Isolongifolanone-based fluorescent probe for detecting Hg < 2 + > as well as preparation method and application of isolongifolanone-based fluorescent probe
By preparing the isolongifolia alkane-based fluorescent probe ABP-HDT, the problems of complex Hg2+ detection methods and low sensitivity in the existing technology were solved, and rapid, sensitive and specific Hg2+ detection was achieved, which is suitable for the accurate detection of Hg2+ in the environment.
Patent Information
- Application Number
- CN202510946981.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-09
- Publication Date
- 2025-09-23
AI Technical Summary
The existing technology lacks a rapid, sensitive and specific Hg2+ detection method, and traditional methods have the problems of complex operation and high cytotoxicity.
The isolongifolia alkane-based fluorescent probe ABP-HDT was prepared through a condensation cyclization reaction. It was reacted with 1,3-propanedithiol and boron trifluoride etherate under a nitrogen atmosphere. The purified fluorescent probe was non-fluorescent under 365nm ultraviolet light and turned green after adding Hg2+, which was used for the detection of Hg2+.
Rapid, sensitive and specific Hg2+ detection was achieved, with a detection limit of 9.0×10-8M, rapid response, easy synthesis and good selectivity.
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Figure CN120682207A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of fluorescence detection technology and relates to a method for detecting Hg 2+ Isolongifolia ketone-based fluorescent probe, preparation method and application thereof. Background Art
[0002] Mercury is a trace element pollutant and a non-biodegradable substance that not only accumulates in the environment through a series of human activities, but also causes health problems through the food chain. Heavy metals have become the main source of environmental pollutants in industry and daily life. Among various known harmful heavy metal ions, mercury ions (Hg 2+ ) is considered one of the most toxic and deadly metals and exists in the form of organic and inorganic compounds. Long-term exposure to Hg 2+ It may cause a series of diseases, such as immune system imbalance, central nervous system damage, hearing loss, abdominal pain, kidney failure, and even death. In addition, the World Health Organization (WHO) has classified Hg in drinking water as 2+ The maximum allowable concentration of Hg is set to 6.0 μg / L. Therefore, an accurate and rapid detection method for Hg 2+ The analysis method is very important.
[0003] For the detection of Hg 2+ Compared with traditional analytical methods (such as atomic absorption spectroscopy, laser-induced breakdown spectroscopy, inductively coupled plasma optical emission spectroscopy, electrochemical detection, etc.), organic small molecule fluorescent probes have the advantages of ease of use, low cytotoxicity, strong real-time imaging capability, good specificity, strong biocompatibility, and clear sensing mechanism. Summary of the Invention
[0004] In view of the shortcomings of the prior art, the present invention aims to provide a method for detecting Hg 2+ The isolongifolia alkane-based fluorescent probe can meet the use requirements. Another technical problem to be solved by the present invention is to provide a method for preparing the fluorescent probe ABP-HDT. The technical problem to be solved by the present invention is to provide an application of the fluorescent probe ABP-HDT.
[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is:
[0006] Isolongifolia ketone-based fluorescent probe ABP-HDT, its structural formula is:
[0007]
[0008] The method for detecting Hg 2+The preparation method of the isolongifolia ketone-based fluorescent probe is characterized in that ABP-HC and 1,3-propanedithiol undergo a condensation cyclization reaction under a nitrogen atmosphere to prepare the fluorescent probe ABP-HDT. The specific preparation method includes:
[0009] (1) 1 mmol of ABP-HC, 1-2 mmol of 1,3-propanedithiol, and 5-10 mL of anhydrous dichloromethane were sequentially added to a three-necked flask equipped with a stirrer. 1-3 mmol of boron trifluoride etherate was added under a nitrogen atmosphere and the mixture was reacted at room temperature for 2-3 h.
[0010] (2) The reaction solution is distilled to recover the solvent, thereby obtaining a crude ABP-HDT product;
[0011] (3) The crude ABP-HDT product was purified by silica gel column chromatography (dichloromethane:methanol=300:1, v / v) to obtain a light yellow solid ABP-HDT.
[0012] The fluorescent probe ABP-HDT is used to detect Hg 2+ The probe solution does not emit fluorescence under 365nm ultraviolet light. 2+ After that, the fluorescence color of the solution changes from colorless to green, which can be used for Hg 2+ Detection.
[0013] Beneficial effect: Compared with the prior art, the fluorescent probe ABP-HDT prepared by the present invention using isolongifolia alkane as raw material can specifically identify Hg 2+ , as a detection of Hg 2+ The fluorescent probe has the advantages of convenient synthesis, rapid response (5 minutes), high sensitivity (9.0×10 -8 M), good selectivity and many other advantages, and has good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS
[0014] Figure 1 The fluorescence probe ABP-HDT is combined with different concentrations of Hg 2+ Fluorescence spectrum of the effect;
[0015] Figure 2 This is the fluorescence spectrum of the fluorescent probe ABP-HDT interacting with different metal ions. DETAILED DESCRIPTION
[0016] The present invention will be further described below with reference to specific embodiments.
[0017] Example 1
[0018] The preparation of the fluorescent probe ABP-HDT is as follows:
[0019]
[0020] 1 mmol of ABP-HC, 1 mmol of 1,3-propanedithiol, and 10 mL of anhydrous dichloromethane were sequentially added to a three-necked flask equipped with a stirrer. Under a nitrogen atmosphere, 1 mmol of boron trifluoride etherate was added and the mixture was allowed to react at room temperature for 2 hours. The solvent was recovered by distillation to obtain the crude product ABP-HDT. The product was then purified by silica gel column chromatography (dichloromethane:methanol = 300:1, v / v) to obtain the fluorescent probe ABP-HDT with a yield of 68.6%. 1 H NMR (600MHz, CDCl3), δ (ppm): 8.03 (s, 1H), 7.69 (t, J = 6.1Hz, 2H), 7.67 (d, J = 2.3Hz, 1H), 7.60 (s, 1H), 7.57 (dd, J = 8.3, 2.3Hz, 1H), 7.41 (d, J = 8. 4Hz, 1H), 7.32 (dd, J=8.1, 1.8Hz, 2H), 7.25-7.23 (m, 1H), 7.01 (d, J=8.4Hz, 1H), 6.62 (s, 1H), 5.54 (s, 1H), 3.12 (ddd, J=14.6, 12.5, 2.4Hz, 2H), 2.97(dt, J=14.2, 3.7Hz, 2H), 2.85(s, 1H), 2.76(d,J=16.5Hz, 1H), 2.27 (d, J=16.5Hz, 1H), 2.23 (dtd, J=11.5, 4.6, 2.5Hz, 1H), 2.04-1.97 (m, 2H ), 1.81 (dd, J=11.3, 7.0Hz, 2H), 1.71 (td, J=12.1, 3.9Hz, 1H), 1.60-1.5 5(m, 4H), 1.28(d, J=10.0Hz, 2H), 0.98(s, 3H), 0.74(s, 3H), 0.67(s, 3H). 13 CNMR (150MHz, CDCl3), δ (ppm): 154.25, 139.82, 133.43, 130.29, 129.84, 128.69, 128.10, 126.92, 126.89, 126.33, 126.04, 125.32, 124.53 ,117.91,58.93,55.74,48.29,47.29,45.72,41.46,37.58,32.66,31 .91, 30.73, 28.58, 26.24, 25.59, 25.09, 25.05, 23.39.MS(m / z): [M+H] + calcd.for C 38 H 41 NOS2+H+ , 592.2708; found, 592.2712.
[0021] Example 2
[0022] The fluorescent probe ABP-HDT was added into the solution (DMSO / PBS buffer solution = 5:5, v / v) to a concentration of 1.0×10 -5 M solution. Using fluorescence spectrophotometry, different concentrations of Hg 2+ The fluorescence emission spectrum of the fluorescent probe ABP-HDT after addition of (0-80 μM) was as follows: Figure 1 The results show that as Hg 2+ With the gradual increase of concentration, the fluorescence emission intensity of the probe at 488 nm gradually increased, indicating that the fluorescent probe ABP-HDT can be used to detect Hg in solution. 2+ The concentration of Hg 2+ The detection limit reached 9.0×10 -8 M.
[0023] Example 3
[0024] The fluorescent probe ABP-HDT was added into the solution (DMSO / PBS buffer solution = 5:5, v / v) to a concentration of 1.0×10 -5 M solution, one portion was used as blank sample, and the other portions were added with other analytes, namely Hg 2+ Mg 2+ 、Cu + , Ca 2+ 、Mn 2+ , K+, Na + 、Ni 2+ 、Co 2+ 、Ba 2+ 、Fe 3+ 、Al 3+ 、Zn 2+ , Pb 2+ 、Cd 2+ Cr 3+ , the fluorescence emission spectrum of the solution was measured, such as Figure 2 The results show that Hg 2+ The addition of 2-HgCl2 significantly enhanced the fluorescence emission intensity of the probe at 488 nm, while the addition of other metal ions did not significantly change the fluorescence spectrum of the probe. This shows that ABP-HDT can be used as a specific detection method for Hg 2+ fluorescent probes.
Claims
1. A method for detecting Hg 2+ The isolongifolia ketone-based fluorescent probe is characterized in that The probe is 3-(1,3-dithian-2-yl)-4′-(1,1,5,5-tetramethyl-1,3,4,5,6,12b-hexahydro-2H-2,4a-methanobenzoacridin-7-yl)-[1,1′-biphenyl]-4-ol (abbreviated as ABP-HDT), and its structural formula is:
2. The method for detecting Hg according to claim 1 2+ The preparation method of the isolongifolia ketone-based fluorescent probe is characterized in that: The preparation process is as follows: ABP-HDT was prepared by condensation and cyclization reaction of an isolongifolone derivative 4-hydroxy-4′-(1,1,5,5-tetramethyl-1,3,4,5,6,12b-hexahydro-2H-2,4a-endimethylenebenzoacridin-7-yl)-[1,1′-biphenyl]-3-carbaldehyde (abbreviated as ABP-HC) with 1,3-propanedithiol.
3. The method for detecting Hg according to claim 2 2+ The preparation method of the isolongifolia ketone-based fluorescent probe is characterized in that: Under a nitrogen atmosphere, ABP-HC undergoes a condensation cyclization reaction with 1,3-propanedithiol to obtain the fluorescent probe ABP-HDT. The specific preparation method includes: (1) 1 mmol of ABP-HC, 1-2 mmol of 1,3-propanedithiol, and 5-10 mL of anhydrous dichloromethane were sequentially added to a three-necked flask equipped with a stirrer. 1-3 mmol of boron trifluoride etherate was added under a nitrogen atmosphere and the mixture was reacted at room temperature for 2-3 h. (2) The reaction solution is distilled to recover the solvent, thereby obtaining a crude ABP-HDT product; (3) The crude ABP-HDT product was purified by silica gel column chromatography (dichloromethane:methanol=300:1, v / v) to obtain a light yellow solid ABP-HDT.
4. The fluorescent probe ABP-HDT according to claim 1 is used to detect Hg 2+ application.
5. The use according to claim 4, characterized in that Under 365nm UV irradiation, the DMSO / PBS buffer solution of the fluorescent probe ABP-HDT did not emit fluorescence. 2+ After that, the fluorescence color of the solution changed from colorless to green, and the detection limit reached 9.3×10 -8 M, the response time is 5 minutes.