorescent probes 2PAL@Q[8], ThT@Q[8] and 2C30@3Q[8] respectively; S2: Prepare anions F at a concentration 5 times that of any supramolecular fluorescent probe in S1. - Cl - ,Br - I - and ClO - Solution; S3: Add any anion solution prepared in S2 to any supramolecular fluorescent probe prepared in S1, and measure its fluorescence emission spectrum at the monitoring wavelength of the supramolecular fluorescent probe for detection.

7. The application of the supramolecular fluorescence sensing array according to claim 6, characterized in that: The 2PAL@Q[8] is green fluorescent. If the fluorescence intensity at 538 nm decreases and the fluorescence distribution remains almost unchanged, it indicates that the anion is Cl. - or ClO - If the fluorescence intensity at 538 nm decreases and the fluorescence color changes to a pale dark green, it indicates that the anion is Br. - If the fluorescence intensity at 538 nm decreases and the fluorescence color changes to a dark green, it indicates that the anion is F. - Or I - ; The ThT@Q[8] is a yellow-green fluorescence. If the fluorescence intensity decreases at 560 nm and the fluorescence distribution remains almost unchanged, it indicates that the anion is ClO. - If the emission peak shifts from 560 nm (blue) to 498 nm, the fluorescence intensity decreases, and the fluorescence color changes to cyan-green, then the anion is F. - or Cl - If the emission peak shifts from 560 nm (blue) to 498 nm, the fluorescence intensity decreases, and the fluorescence color changes to bright green, it indicates that the anion is Br. - Or I - ; The 2C30@3Q[8] exhibits bright yellow fluorescence. If the emission peak at 535 nm shifts to 531 nm, and a shoulder peak appears at 591 nm with the fluorescence color turning pale yellow, it indicates that the anion is F. - If the emission peak at 535 nm shifts to 530 nm, and a shoulder peak appears at 591 nm with the fluorescence color changing to yellow-green, then the anion is Cl. - If the emission peak at 535 nm shifts to blue at 528 nm, and a shoulder peak appears at 698 nm with the fluorescence color turning green, then the anion is Br. - If the emission peak at 535 nm shifts to blue at 502 nm and the emission peak at 535 nm decreases, and the fluorescence color turns green, it indicates that the anion is I. - ; If the emission peak at 535 nm shifts to 465 nm and the emission peak at 535 nm decreases, and the fluorescence color turns blue, it indicates that the anion is ClO. - .

8. The application of the supramolecular fluorescence sensing array according to claim 7, characterized in that: Three supramolecular fluorescent probes, 2PAL@Q[8], ThT@Q[8] and 2C30@3Q[8], were combined with five anions, F - Cl - ,Br - I - and ClO - The solutions were combined one by one to obtain a mixed sample solution. The fluorescence spectrum of the mixed sample solution and the fluorescence intensity at the monitoring wavelength were detected. Ten parallel experiments were performed to obtain a data matrix consisting of three supramolecular fluorescent probes × five anions × ten parallel experiments. The data matrix was analyzed using software to obtain the standard model.

9. The application of the supramolecular fluorescence sensing array according to claim 8, characterized in that: The data matrix was subjected to linear discriminant analysis using SPSS software to obtain the standard model of linear discriminant analysis.

10. The application of the supramolecular fluorescence sensing array according to any one of claims 8-9, characterized in that: The standard model is used to test fluoride toothpaste.

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