Perylene monoimide-borate derivatives, their preparation methods and clinical tumor screening applications

Abstract

The present invention provides a perylene monoimide-borate derivative, a preparation method thereof, and a clinical tumor screening application. The preparation method is to react a perylene monoimide intermediate PMI-H with liquid bromine to generate a perylene monoimide compound PMI-Br; then react PMI-Br with bis(pinacolato)diboron, potassium acetate, and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium under light-shielded conditions, and separate to obtain the perylene monoimide-borate derivative. The present invention also provides an application of the derivative in the detection of biogenic amines. The present invention realizes the selective recognition of biogenic amines, realizes the sensing of spermine under simulated urine conditions, and then selects 26 clinical urine samples for detection, realizing the diagnosis of breast cancer patients. This patent has potential application value in the screening of tumor patients.

Description

Technical Field

[0001] The present invention relates to the technical fields of chemistry and medical detection, and particularly relates to a perylene monoimide-borate derivative, a preparation method thereof, and a clinical tumor screening application. Background Art

[0002] Biogenic amines (BAs) are a class of small nitrogen-containing molecules, which are produced by the decarboxylation reaction of amino acid compounds in organisms (humans, bacteria, and molds, etc.) (Nat. Commun., 2021, 12, 5529.). As biomarkers, they are of great significance in clinical diagnosis and the food industry. Among them, the main biogenic amines as biomarkers include cadaverine, putrescine, tyramine, tryptamine, spermine, etc. (Trends Food Sci. Tech., 2021, 112, 75 - 87; J. Chromatogr. A, 2021, 1651, 462319.). Therefore, the detection of biogenic amines has always been a research hotspot in clinical diagnosis and the food industry. Currently, the detection methods of biogenic amines mainly include chromatography (GC-MS, HPLC, and IEC, etc.) and spectroscopy (colorimetry, UV-Vis, and fluorescence, etc.). Among them, spectroscopy has the advantages of high sensitivity, rapidity, simple experimental operation steps, and cheap instrument equipment. The detection mechanisms (J. Mater. Chem. B, 2018, 6, 4872 - 4902; Anal. Methods, 2020, 12, 3560 - 3574.) mainly include photoinduced electron transfer (PET), intramolecular charge transfer (ICT), aggregation-induced fluorescence emission (AIE), and fluorescence resonance energy transfer (FRET), etc. In recent years, the development of new sensing mechanisms has provided new ways and ideas for the detection of biogenic amines, and promoted their application in clinical diagnosis and the food industry, such as organic amine sensing based on the initiation of a photochemical reaction (Angew. Chem. Int. Ed., 2017, 56, 1914 - 1918.) and fluorescence sensing with proton-regulated structural changes (Nat. Commun., 2019, 10, 795.), etc.

[0003] Borate esters are widely used as sensing molecules for the sensing of biomarkers such as reactive oxygen species and reactive nitrogen species in living organisms (Acc. Chem. Res., 2019, 52, 2582 - 2597.). The mechanism is that negatively charged reactive oxygen or nitrogen species attack the boron atom, and the boron atom is converted into an oxygen atom through Baeyer - Villiger oxidation rearrangement (Acc. Chem. Res., 2011, 44, 793 - 804.). Currently, there is no report on the detection of biogenic amines using borate esters as sensing molecules. We found that the precursor of reactive oxygen or nitrogen species is superoxide anion. The generation of superoxide anion is mainly through the reaction of electrons with oxygen, and superoxide anion can still be generated under hypoxic conditions. In addition, the dissolution of biogenic amines in aqueous solution will cause different oxygen contents in the solution. Therefore, we developed perylene monoimide - borate ester molecules. Based on photo - promoted photoreaction and deprotonation regulated by different pH values of biogenic amines, selective recognition of biogenic amines was achieved, and the sensing of spermine was realized under simulated urine conditions. Furthermore, 26 clinical urine samples were selected for detection, and the diagnosis of breast cancer patients was achieved. This patent has potential application value in the screening of tumor patients. Summary of the Invention

[0004] The object of the present invention is to provide a perylene monoimide - borate ester derivative, its preparation method and clinical tumor screening application, so as to provide a new detection method for biogenic amines and a way for early screening of clinical tumor patients.

[0005] The technical solution of the present invention is: a perylene monoimide - borate ester derivative, represented by PMI - B, and its structural formula is as follows:

[0006]

[0007] The preparation method of the above - mentioned perylene monoimide - borate ester derivative includes the following steps:

[0008] (a) Dissolve the perylene monoimide intermediate PMI - H in glacial acetic acid solution, then add liquid bromine thereto, and react at room temperature for 8 - 12 hours; add dichloromethane to the reaction solution, and wash it successively with saturated sodium bicarbonate solution, water and saturated sodium chloride solution. The obtained organic phase is dried with anhydrous sodium sulfate and then separated by column chromatography to obtain a red solid perylene monoimide compound PMI - Br;

[0009] (b) Dissolve the compound PMI - Br obtained in step (a) in dioxane, add bis(pinacolato)diboron, potassium acetate and dichlorobis[(1,1'-bis(diphenylphosphino)ferrocene)palladium]; then, under light - shielding conditions, replace the reaction system with N in a Schlenk flask 2For several times, react at 70 - 80 °C for 6 - 10 hours. After the reaction is completed, cool to room temperature, distill off the solvent. The obtained solid is dissolved in dichloromethane and then separated by column chromatography to obtain the red solid PMI - B.

[0010] In step (a), the dosage ratio of the perylene monoimide intermediate PMI - H to liquid bromine is 600 mg : 1 - 3 mL; the eluent used for column chromatography separation is a mixed solvent of dichloromethane and petroleum ether with a volume ratio of 0.5 - 1.5 : 1;

[0011] In step (b), the dosage ratio of the compound PMI - Br to bis(pinacolato)diboron, potassium acetate, and dichlorobis[1,1'-bis(diphenylphosphino)ferrocene]palladium is 400 - 600 mg : 260 - 280 mg : 130 - 150 mg : 25 - 35 mg; the eluent used for column chromatography separation is a mixed solvent of dichloromethane and petroleum ether with a volume ratio of 1 - 2 : 1, and the column chromatography separation under light - avoiding conditions is a key step.

[0012] Application of the above - mentioned perylene monoimide - borate derivatives in the detection of biogenic amines.

[0013] Application of the perylene monoimide - borate derivatives in a biogenic amine sensing system. The biogenic amines include 1,4 - butanediamine, 1,5 - pentanediamine, spermine, histamine, and tryptamine. Mix the sensing system with the sample to be detected for reaction, and then calculate the content of biogenic amines in the sample by detecting the characteristic absorption peak of the reaction system at 600 - 800 nm.

[0014] Application of the perylene monoimide - borate derivatives in a visual sensor for biogenic amines. The visual sensor for biogenic amines is a PA membrane loaded with PMI - B.

[0015] Application of the perylene monoimide - borate derivatives in the detection of spermine.

[0016] Application of the perylene monoimide - borate derivatives in a reagent or test strip for tumor screening.

[0017] The sample for tumor screening is urine, and the tumor is breast cancer.

[0018] Based on the photo - promoted photochemical reaction and the deprotonation regulated by different pH values of biogenic amines, the present invention realizes the selective recognition of biogenic amines, and realizes the sensing of spermine under simulated urine conditions. Furthermore, 26 clinical urine samples are selected for detection, realizing the diagnosis of breast cancer patients. This patent has potential application value in the screening of tumor patients. The detection process of the present invention is simple and convenient, enabling visual detection, with high efficiency and good sensitivity. Through linear fitting, the detection limit for detecting spermine is 3.37 μmol / L. The present invention can achieve accurate diagnosis of breast cancer patients and is suitable for popularization and application. Description of the Drawings

[0019] Figure 1 (a) UV - Vis spectra; (b) Fluorescence spectra (λ ex = 481 nm) of compound PMI - B in different solvents.

[0020] Figure 2 (a) UV - Vis spectra; (b) Fluorescence spectra (λ ex = 678 nm); (c) Fluorescence spectra (λ ex = 481 nm) of the reaction of compound PMI - B with different biogenic amines under normoxic conditions.

[0021] Figure 3 (a) UV - Vis spectra; (b) Fluorescence spectra (λ ex = 678 nm); (c) Fluorescence spectra (λ ex = 481 nm) of the reaction of compound PMI - B with different biogenic amines under hypoxic conditions; (d) UV - Vis spectra; (e) Fluorescence spectra (λ ex = 678 nm); (f) Fluorescence spectra (λ ex = 481 nm) of the reaction of compound PMI - B with different biogenic amines under hypoxic conditions and xenon lamp illumination for 30 minutes.

[0022] Figure 4 EPR results of the reaction of compound PMI - B with DMPO under illuminated and non - illuminated conditions.

[0023] Figure 5 UV - Vis spectra of compound PMI - OH under different pH conditions.

[0024] Figure 6 Visual sensing of biogenic amines by PMI - B loaded on PA membrane, where 1: PMI - B, 2: PMI - B reacting with water, 3: PMI - B reacting with 1,4 - butanediamine, 4: PMI - B reacting with 1,5 - pentanediamine, 5: PMI - B reacting with spermine, 6: PMI - B reacting with histamine, 7: PMI - B reacting with tryptamine.

[0025] Figure 7 UV-Vis spectra (a), fluorescence spectra (b), and sensitivity curves (c) of compound PMI-B interacting with different amounts of spermine.

[0026] Figure 8 Using mouse urine as a model, different amounts of spermine were added to simulate the urine characteristics of tumor patients. (a) UV-Vis spectra of compound PMI-B interacting with urine containing different amounts of spermine; (b) fluorescence spectra (λ ex = 678 nm); (c) fluorescence spectra (λ ex = 481 nm).

[0027] Figure 9 Ultraviolet-visible spectra of PMI-B interacting with clinical urine (a-c), absorbance intensity ratios A 741 / A 516 (d), A 741 / A 491 (e), and FL 766 (f) analysis results, as well as detection of PA membrane for urine samples from different patients and normal individuals (g), where 1: PMI-B, 2 and 3: urine from normal individuals, 4, 5, and 6: urine from patients with other tumors and precancerous lesions, 7, 8, and 9: urine from breast cancer patients. Detailed implementation manners

[0028] The present invention will be further described below in conjunction with embodiments. The processes and methods not described in detail in the following embodiments are conventional methods well known in the art. The raw materials or reagents used in the embodiments are commercially available products unless otherwise specified and can be obtained through commercial channels.

[0029] Example 1

[0030] Preparation of perylene monoimide-borate derivatives:

[0031] (a) Dissolve perylene monoimide intermediate PMI-H (600 mg, 1.25 mmol) in glacial acetic acid solution (120 mL), and then add liquid bromine (2 mL, 125 mmol) thereto. React at room temperature for 10 hours. Add dichloromethane (500 mL) to the reaction solution, wash it 3 times with saturated sodium bicarbonate solution (100 mL), and then wash it once with water (100 mL) and saturated sodium chloride (100 mL) respectively. Dry the organic phase with anhydrous sodium sulfate and separate it by column chromatography. The eluent is dichloromethane: petroleum ether (volume ratio 1:1) to obtain a red solid perylene monoimide compound PMI-Br with a yield of 68.5%;

[0032] (b) Dissolve the compound PMI-Br obtained in step (a) in dioxane (20 mL), add bis(pinacolato)diboron (272 mg, 1.08 mmol), potassium acetate (140 mg, 1.43 mmol) and dichlorobis[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) (30 mg, 0.03 mmol) thereto. The reaction system is purged with N 2 three times in a Schlenk flask under light protection and reacted at 75 °C for 8 h. Cool to room temperature and evaporate the solvent. The obtained solid is dissolved in 200 mL of dichloromethane and washed with water three times (50 mL×3). The organic phase is dried over anhydrous sodium sulfate and separated by column chromatography. The eluent is dichloromethane:petroleum ether (volume ratio 1.5:1) to obtain a red solid PMI-B with a yield of 66.1%.

[0033] The reaction formula is as follows:

[0034]

[0035] The perylene monoimide intermediate PMI-H can be prepared by the methods known in the prior art, such as the method reported in the patent (Chinese Patent ZL201610572267.7).

[0036] The characterization results of this compound are as follows:

[0037] m.p.>250 °C; 1 H NMR(CDCl 3 , 400 MHz): δ1.20 (d, J = 6.8 Hz, 12H, -CH 3 ), 2.78 (m, 2H, -CH), 7.36 (d, J = 7.6 Hz, 2H, Ar-H), 7.48 (t, J = 8.0 Hz, 1H, Ar-H), 7.68 (t, J = 8.4 Hz, 1H, Ar-H), 8.22 (d, J = 7.6 Hz, 1H, Ar-H), 8.45 (d, J = 8.0 Hz, 1H, Ar-H), 8.48 (t, J = 7.6 Hz, 3H, Ar-H), 8.68 (dd, J = 4.0 Hz, 4.0 Hz, 2H, Ar-H); 13 H NMR(CDCl 3 , 100 MHz): δ24.0, 25.0, 29.1, 84.2, 120.3, 120.8, 121.3, 122.7, 123.7, 124.0, 126.9, 127.7, 129.4, 132.1, 136.3, 137.4, 138.0, 145.7, 164.0; HRMS: calcd for C 40 H 39 BNO4 ,608.2966,found 608.2970.

[0038] (c) Synthesis of compound PMI-OH

[0039] Dissolve PMI-B (100 mg, 0.14 mmol) in 18 mL of DMF solution, add 2 mL of 35% hydrazine hydrate solution, react at room temperature for 40 minutes, evaporate the solvent under reduced pressure, and separate by column chromatography. The eluent is petroleum ether / acetone (volume ratio 2:1) to obtain compound PMI-OH with a yield of 98.3%.

[0040] The characterization results of this compound are as follows:

[0041] m.p. > 250 °C; 1 H NMR (DMSO-d 6 , 400 MHz): δ 1.10 (d, J = 7.2 Hz, 12H, -CH 3 ), 2.68 (m, 2H, -CH), 7.15 (d, J = 8.4 Hz, 1H, Ar-H), 7.37 (d, J = 7.6 Hz, 2H, Ar-H), 7.47 (t, J = 8.0 Hz, 1H, Ar-H), 7.68 (d, J = 8.0 Hz, 1H, Ar-H), 8.32 (d, J = 8.0 Hz, 1H, Ar-H), 8.47 (s, 2H, Ar-H), 8.51 (d, J = 8.0 Hz, 1H, Ar-H), 8.61 (d, J = 8.4 Hz, 1H, Ar-H), 8.67 (d, J = 8.4 Hz, 1H, Ar-H), 8.74 (d, J = 7.6 Hz, 1H, Ar-H); 13 C NMR (DMSO-d 6 , 100 MHz): δ 24.1, 29.0, 111.1, 118.2, 119.2, 119.9, 120.7, 124.1, 126.1, 126.6, 128.6, 129.4, 132.4, 138.3, 138.9, 145.9, 145.9, 157.8, 163.9; HRMS: calcd for C 34 H 27 NNaO 3 , 520.1883, found 520.1875.

[0042] Example 2 Stability study of compound PMI-B

[0043] Take 2×10 -5The compound PMI-B of M was dissolved in solvents such as DMSO, tetrahydrofuran, acetone, methanol, chloroform, acetonitrile, and ethyl acetate. As Figure 1 shown in a, PMI-B has characteristic absorption peaks in the range of 400 - 550 nm. When excited at 481 nm, compound PMI-B has a fluorescence emission peak in the range of 500 - 700 nm ( Figure 1 b). In different solvents, the maximum absorption peak and the maximum fluorescence emission peak of compound PMI-B have different degrees of displacement, but the peak shapes are basically the same. The results indicate that PMI-B has good solubility in common organic solvents, the solvent has no effect on the structure of compound PMI-B, and PMI-B has stability in common solvents.

[0044] Example 3 Sensing study of PMI-B for different biogenic amines under normoxic conditions

[0045] Under normoxic conditions (21% O 2 ), 50-fold amounts of biogenic amines, including 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, spermine, histamine, and tryptamine, were added to the DMSO solution of PMI-B (2×10 -5 M). As Figure 2 shown in a, a new absorption peak appears in the range of 600 - 800 nm, and the maximum peak is located at 741 nm. Especially for spermine, the ratio of A 741 / A 516 is about 2.0, while the A 741 / A 516 ratios of other amines are lower than 0.4, indicating that PMI-B has a selective recognition effect on spermine. The fluorescence spectra of the interaction between PMI-B and biogenic amines show that when PMI-B is excited at 481 nm, the intensity of its own fluorescence emission peak decreases, while when excited at 678 nm, the fluorescence emission peak intensity of the transformed substance of PMI-B increases. The research results indicate that after the interaction between PMI-B and biogenic amines, it is transformed into a substance with near-infrared absorption characteristics and has a selective recognition effect on spermine among the tested biogenic amines.

[0046] Example 4 Sensing study of PMI-B for different biogenic amines under hypoxic conditions

[0047] As Figure 3 shown in a - c, under hypoxic conditions (1.0% O 2 , 94% N 2 and 5% CO 2 ), in the PMI-B (2×10 -5To 50-fold amounts of bioamines, including 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, spermine, histamine, and tryptamine, were added to DMSO solutions of PMI-B. The perylene monoimide-borate derivative PMI-B interacted with the bioamines, and a new strong absorption peak appeared in the 600 - 800 nm range. However, its intensity was weaker than that under normal oxygen conditions. Among them, PMI-B still had a selective recognition effect on spermine, with the maximum absorption intensity at 741 nm, and the A 741 / A 516 ratio was approximately 0.36, indicating that the sensing of PMI-B to bioamines was related to the oxygen content.

[0048] As Figure 3 shown in d - f, under hypoxic conditions (1.0% O 2 , 94% N 2 and 5% CO 2 ), after irradiating with a 250-watt xenon lamp for 30 minutes and allowing PMI-B to interact with the bioamines, the strong absorption peak in the 600 - 800 nm range was significantly enhanced, while the absorption peak intensity in the 400 - 600 nm range decreased. Among them, after PMI-B interacted with spermine, the A 741 / A 516 ratio was approximately 2.0, which was basically consistent with the results under normal oxygen conditions. For the other amines tested, the A 741 / A 517 ratio was lower than 0.82, indicating that light could promote the recognition of PMI-B to bioamines.

[0049] Example 5 Mechanism study of the interaction between PMI-B and bioamines

[0050] EMPO is a general reagent for detecting superoxide anions. After it reacts with superoxide anions, DMPO-O2 ·- is generated, showing an EPR signal. 200 μL of 0.5 mg / mL PMI-B was mixed with 200 μL of 100 μmol / L DMPO. Under normal oxygen conditions, after irradiating for 10 minutes, as Figure 4 shown, 4 EPR signals were shown, while the unirradiated sample had no EPR signal peak, indicating that PMI-B could efficiently generate superoxide anions under light irradiation.

[0051] The interaction between PMI-B and bioamines led to the generation of a new absorption peak in the 600 - 800 nm range. After column chromatography separation and characterization by 1 H NMR and HRMS, etc., its structure was a hydroxy-substituted compound PMI-OH. Furthermore, the spectral characteristics under different pH conditions were studied by pH-related UV-Vis spectra. As Figure 5 shown, at a concentration of 2×10 -5In the PMI-OH solution of M, in the pH range of 3 to 6, PMI-OH exists in the hydroxyl form, and the maximum intensity of the characteristic absorption peak is at 554 nm. Between pH 9 and 12, under alkaline conditions, PMI-OH is completely converted to PMI-O - , and the maximum intensity of the characteristic absorption peak is located at 731 nm. When the pH value is between 7 and 8, both PMI-OH and PMI-O - exist and have absorption in the range of 400 - 800 nm. Therefore, we confirmed that the selective sensing of biogenic amines by PMI-B is due to the photo-promoted photoreaction, in which PMI-B is converted to PMI-OH, and PMI-OH is sensitive to pH and is converted to PMI-O - under neutral and alkaline conditions, with near-infrared absorption characteristics.

[0052] The research results show that the mechanism of the interaction between PMI-B and biogenic amines is the combination of photo-promoted photoreaction and pH-regulated deprotonation. Under light irradiation, PMI-B generates superoxide anions, which attack the boron atom and are converted to the hydroxyl compound PMI-OH through Baeyer-Villiger oxidation rearrangement. PMI-OH undergoes deprotonation under neutral and alkaline conditions to be converted to PMI-O - , and PMI-O - has a characteristic absorption peak in the range of 600 - 800 nm.

[0053] Example 6: Study on the sensing of biogenic amines by PA membrane loaded with PMI-B

[0054] The PA membrane was immersed in a methanol solution of PMI-B (1.0×10 -3 mol / L), taken out after 2 hours, and air-dried in the dark. The PA membrane loaded with PMI-B was immersed in aqueous solutions such as water, 1,4-butanediamine (concentration 1000 mg / kg), 1,5-pentanediamine (concentration 1000 mg / kg), spermine (concentration 1000 mg / kg), histamine (concentration 500 mg / kg), and tryptamine (concentration 800 mg / kg) for 1 second and then taken out, divided into a light-irradiated group (irradiated for 10 minutes) and a non-light-irradiated group. It was visually observed that the color change of PMI-B under light irradiation for 1,4-butanediamine, 1,5-pentanediamine, and spermine was obvious, showing light purple, purple, and light green respectively. In the non-light-irradiated group, only spermine changed to light green. The results show that PMI-B attached to the PA membrane can achieve the sensing of biogenic amines, especially spermine.

[0055] Example 7: Detection limit of PMI-B and spermine

[0056] PMI-B (2×10 -5In DMSO solutions of PMI-B (

[0057] Example 8 Study on the Interaction between PMI-B and Spermine in Urine

[0058] The amount of spermine is related to cancer patients. According to literature reports, the content of spermine in the urine of breast cancer patients and prostate cancer patients is significantly increased. Therefore, using mouse urine as a model, different amounts of spermine were added to the urine to prepare simulated tumor patient urine containing different amounts of spermine. In DMSO solutions of PMI-B (2×10 -5 M), 20 μL of urine containing different amounts of spermine was added respectively. Taking the urine without added spermine as a blank test, after irradiation with xenon lamp for 30 minutes, their interaction was studied by UV-Vis spectroscopy and fluorescence spectroscopy. As Figure 8 shown, characteristic absorption peaks appeared at 600 - 800 nm, and the absorption peak intensity increased with the increase of spermine content. The fluorescence emission peaks at 770 nm and 580 nm increased and decreased respectively. The results indicate that PMI-B still responds to spermine under urine conditions. The research results show that PMI-B has potential application value in the screening of cancer patients.

[0059] Example 9 Study on the Interaction between PMI-B and Urine of Clinical Patients

[0060] The response of PMI-B to 26 clinical urine samples was studied by ultraviolet-visible spectroscopy, fluorescence spectroscopy, PA film color development and other tests, including 10 urine samples of normal people, 8 urine samples of breast cancer patients, and 8 urine samples of other tumors and their precancerous lesions patients. When 10 μL of normal human urine was added, the intensity of the ultraviolet-visible absorption peak of compound PMI-B at 741 nm increased, and the intensity range was between 0.0087 and 0.024; when breast cancer patient urine was added, the absorbance intensity at 741 nm increased significantly, and the range was between 0.054 and 0.16; when urine samples of other female tumors and precancerous lesions patients were added, the absorbance intensity at 741 nm increased, and the range was between 0.017 and 0.051. The results show that PMI-B has a selective recognition effect on the urine of breast cancer patients and can be used as a biomarker for breast cancer. Furthermore, we compared A 741 / A 516 、A 741 / A 491 and FL 766The statistical results showed that breast cancer patients > other tumor and precancerous lesion patients > normal people. The membrane color development has visual characteristics, which is more conducive to actual clinical applications. We respectively selected the urine of 2 normal people, the urine of 3 other tumor and precancerous lesion patients, and the urine of 3 breast cancer patients. The PA-loaded PMI-B still showed a specific response to the urine of breast cancer patients. These research results indicate that the PMI-B molecule has a specific response to breast cancer patients both in solution and when loaded onto the PA membrane, and has potential application value in the early screening of tumors.

Claims

1. Use of perylene monoimide-borate derivatives in the preparation of spermine detection reagents. The perylene monoimide-borate derivatives are represented by PMI-B, and their structural formula is as follows: 。 2. The use according to claim 1, wherein, it is the use of the perylene monoimide-borate derivatives in a spermine sensing system. The sensing system is mixed and reacted with the sample to be detected, and then the content of spermine in the sample is calculated by detecting the characteristic absorption peak of the reaction system at 600 - 800 nm.

3. The use according to claim 1, wherein, it is the use of the perylene monoimide-borate derivatives in a spermine visual sensor.

4. The use according to claim 3, wherein, the spermine visual sensor is a PA membrane loaded with PMI-B.

5. Use of perylene monoimide-borate derivatives in the preparation of reagents or test strips for tumor screening by detecting spermine. The perylene monoimide-borate derivatives are represented by PMI-B, and their structural formula is as follows: 。 6. The use according to claim 5, wherein, the sample for tumor screening is urine, and the tumor is breast cancer.

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