Fluorescence detection probe as well as preparation method and application thereof
Patent Information
- Application Number
- CN202510216338.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-26
- Publication Date
- 2025-05-23
AI Technical Summary
The prior art has problems such as cumbersome, labor-intensive and heavily dependent on equipment in detecting ethylene, and the new sensors have problems such as difficulty in precise control, high cost and low reliability during the preparation and use.
The fluorescence detection probe was prepared by composited metal organic frame material with enofloxacin. Its high pore size, high adsorption property and large specific surface area characteristics were used to combine enofloxacin to achieve specific fluorescence recognition of ethylene.
It realizes fast and efficient detection of ethylene, breaks away from the limitations of instrument detection, reduces the cost and difficulty of detection, and improves the accuracy and reliability of detection.
Smart Images
Figure CN120025814A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of luminescent detection materials, and specifically discloses a fluorescent detection probe and a preparation method and application thereof. Background Art
[0002] Ethephon (ETH) is one of the most popular plant growth regulators in the world and a pre-harvest and post-harvest ripening enhancer for fruits, vegetables, and grains. However, excessive use of ethephon has been known to be harmful to human health. Long-term intake of foods containing ethephon can cause gastrointestinal irritation and erode the digestive system. Large intake of foods containing ethephon can be harmful to the kidneys and brain. Therefore, the detection of ethephon in plant-based foods has become an urgent issue to be addressed.
[0003] Traditional detection methods mainly include gas chromatography (GC), high performance liquid chromatography (HPLC) and ion chromatography (IC). Although the above technologies have extremely high responsiveness and accuracy for pesticide detection, they are cumbersome, labor-intensive and heavily dependent on equipment, which brings many inconveniences to the detection of ethephon. New ethephon rapid detection technologies have also made great progress, such as the detection of ethephon by gold nanoparticle-loaded molecular imprinting switch sensors. To a certain extent, these methods make up for the shortcomings of instrumental analysis methods, but the reaction conditions of gold nanoparticle-loaded molecular imprinting switch sensors need to be precisely controlled during the preparation process, which greatly increases the difficulty and cost. The shedding, deformation and aging of the membrane layer will affect the reliability of the sensor. Due to the large interface resistance between gold nanoparticles and molecular imprinting polymers or the poor electron transfer path, the sensor response speed slows down or the signal attenuates, thereby affecting the detection effect.
[0004] Based on this, developing a method that can quickly and accurately detect ethephon has important practical significance for food safety control. Summary of the invention
[0005] In view of the shortcomings of the existing methods for detecting ethephon, the present invention provides a fluorescent detection probe and a preparation method and application thereof. The fluorescent detection probe is a composite material of a metal organic framework material and enoxacin. The metal organic framework material has high porosity, high adsorption and large specific surface area. In combination with enoxacin, the specific fluorescent recognition of ethephon can be realized, thereby achieving the purpose of rapid and efficient detection of ethephon.
[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions: The first aspect of the present invention provides a fluorescent detection probe, which comprises a metal organic framework material and enoxacin; wherein the ligands of the metal organic framework material are 1,3,5-benzenetricarboxylic acid and 2,5-dihydroxyterephthalic acid, and the carboxyl group thereof is coordinated with Eu3+ .
[0007] Compared with the prior art, the present invention uses a metal organic framework material and enoxacin to prepare a fluorescent detection probe that can quickly identify ethephon. The metal organic framework material uses 1,3,5-benzenetricarboxylic acid and 2,5-dihydroxyterephthalic acid as ligands, and Eu is coordinated to the carboxyl group in the ligand. 3+ The metal organic framework material has the characteristics of high porosity, high adsorption and large specific surface area. It can not only adsorb ethephon molecules, but also introduce enoxacin molecules into the framework material, and combine with the hydroxyl groups in the metal organic framework material to achieve specific fluorescence recognition of ethephon. Due to the effect of phosphoric acid, a hydrolysis product of ethephon, there is a strong binding affinity between phosphoric acid and the Eu-O node in the metal organic framework material, which reduces the ligand-metal charge transfer and leads to fluorescence enhancement, so that the residue of ethephon can be quickly identified by naked eyes. The fluorescence detection probe provided by the present invention gets rid of the limitation of instrument detection and realizes the rapid and efficient detection of ethephon.
[0008] The second aspect of the present invention provides a method for preparing the fluorescent detection probe, comprising the following steps: Step 1, adding triethylamine to the 1,3,5-benzenetricarboxylic acid aqueous solution, mixing evenly, to obtain a 1,3,5-benzenetricarboxylic acid mixed solution; adding triethylamine to the 2,5-dihydroxyterephthalic acid aqueous solution, mixing evenly, to obtain a 2,5-dihydroxyterephthalic acid mixed solution; Step 2: Add the europium ion solution, the 1,3,5-benzenetricarboxylic acid mixed solution and the 2,5-dihydroxyterephthalic acid mixed solution to the alcohol solution, mix them evenly, and perform a synthesis reaction at 0-40° C. to obtain a Eu-MOF material; Step 3: Disperse the Eu-MOF material in deionized water to obtain a Eu-MOF solution; mix the Eu-MOF solution and enoxacin solution to obtain a fluorescent detection probe.
[0009] Preferably, in step 1, the concentration of the aqueous solution of 1,3,5-benzenetricarboxylic acid is 0.08 mol / L-0.12 mol / L.
[0010] Preferably, in step 1, the concentration of the aqueous solution of 2,5-dihydroxyterephthalic acid is 0.08 mol / L-0.12 mol / L.
[0011] Preferably, in step 1, the volume ratio of the 1,3,5-benzenetricarboxylic acid aqueous solution to the triethylamine is 1:0.1-1:0.2.
[0012] Preferably, the volume ratio of the 2,5-dihydroxyterephthalic acid aqueous solution to the triethylamine is 1:0.1-1.0.2.
[0013] Preferably, in step 2, the concentration of the europium ion solution is 0.08 mol / L-0.12 mol / L.
[0014] Preferably, in step 2, the volume ratio of the europium ion solution, the 1,3,5-benzenetricarboxylic acid mixed solution and the 2,5-dihydroxyterephthalic acid mixed solution is 1:1:1-1:1.1:1.1.
[0015] Preferably, in step 2, the volume ratio of the total volume of the europium ion solution, the 1,3,5-benzenetricarboxylic acid mixed solution and the 2,5-dihydroxyterephthalic acid mixed solution to the alcohol solution is 1:1-1:1.2.
[0016] Preferably, in step 2, the synthesis reaction time is 10 min-60 min.
[0017] Preferably, in step three, the mass concentration of the Eu-MOF solution is 500 mg / L-700 mg / L.
[0018] Preferably, in step three, the concentration of the enoxacin solution is 300 μmol / L-500 μmol / L.
[0019] Preferably, in step three, the volume ratio of the Eu-MOF solution to the enoxacin solution is 1:1-1:1.1.
[0020] The third aspect of the present invention provides an application of the fluorescent detection probe in detecting ethephon.
[0021] In summary, the present invention provides a fluorescent detection probe ENX@Eu-MOF that can realize rapid and efficient detection of ethephon. The fluorescent detection probe is a composite material of a metal organic framework material and enoxacin. The high porosity, high adsorption and large specific surface area of the metal organic framework material are utilized, and combined with enoxacin, specific fluorescent recognition of ethephon can be realized, thereby achieving the purpose of rapid and efficient detection of ethephon. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 Schematic diagram of the structure of Eu-MOF obtained in each embodiment; Figure 2 This is a scanning electron microscope image of the Eu-MOF obtained in Example 1; Figure 3 The fluorescence spectrum of the fluorescence detection probe obtained in Example 1 detecting ethephon; Figure 4This is a fitting curve diagram of the fluorescence detection probe obtained in Example 1 detecting ethephon; Figure 5 This is a diagram showing the effect of the fluorescent detection probe obtained in Example 1 in detecting ethephon. DETAILED DESCRIPTION
[0023] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0024] Example 1 This embodiment provides a method for preparing a fluorescent detection probe ENX@Eu-MOF, which specifically includes the following steps: Step 1: add 0.125 mL of triethylamine to 3 mL of 0.1 mol / L aqueous solution of 1,3,5-benzenetricarboxylic acid, mix well, and obtain a 1,3,5-benzenetricarboxylic acid mixed solution; add 0.125 mL of triethylamine to 3 mL of 0.1 mol / L aqueous solution of 2,5-dihydroxyterephthalic acid, mix well, and obtain a 2,5-dihydroxyterephthalic acid mixed solution; Step 2: Add 3 mL of 0.1 mol / L europium nitrate solution, 1,3,5-benzenetricarboxylic acid mixed solution and 2,5-dihydroxyterephthalic acid mixed solution to 10 mL of 50% ethanol solution by volume, mix well, perform synthesis reaction at 25 ° C for 50 min, centrifuge at 6000 rpm for 10 min, discard the supernatant, wash with ethanol 3 times, and vacuum dry at 80 ° C and vacuum degree of 0.7 MPa for 12 h to obtain Eu-MOF material; Step 3: Disperse 500 mg of the Eu-MOF material in 1 L of deionized water to obtain a Eu-MOF solution; mix the Eu-MOF solution and 400 μmol / L of enoxacin solution in a volume ratio of 1:1 to obtain the fluorescent detection probe.
[0025] Example 2 This embodiment provides a method for preparing a fluorescent detection probe ENX@Eu-MOF, which specifically includes the following steps: Step 1: add 0.125 mL of triethylamine to 3 mL of 0.1 mol / L aqueous solution of 1,3,5-benzenetricarboxylic acid, mix well, and obtain a 1,3,5-benzenetricarboxylic acid mixed solution; add 0.125 mL of triethylamine to 3 mL of 0.1 mol / L aqueous solution of 2,5-dihydroxyterephthalic acid, mix well, and obtain a 2,5-dihydroxyterephthalic acid mixed solution; Step 2: Add 3 mL of 0.1 mol / L europium nitrate solution, 1,3,5-benzenetricarboxylic acid mixed solution and 2,5-dihydroxyterephthalic acid mixed solution to 10 mL of 50% ethanol solution by volume, mix well, perform synthesis reaction at 35 ° C for 45 min, centrifuge at 6000 rpm for 10 min, discard the supernatant, wash with ethanol 3 times, and vacuum dry at 80 ° C and vacuum degree of 0.7 MPa for 12 h to obtain Eu-MOF material; Step 3: Disperse 500 mg of the Eu-MOF material in 1 L of deionized water to obtain a Eu-MOF solution; mix the Eu-MOF solution and 400 μmol / L of enoxacin solution in a volume ratio of 1:1 to obtain the fluorescent detection probe.
[0026] Example 3 This embodiment provides a method for preparing a fluorescent detection probe ENX@Eu-MOF, which specifically includes the following steps: Step 1: add 0.125 mL of triethylamine to 3 mL of 0.09 mol / L aqueous solution of 1,3,5-benzenetricarboxylic acid, mix well, and obtain a 1,3,5-benzenetricarboxylic acid mixed solution; add 0.125 mL of triethylamine to 3 mL of 0.09 mol / L aqueous solution of 2,5-dihydroxyterephthalic acid, mix well, and obtain a 2,5-dihydroxyterephthalic acid mixed solution; Step 2: Add 3 mL of 0.09 mol / L europium nitrate solution, 1,3,5-benzenetricarboxylic acid mixed solution and 2,5-dihydroxyterephthalic acid mixed solution to 10 mL of 50% ethanol solution by volume, mix well, perform synthesis reaction at 30°C for 40 min, centrifuge at 6000 rpm for 10 min, discard the supernatant, wash with ethanol 3 times, and vacuum dry at 80°C and 0.7 MPa for 12 h to obtain Eu-MOF material; Step 3: Disperse 500 mg of the Eu-MOF material in 1 L of deionized water to obtain a Eu-MOF solution; mix the Eu-MOF solution and 400 μmol / L of enoxacin solution in a volume ratio of 1:1 to obtain the fluorescent detection probe.
[0027] In order to further demonstrate the technical effect of the present invention, the present invention conducted a scanning electron microscope test on the Eu-MOF material obtained in Example 1, and the results were as follows Figure 2 As shown. Figure 2 It can be seen that the Eu-MOF material has a regular dendritic structure.
[0028] The present invention also tests the fluorescent detection probe obtained in Example 1 for detecting ethephon; 1 mL of the aqueous solution of the ENX@Eu-MOF fluorescent detection probe obtained in Example 1 was mixed with 1 mL of a fruit and vegetable extract containing ethephon residues (mass concentration of 0.6 g / mL), and after oscillation and mixing, the fluorescence intensity of the test solution at an excitation wavelength of 365 nm, and emission wavelengths of 520 nm and 613 nm was recorded. The results are as follows: Figure 3 As shown, the present invention also uses the ratio of the fluorescence intensity at the emission wavelength of 520nm and 613nm to perform nonlinear fitting on different concentrations of ethephon. The results are as follows Figure 4 As shown. Figure 3 and Figure 4 It can be seen that due to the action of phosphoric acid, the hydrolysis product of ethephon, there is a strong binding affinity between phosphoric acid and the Eu-O node, which reduces the ligand-metal charge transfer and ultimately restores the fluorescence of the ligand 2,5-dihydroxyterephthalic acid. The detection of ethephon meets the linear fitting conditions. After calculation, the detection limit is 1 mg / L.
[0029] The Eu-MOF material provided in Example 1 was dispersed in deionized water at a concentration of 2 g / L to obtain a Eu-MOF suspension. 5 mL of the Eu-MOF suspension was taken, and the test paper was soaked in the Eu-MOF suspension for 24 hours, and then naturally air-dried. A 200 μmol / L enoxacin aqueous solution was added to the surface of the test paper to prepare an ENX@Eu-MOF paper-based sensor. Fruit and vegetable extracts containing different concentrations of ethephon (10 mg / L, 20 mg / L and 30 mg / L) were added to the ENX@Eu-MOF paper-based sensor. The specific preparation method of the fruit and vegetable extract includes the following steps: 6 g of fruit and vegetable samples were sliced and transferred to a test tube with 2 mL of water, vortexed for 20 minutes, and after centrifugation at 6000 rpm in a centrifuge for 10 minutes, the supernatant was taken to obtain a fruit and vegetable extract. The color change was observed with the naked eye under an ultraviolet lamp with a wavelength of 365 nm. The results are as follows: Figure 5 As shown. Figure 5 It can be seen that the fluorescence of the paper-based sensor gradually changes from red to green as the ethephon content increases, and the ethephon content can be detected by naked eyes.
[0030] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent substitution or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims
1. A fluorescent detection probe, characterized in that: The fluorescent detection probe comprises a metal organic framework material and enoxacin; wherein the ligand of the metal organic framework material is 1,3,5-benzenetricarboxylic acid and 2,5-dihydroxyterephthalic acid, and the carboxyl group thereof is coordinated with Eu 3+ .
2. The method for preparing a fluorescent detection probe according to claim 1, wherein: The steps include: Step 1, adding triethylamine to the 1,3,5-benzenetricarboxylic acid aqueous solution, mixing evenly, to obtain a 1,3,5-benzenetricarboxylic acid mixed solution; adding triethylamine to the 2,5-dihydroxyterephthalic acid aqueous solution, mixing evenly, to obtain a 2,5-dihydroxyterephthalic acid mixed solution; Step 2: Add the europium ion solution, the 1,3,5-benzenetricarboxylic acid mixed solution and the 2,5-dihydroxyterephthalic acid mixed solution to the alcohol solution, mix them evenly, and perform a synthesis reaction at 0-40° C. to obtain a Eu-MOF material; Step 3: Disperse the Eu-MOF material in deionized water to obtain a Eu-MOF solution; mix the Eu-MOF solution and enoxacin solution to obtain a fluorescent detection probe.
3. The method for preparing a fluorescent detection probe according to claim 2, characterized in that: In step 1, the concentration of the 1,3,5-benzenetricarboxylic acid aqueous solution is 0.08 mol / L-0.12 mol / L; and / or In step 1, the concentration of the 2,5-dihydroxyterephthalic acid aqueous solution is 0.08 mol / L-0.12 mol / L.
4. The method for preparing a fluorescent detection probe according to claim 2, wherein: In step 1, the volume ratio of the 1,3,5-benzenetricarboxylic acid aqueous solution to the triethylamine is 1:0.1-1:0.2; and / or The volume ratio of the 2,5-dihydroxyterephthalic acid aqueous solution to the triethylamine is 1:0.1-1:0.
2.
5. The method for preparing a fluorescent detection probe according to claim 2, wherein: In step 2, the concentration of the europium ion solution is 0.08 mol / L-0.12 mol / L; and / or In step 2, the volume ratio of the europium ion solution, the 1,3,5-benzenetricarboxylic acid mixed solution and the 2,5-dihydroxyterephthalic acid mixed solution is 1:1:1-1:1.1:1.
1.
6. The method for preparing a fluorescent detection probe according to claim 2, wherein: In step 2, the volume percentage of the solute in the alcohol solution is 45%-55%; and / or In step 2, the volume ratio of the total volume of the europium ion solution, the 1,3,5-benzenetricarboxylic acid mixed solution and the 2,5-dihydroxyterephthalic acid mixed solution to the alcohol solution is 1:1-1:1.
2.
7. The method for preparing a fluorescent detection probe according to claim 2, wherein: In step 2, the synthesis reaction time is 10 min-60 min.
8. The method for preparing a fluorescent detection probe according to claim 2, wherein: In step 3, the mass concentration of the Eu-MOF solution is 500 mg / L-700 mg / L; and / or In step 3, the concentration of the enoxacin solution is 300 μmol / L-500 μmol / L; and / or In step three, the volume ratio of the Eu-MOF solution to the enoxacin solution is 1:1-1:1.
1.
9. Use of the fluorescent detection probe as claimed in claim 1 in detecting ethephon.