A bifunctional norpinyl acridine fluorescent probe capable of simultaneously detecting cadaverine and hydrazine, its preparation method and application

Abstract

This invention discloses a bifunctional norpinel acridine fluorescent probe capable of simultaneously detecting cadaverine and hydrazine, its preparation method, and its application. The probe is 9-(2-carboxyphenyl)-6-(diethylamino)-4-((5-(4-(3,3-dimethyl-1,2,3,4-tetrahydro-2,4-bridged methylene acridine-9-yl)phenyl)furan-2-yl)-methylene-1,2,3,4-tetrahydro-cottonium (TAPF-CPTX). This probe specifically reacts with cadaverine and hydrazine. Under ultraviolet light irradiation, the TAPF-CPTX solution does not emit fluorescence. Upon addition of cadaverine and hydrazine, respectively, the fluorescence color of the probe solution changes from colorless to green and orange-yellow. The linear detection ranges for cadaverine and hydrazine are 0-25.0 μM and 0-4.0 μM, respectively, with detection limits of 18 nM and 10 nM, and response times of 45 s and 20 s, respectively. Therefore, the TAPF-CPTX probe can serve as a bifunctional fluorescent probe capable of simultaneously detecting cadaverine and hydrazine, possessing advantages such as good selectivity, high sensitivity, and short response time.

Description

Technical Field

[0001] This invention belongs to the field of fluorescent probe technology, and relates to a bifunctional norpinyl acridine fluorescent probe capable of simultaneously detecting cadaverine and hydrazine, its preparation method, and its application. Background Technology

[0002] Cadaverine, a typical biogenic amine, chemically named 1,5-pentanediamine, primarily originates from the decarboxylation of lysine during protein spoilage under the action of amino acid decarboxylases. Its content is often used as an important indicator for assessing the degree of food spoilage and environmental pollution levels. Although cadaverine itself has low acute toxicity, it can indirectly enhance the toxicity of histamine and other biogenic amines by inhibiting the activity of histamine and tyramine metabolic enzymes. Furthermore, cadaverine reacts with nitrite to form nitrosamines, which have potential carcinogenic toxicity and pose a long-term threat to human health. Currently, the detection of cadaverine mainly relies on high-performance liquid chromatography (HPLC) or gas chromatography-mass spectrometry (GC-MS). While these methods have high sensitivity, they suffer from drawbacks such as complex sample pretreatment, long analysis time, expensive instruments, and difficulty in achieving rapid on-site detection.

[0003] Hydrazine (N₂H₄) is an important industrial chemical widely used in chemical synthesis, rocket propellants, and pharmaceutical production. Hydrazine is toxic to multiple organs in the human body, damaging the nervous system, liver, and kidneys. The International Agency for Research on Cancer (IARC) classifies it as a Group 2B carcinogen. Hydrazine easily remains in wastewater and soil, causing persistent damage to ecosystems. Existing methods for detecting hydrazine mainly include gas chromatography-mass spectrometry, electrochemical methods, and titration. These methods also suffer from problems such as long response times, cumbersome operation, reliance on large instruments, and difficulty in meeting the needs of real-time on-site monitoring.

[0004] Addressing the numerous shortcomings of existing detection methods, fluorescent probe technology exhibits significant advantages due to its unique detection mechanism. Fluorescent probes typically consist of a recognition group and a fluorescent reporter group, capable of specifically reacting with the target analyte, causing significant changes in fluorescence intensity and emission wavelength, thereby achieving highly sensitive and selective identification of the target analyte. Compared to traditional methods, fluorescent probe methods offer outstanding advantages such as ease of operation, rapid response, no need for complex sample pretreatment, low instrument cost, and the ability to achieve in-situ visual detection. In particular, combining fluorescent probes with flexible materials such as hydrogels and filter paper can further create portable sensing platforms, meeting the needs of rapid on-site screening and real-time dynamic monitoring, showing broad application prospects in fields such as food safety, environmental monitoring, and bioimaging. Therefore, developing novel fluorescent probes for the detection of cadaverine and hydrazine has significant practical value in overcoming the limitations of existing technologies and improving detection efficiency and convenience.

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:

[0006] A bifunctional norpinyl acridine fluorescent probe capable of simultaneously detecting cadaverine and hydrazine has the following structural formula:

[0007]

[0008] The molecular formula of the fluorescent probe is C. s0 H 45 N2O4, chemically named 9-(2-carboxyphenyl)-6-(diethylamino)-4-((5-(4-(3,3-dimethyl-1,2,3,4-tetrahydro-2,4-bridged methylene acridine-9-yl)phenyl)furan-2-yl)methylene-1,2,3,4-tetrahydro-cottonium, abbreviated as TAPF-CPTX.

[0009] The method for preparing a bifunctional norpinyl acridine fluorescent probe capable of simultaneously detecting cadaverine and hydrazine involves using 5-(4-(3,3-dimethyl-1,2,3,4-tetrahydro-2,4-bridged methylene acridine-9-yl)phenyl)furan-2-carboxaldehyde (TAPF-C) as a raw material, and reacting it with 9-(2-carboxyphenyl)-6-(diethylamino)-1,2,3,4-tetrahydro-cottonium (CPTX) to obtain the probe TAPF-CPTX. The specific preparation steps are as follows:

[0010] (1) Dissolve 340-510g (1-1.5mol) of TAPF-C in acetic acid, add 3-4mol of CPTX under nitrogen protection, and reflux for 10-12h until the raw materials are completely reacted;

[0011] (2) After the reaction is complete, the reaction solution is cooled to room temperature, and the precipitated solid product is filtered to obtain the crude product of TAPF-CPTX;

[0012] (3) After washing the crude TAPF-CPTX product three times with 1-1.5L of cold ethanol, the product was dried to obtain black powder TAPF-CPTX.

[0013] The application of the bifunctional norpinyl acridine fluorescent probe in the detection of cadaverine and hydrazine lies in the fact that the compound APF-CPTX can specifically react with cadaverine and hydrazine. Under 365 nm ultraviolet light irradiation, after adding cadaverine and hydrazine to the solution of the probe TAPF-CPTX, respectively, strong fluorescence is emitted at 495 nm and 578 nm, respectively, and the fluorescence color changes from colorless to green and orange-yellow, respectively. The linear detection ranges for cadaverine and hydrazine are 0-25.0 μM and 0-4.0 μM, respectively, the detection limits are 18 nM and 10 nM, respectively, and the response times are 45 s and 20 s, respectively.

[0014] Beneficial effects: Compared with the prior art, the compound TAPF-CPTX obtained by condensing TAPF-C with CPTX in this invention can specifically identify cadaverine and hydrazine, and can sensitively detect the content of cadaverine and hydrazine in solution. It has many advantages such as convenient synthesis, good selectivity and high sensitivity, and has good application prospects. Attached Figure Description

[0015] Figure 1 The fluorescence spectra of the probe TAPF-CPTX in different concentrations of cadaverine environments are shown.

[0016] Figure 2 This is the fluorescence spectrum of the probe TAPF-CPTX in hydrazine environments at different concentrations. Detailed Implementation

[0017] The present invention will be further described below with reference to specific embodiments.

[0018] Example 1

[0019] The reaction formula for preparing the probe TAPF-CPTX is as follows:

[0020]

[0021] The specific steps are as follows:

[0022] Preparation of TAPF-CPTX:

[0023] 1 mmol of TAPF-C was dissolved in 10-15 mL of acetic acid, and then 4 mmol of CPTX was added. The mixture was refluxed for 12 h. The reaction solution was cooled to room temperature, and the precipitated solid product was filtered to obtain crude TAPF-CPTX. The crude product was washed three times with cold ethanol and dried to obtain 0.45 g of black powder TAPF-CPTX, with a yield of 65%. 1H NMR (600MHz, CDCl3) δ: 8.34 (s, 1H), 8.18 (d, J=7.8Hz, 1H), 7.98-7.92 (m, 2H), 7.72 (dt, J=24.8, 7.6Hz, 3H), 7.63 (t, J=7.6Hz, 1H), 7.54-7.46 (m, 2H), 7.40 (dd, J=20.4, 8.1Hz, 2H), 7.21 (d, J=7.6Hz, 1H), 7.01 (dd, J=35.2, 3.6H z, 2H), 6.90 (d, J=7.7Hz, 1H), 6.81-6.77 (m, 1H), 6.66 (s, 1H), 3.56-3.51 (m, 3H), 2.86 (dd, J=10.4, 4.2Hz, 3H), 2 .40-2.27(m, 3H), 2.14-2.00(m, 4H), 1.84(s, 3H), 1.64(dd, J=14.9, 7.5Hz, 2H), 1.51-1.43(m, 6H), 0.78(s, 5H). 13 C NMR (150MHz, DMSO) δ: 209.87, 181.11, 166.68, 159.18, 153.16, 152.34, 142.31, 141.62, 140.11, 138.27, 135.45, 134.28, 131.75, 131.03, 130.41, 129.12, 127.98, 126.83, 126.69, 125.31, 123.68, 116.08, 115.9 7, 115.55, 115.07, 114.17, 114.06, 113.02, 110.49, 106.91, 93.54, 89.38, 83.86, 74.70, 73.49, 61.01, 57.30, 55.10, 54.21, 53.83, 53.22, 35.08, 31.68, 27.48, 25.69, 20.44, 19.27, 18.52, 16.42, 14.61, 11.25.

[0024] Example 2

[0025] TAPF-CPTX was prepared to a concentration of 1×10⁻⁶. -5 Prepare PBS buffer solution (pH = 7.4, 10 mmol / L) and simultaneously dissolve cadaverine in pure water to prepare solutions with concentrations of 0 and 2.5 × 10⁻⁶ mol / L. -6 5.0×10 -6 10.0×10 -6 15.0×10 -6 20.0×10 -6 25.0×10-6 30.0×10 -6 35.0×10 -6 40.0×10 -6 A mol / L solution. The fluorescence emission spectra of TAPF-CPTX in the presence of different concentrations of cadaverine were measured using a fluorescence spectrophotometer via fluorescence spectrophotometric titration. For example... Figure 1 As shown, as the concentration of cadaverine in the solution gradually increased from 0 mol / L to 40.0 × 10⁻⁶, -6 At a concentration of mol / L, the fluorescence emission intensity of this compound gradually increases at 495 nm. This indicates that the compound can be used as a sensitive fluorescent probe for the detection of cadaverine.

[0026] Example 3

[0027] TAPF-CPTX was prepared to a concentration of 1×10⁻⁶. -5 Prepare 10 mmol / L PBS buffer solution (pH = 7.4), and simultaneously dissolve hydrazine in PBS buffer to prepare solutions with concentrations of 0 and 1.0 × 10⁻⁶ mol / L. -6 1.5×10 -6 2.0×10 -6 2.5×10 -6 2.75×10 -6 3.0×10 -6 3.5×10 -6 3.75×10 -6 4.0×10 -6 A mol / L solution. Fluorescence emission spectra of TAPF-CPTX in the presence of different concentrations of hydrazine were measured using a fluorescence spectrophotometer via fluorescence titration. For example... Figure 2 As shown, as the concentration of hydrazine in the solution gradually increases from 0 mol / L to 4.0 × 10⁻⁶, -6 At a concentration of mol / L, the fluorescence emission intensity of this compound gradually increases at 578 nm. This indicates that the compound can be used as a sensitive fluorescent probe for the detection of hydrazine.

Claims

1. A bifunctional norpinyl acridine fluorescent probe capable of simultaneously detecting cadaverine and hydrazine, its preparation method and application, characterized in that, The fluorescent probe is 9-(2-carboxyphenyl)-6-(diethylamino)-4-((5-(4-(3,3-dimethyl-1,2,3,4-tetrahydro-2,4-bridged methylene acridine-9-yl)phenyl)furan-2-yl)methylene-1,2,3,4-tetrahydroketonium, abbreviated as TAPF-CPTX, and its structural formula is:

2. The method for preparing a bifunctional norpinyl acridine fluorescent probe capable of simultaneously detecting cadaverine and hydrazine as described in claim 1, characterized in that, The preparation method of the probe TAPF-CPTX is as follows: The probe TAPF-CPTX was prepared by condensing 5-(4-(3,3-dimethyl-1,2,3,4-tetrahydro-2,4-bridged methylene acridine-9-yl)phenyl)furan-2-carboxaldehyde (TAPF-C) with 9-(2-carboxyphenyl)-6-(diethylamino)-1,2,3,4-tetrahydro-cottonium (CPTX).

3. The method for preparing a bifunctional norpinyl acridine fluorescent probe TAPF-CPTX capable of simultaneously detecting cadaverine and hydrazine according to claim 2, characterized in that, The specific preparation steps of TAPF-CPTX are as follows: (1) Dissolve 340-510g (1-1.5mol) of TAPF-C in acetic acid, add 3-4mol of CPTX under nitrogen protection, and reflux for 10-12h until the raw materials are completely reacted; (2) After the reaction is complete, the reaction solution is cooled to room temperature, and the precipitated solid product is filtered to obtain the crude product of TAPF-CPTX; (3) After washing the crude TAPF-CPTX product three times with 1-1.5L of cold ethanol, the product was dried to obtain black powder TAPF-CPTX.

4. The application of the bifunctional norpinel acridine fluorescent probe of claim 1 in the detection of cadaverine and hydrazine.

5. The application according to claim 4, characterized in that, The fluorescent probe TAPF-CPTX specifically reacts with cadaverine and hydrazine. Under 365 nm UV irradiation, after adding cadaverine and hydrazine to the probe solution, the probe TAPF-CPTX emits strong fluorescence at 495 nm and 578 nm, respectively, and the fluorescence color changes from colorless to green and orange-yellow, respectively. The linear detection ranges for cadaverine and hydrazine are 0-25.0 μM and 0-4.0 μM, respectively, with detection limits of 18 nM and 10 nM, respectively, and response times of 45 s and 20 s, respectively.

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