Method for directly detecting triacetone triperoxide by using europium-based metal organic framework sensing reagent

Abstract

The invention provides a method for directly detecting triacetone triperoxide by using a europium-based metal organic framework sensing reagent, which comprises the following steps: mixing europium nitrate hexahydrate and 2, 5-dihydroxyterephthalic acid to obtain a europium-based metal organic framework material, and mixing the obtained material with an acetonitrile solvent to prepare the europium-based metal organic framework sensing reagent. When the europium-based metal organic framework sensing reagent is used for detecting triacetone triperoxide, a green fluorescence lightening phenomenon appears, the response speed is high (less than 1s), the detection sensitivity is high, and the detection limit is as low as 36.1 nM; high selectivity is achieved, other common structures and property analogues have no interference on detection, and real-time detection can be achieved. The glass fiber sheet loaded with the europium-based metal organic framework sensing reagent is constructed by using a soaking method, and on-site rapid detection of triacetone triperoxide solid particles can be efficiently and conveniently realized without pre-treatment of an object to be detected.

Description

Technical Field

[0001] The invention relates to a method for directly detecting triacetone triperoxide with a europium-based metal organic framework sensing reagent. The detection reagent has fast detection speed, strong anti-interference performance and high sensitivity, and can achieve the purpose of visually directly detecting a triacetone triperoxide solution and solid particles. Background Art

[0002] Cascade reaction (CR) refers to the process of converting a substrate into a product during multiple chemical reactions, which then becomes the substrate for the next reaction. In recent years, cascade reactions have been widely used in catalysis, sensing, tumor diagnosis and treatment, etc., because they can trigger continuous chemical transformations, reduce the separation and purification steps in traditional multi-step reactions, overcome the problem of unstable or difficult to handle intermediate products, and thus improve reaction activity and selectivity. In the field of sensing, cascade reactions have unique advantages, including preferential response to target analytes, high signal-to-noise ratio, and accumulation and amplification of target signals at each reaction stage, which makes them play an increasingly important role in basic research and environmental monitoring, medical diagnosis, food quality testing, etc. There are many different sensing materials based on cascade reactions, such as nanozymes, metal-organic frameworks (MOFs), polymers, fluorescent dyes, etc. Among them, MOFs are favored by cascade reaction researchers because of their high specific surface area and customizable structure, the tunability of metal sites and organic ligands, and the ability to precisely optimize and adjust pore size and microenvironment. Therefore, how to propose a design strategy for MOFs probes based on cascade reactions from the perspective of regulating the energy transfer process between organic ligands and metal centers, and establish a feasible scheme to identify low-activity analytes with high selectivity and high signal-to-noise ratio is a very challenging problem.

[0003] Triacetone triperoxide, also known as the mother of Satan, is prepared from acetone and hydrogen peroxide under acid catalysis. There is no nitro or aromatic ring in the structure of triacetone triperoxide, so there is no obvious fluorescence and absorption characteristics in the ultraviolet and visible light regions. At present, the commonly used detection methods of triacetone triperoxide include mass spectrometry, ion mobility spectrometry, electrochemical sensing, visual optical sensing (fluorescence, colorimetry), etc. Among them, most of the detection strategies for triacetone triperoxide are based on its easy decomposition characteristics, and indirect detection of triacetone triperoxide is achieved by detecting one of its decomposition products (hydrogen peroxide or acetone). However, these indirect detection methods require strong acid to decompose triacetone triperoxide. At the same time, indirect detection methods have problems such as low specificity and sensitivity, slow response speed, and secondary damage to the environment, which limits their application in practical scenarios. The detection reagent constructed based on the europium-based metal organic framework material of the present invention can detect triacetone triperoxide by visual direct on-site fluorescence lighting, does not need to be pre-treated, has low cost, is easy to operate, has a fast response speed, and has high detection sensitivity. Summary of the invention

[0004] The object of the present invention is to provide a method for directly detecting triacetone triperoxide with a europium-based metal organic framework sensor reagent. The method comprises mixing europium nitrate hexahydrate with 2,5-dihydroxyterephthalic acid to obtain a europium-based metal organic framework material, and then mixing the obtained material with an acetonitrile solvent to prepare a europium-based metal organic framework sensor reagent; when the europium-based metal organic framework sensor reagent is used to directly detect triacetone triperoxide, a green fluorescence lighting phenomenon is presented, the response speed is fast (<1s), the detection sensitivity is high, and the detection limit is as low as 36.1nM; it has high selectivity, and other common structural and property analogs have no interference with the detection, and real-time detection can be achieved. A glass fiber sheet loaded with a europium-based metal organic framework sensor reagent is constructed by an immersion method, and no pretreatment of the object to be detected is required, and on-site rapid detection of triacetone triperoxide solid particles can be achieved efficiently and conveniently. The problem that the prior art requires acidification pretreatment to decompose triacetone triperoxide into hydrogen peroxide, and can only indirectly detect triacetone triperoxide is overcome.

[0005] The method for directly detecting triacetone triperoxide with a europium-based metal organic framework sensing reagent of the present invention is carried out according to the following steps:

[0006] Preparation of Europium-based Metal-Organic Framework Materials:

[0007] a. Dissolve europium nitrate hexahydrate and 2,5-dihydroxyterephthalic acid in 7.3 mL N,N-dimethylformamide solution, add 2-fluorobenzoic acid, and mix the solution evenly by ultrasonication for 30 minutes; then add 0.6 mL of water and 0.2 mL of 3.5 mol / L nitric acid solution diluted with N,N-dimethylformamide, and mix evenly by ultrasonication for 30 minutes. After mixing evenly, put the mixture into a 50 mL reactor lined with polytetrafluoroethylene;

[0008] b. Place the reactor in step a in an oven, react at 120°C for 48 hours, cool and centrifuge for 3 times with N,N-dimethylformamide and methanol at a speed of 10,000 rpm for 3 minutes; dry the product in a vacuum oven at 50°C for 12 hours to obtain a europium-based metal organic framework material;

[0009] Preparation of Europium-based Metal-Organic Framework Sensing Reagents:

[0010] c. Dissolve the europium-based metal organic framework material obtained in step b in acetonitrile, mix evenly by ultrasonication for 10 minutes, and obtain a europium-based metal organic framework sensing reagent, and encapsulate the detection reagent in a brown reagent bottle;

[0011] Direct detection of triacetone triperoxide solution:

[0012] d. Weigh the solid particles of triacetone triperoxide, add 2 mL of acetonitrile solvent to prepare a triacetone triperoxide solution with a concentration of 20 mmol / L, measure 0-40 μL of the 20 mmol / L triacetone triperoxide solution and add it to the europium-based metal organic framework sensing reagent obtained in step c, then add 20 μL of ultrapure water, dilute to 0.5 mL with acetonitrile, and measure the fluorescence spectrum under the condition of an excitation wavelength of 365 nm, and the fluorescence color gradually changes from colorless to green;

[0013] e. Linearly fitting the fluorescence intensity at an emission wavelength of 533 nm with the corresponding concentration of triacetone triperoxide solution to obtain a standard curve for quantitative analysis of the content of triacetone triperoxide in the sample to be tested;

[0014] Or directly detect triacetone triperoxide solid particles:

[0015] d. Dissolve 0.0025 g of the europium-based metal organic framework sensing reagent obtained in step c in 3.9 mL of acetonitrile, mix evenly by ultrasonication for 10 min, take 1 mL of the evenly mixed europium-based metal organic framework sensing reagent, add 4 mL of acetonitrile, and then add 100 μL of ultrapure water, mix evenly by ultrasonication for 10 min, and obtain the diluted europium-based metal organic framework sensing reagent;

[0016] e. Select an area of ​​1cm 2A glass fiber sheet is immersed in the diluted europium-based metal organic framework sensing reagent obtained in step d, and taken out after 30 seconds to obtain a glass fiber sheet containing the europium-based metal organic framework sensing reagent; triacetone triperoxide particles are sprayed on the obtained glass fiber sheet of the europium-based metal organic framework sensing reagent, and the change of fluorescence color is observed with naked eyes under the condition of an excitation wavelength of 365nm, from colorless to green.

[0017] The method for directly detecting triacetone triperoxide using a europium-based metal organic framework sensing reagent of the present invention is based on a reaction mechanism of a cascade reaction for directly detecting triacetone triperoxide. The specific reaction process is as follows:

[0018] There is a strong intramolecular hydrogen bond between the hydroxyl group on the organic ligand of the europium-based metal organic framework sensor reagent and the oxygen atom on the carboxylic acid, which blocks the charge transfer from the ligand to the metal center europium, resulting in the europium-based metal organic framework material being in a non-fluorescent state in acetonitrile solvent. When a trace amount of water is added to the solution, the hydrogen atoms on the water will form a strong hydrogen bond with the oxygen atoms on the carboxylic acid, and at the same time, the oxygen atoms on the water will also form a hydrogen bond with the hydrogen atoms on the hydroxyl group of the ligand. Under the dual action of water, the europium-based metal organic framework sensor material shows a weak yellow fluorescence in the acetonitrile solution. After adding triacetone triperoxide, the strong oxidizing property of triacetone triperoxide further promotes the breaking of the oxygen-hydrogen bond on the hydroxyl group, causing the ligand to change from the original enol structure to the keto structure, thereby producing bright green fluorescence. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 The fluorescence spectrum of the present invention is a reaction after adding 0.36 mL of acetonitrile solvent, 20 μL of ultrapure water, and 20 μL of triacetone triperoxide acetonitrile solution with a concentration of 0-40 mmol / L to 0.1 mL of a 2.5 mg / 3.9 mL europium-based metal organic framework sensor reagent solution;

[0020] Figure 2 The present invention is a curve showing the change of the fluorescence peak intensity at 533 nm with the concentration of triacetone triperoxide after 0.36 mL of acetonitrile solvent, 20 μL of ultrapure water, and 20 μL of acetonitrile solution of triacetone triperoxide with a concentration of 0-40 mmol / L are added to 0.1 mL of a 2.5 mg / 3.9 mL europium-based metal organic framework sensor reagent solution respectively for reaction;

[0021] Figure 3 The present invention is a curve of fluorescence peak intensity at 533 nm and reaction time after 0.36 mL of acetonitrile solvent, 20 μL of ultrapure water, and 20 μL of acetone triperoxide acetonitrile solution with a concentration of 0-40 mmol / L are added to 0.1 mL of a 2.5 mg / 3.9 mL europium-based metal organic framework sensor reagent solution to react;

[0022] Figure 4 According to the present invention, 0.36 mL of acetonitrile solvent, 20 μL of ultrapure water, and 20 μL of acetonitrile solution of triacetone triperoxide (TATP) with a concentration of 20 mmol / L are added to 0.1 mL of 2.5 mg / 3.9 mL europium-based metal organic framework sensing reagent solution; 0.38 mL of acetonitrile solvent, 20 μL of dinitrotoluene (DNT) with a concentration of 20 mmol / L, 2,4,6-trinitrophenol (PA), urea (Urea), NaClO4, KClO3, NaNO3, NaNO2, Zn(NO3)2, NH4NO3, NaCl, NH4Cl, KMnO4, K2Cr2O7, KBr, glucose (Glu), sucrose (Suc), starch (Starch), microcrystalline cellulose (MCC), and tea polyphenols (GTP) aqueous solution are added to 0.1 mL of 2.5 mg / 3.9 mL probe solution, and the fluorescence spectra are obtained after the reaction;

[0023] Figure 5 The present invention sprays triacetone triperoxide (TATP), 2,4,6-trinitrotoluene (TNT), dinitrotoluene (DNT), 2,4,6-trinitrophenol (PA), S, urea (Urea), NaClO4, KClO3, NaBrO3, NaNO3, NaNO2, KNO3, NH4NO3, NaCl, NH4Cl, KMnO4, K2Cr2O7, KBr, KI, microcrystalline cellulose (MCC), tea polyphenols (GTP), glucose (Glu), sucrose (Suc), starch (Starch), flour (Flour), monosodium glutamate (MSG), edible sugar (Sugar), rouge (Rouge), washing powder (Washing power) particles on a glass fiber sheet containing a europium-based metal organic framework sensing reagent, and a fluorescence image of the particles is taken by a camera. DETAILED DESCRIPTION

[0024] The present invention is further described below by means of specific examples, but the invention is not limited to these examples.

[0025] Example 1

[0026] Preparation of Europium-based Metal-Organic Framework Materials:

[0027] a. Dissolve 0.0647g europium nitrate hexahydrate and 0.0287g 2,5-dihydroxyterephthalic acid in 7.3mL N,N-dimethylformamide solution, add 0.0834g 2-fluorobenzoic acid, and mix the solution evenly by ultrasonication for 30 minutes; then add 0.6mL water and 0.2mL 3.5mol / L nitric acid solution diluted with N,N-dimethylformamide, and mix evenly by ultrasonication for 30 minutes. After mixing evenly, put the mixture into a 50mL reactor lined with polytetrafluoroethylene;

[0028] b. Place the reactor in step a in an oven, react at 120°C for 48 hours, cool and centrifuge for 3 times with N,N-dimethylformamide and methanol at a speed of 10,000 rpm for 3 minutes; dry the product in a vacuum oven at 50°C for 12 hours to obtain a europium-based metal organic framework material;

[0029] Preparation of Europium-based Metal-Organic Framework Sensing Reagents:

[0030] c. Dissolve 0.0025 g of the europium-based metal organic framework material obtained in step b in 3.9 mL of acetonitrile, mix evenly by ultrasonication for 10 min to obtain a europium-based metal organic framework sensing reagent, and encapsulate the detection reagent in a brown reagent bottle;

[0031] Direct detection of triacetone triperoxide solution:

[0032] d. Weigh 0.0089 g of triacetone triperoxide solid particles, add 2 mL of acetonitrile solvent to prepare a triacetone triperoxide solution with a concentration of 20 mmol / L, measure 0-40 μL of the triacetone triperoxide solution with a concentration of 20 mmol / L, add it to the europium-based metal organic framework sensing reagent obtained in step c, then add 20 μL of ultrapure water, and dilute to 0.5 mL with acetonitrile. After the reaction, perform a fluorescence spectrum test. Under the condition of an excitation wavelength of 365 nm, the fluorescence spectrum is measured, and its fluorescence color gradually changes from colorless to green;

[0033] e. Linearly fit the fluorescence intensity at the emission wavelength of 533 nm with the corresponding concentration of triacetone triperoxide solution to obtain a standard curve for quantitative analysis of the content of triacetone triperoxide in the sample to be tested. Figure 1 As shown, with the increase of the concentration of triacetone triperoxide in the mixed solution, the fluorescence intensity at 533 nm gradually increased.

[0034] Example 2

[0035] The linear relationship between the fluorescence intensity at 533nm and the concentration of triacetone triperoxide after the europium-based metal organic framework sensor material reagent reacts with triacetone triperoxide solution:

[0036] 0.0025 g of the europium-based metal organic framework sensing material reagent in Example 1 was dissolved in 3.9 mL of acetonitrile solvent, and then 0-40 μL of a 20 mmol / L triacetone triperoxide solution was added to 100 μL of the europium-based metal organic framework sensing reagent, and then 20 μL of ultrapure water was added, and the volume was fixed to 0.5 mL with acetonitrile solvent. After the reaction, the fluorescence spectrum was tested, and the fluorescence emission intensity of the solution at 533 nm and the concentration of triacetone triperoxide were used as a standard graph. According to the fluorescence spectrum standard graph (such as Figure 2 As shown), it can be seen that with the increase of the concentration of triacetone triperoxide, the fluorescence emission intensity at 533nm presents two states with different growth rates, and both show a good linear relationship. The detection limit calculated by the formula LOD = 3σ / K (K = 195233.93, σ = 2.352) is 36.1nM.

[0037] Example 3

[0038] Response time of europium-based metal organic framework sensing material reagent to triacetone triperoxide solution:

[0039] 0.0025 g of the europium-based metal organic framework sensor material reagent in Example 1 was dissolved in 3.9 mL of acetonitrile solvent, and then 100 μL of the europium-based metal organic framework sensor material reagent solution was added with 0.36 mL of acetonitrile solvent, and then 20 μL of 20 mmol / L triacetone triperoxide solution and 20 μL of deionized water were added, and a scatter plot was made between the fluorescence emission intensity of the solution at 533 nm and the reaction time, as shown in FIG. Figure 3 As shown, the response time is less than 1s.

[0040] Example 4

[0041] Specific detection and recognition of triacetone triperoxide solution by europium-based metal organic framework sensing material reagent:

[0042] Take 0.0025g of the europium-based metal organic framework sensing material reagent in Example 1 and dissolve it in 3.9mL of acetonitrile solvent, then take 100μL of the europium-based metal organic framework sensing material reagent solution, add 0.36mL of acetonitrile solvent, then add 20μL of deionized water, and then add 20μL of 20mmol / L triacetone triperoxide (TATP) solution, dinitrotoluene (DNT), 2,4,6-trinitrophenol (PA), urea (Urea), NaClO4, KClO3, NaNO3, NaNO2, Zn(NO3)2, NH4NO3, NaCl, NH4Cl, KMnO4, K2Cr2O7, KBr, glucose (Glu), sucrose (Suc), starch (Starch), microcrystalline cellulose (MCC), tea polyphenol (GTP) solution, and perform fluorescence spectrum test after the reaction. Figure 4 As shown, the fluorescence emission peak appears at 533 nm only when the triacetone triperoxide solution is added, while there is almost no fluorescence change when other common interferences are added, indicating that the europium-based metal organic framework sensing reagent has good specificity for the detection of triacetone triperoxide.

[0043] Example 5

[0044] Preparation of Europium-based Metal-Organic Framework Materials:

[0045] a. Dissolve 0.0647g europium nitrate hexahydrate and 0.0287g 2,5-dihydroxyterephthalic acid in 7.3mL N,N-dimethylformamide solution, add 0.0834g 2-fluorobenzoic acid, and mix the solution evenly by ultrasonication for 30 minutes; then add 0.6mL water and 0.2mL 3.5mol / L nitric acid solution diluted with N,N-dimethylformamide, and mix evenly by ultrasonication for 30 minutes. After mixing evenly, put the mixture into a 50mL reactor lined with polytetrafluoroethylene;

[0046] b. Place the reactor in step a in an oven, react at 120°C for 48 hours, cool and centrifuge for 3 times with N,N-dimethylformamide and methanol at a speed of 10,000 rpm for 3 minutes; dry the product in a vacuum oven at 50°C for 12 hours to obtain a europium-based metal organic framework material;

[0047] Preparation of Europium-based Metal-Organic Framework Sensing Reagents:

[0048] c. Dissolve 0.0025 g of the europium-based metal organic framework material obtained in step b in 3.9 mL of acetonitrile, mix evenly by ultrasonication for 10 min to obtain a europium-based metal organic framework sensing reagent, and encapsulate the detection reagent in a brown reagent bottle;

[0049] Direct detection of triacetone triperoxide solid particles:

[0050] d. Dissolve 0.0025 g of the europium-based metal organic framework sensing reagent obtained in step c in 3.9 mL of acetonitrile, mix evenly by ultrasonication for 10 min, take 1 mL of the evenly mixed europium-based metal organic framework sensing reagent, add 4 mL of acetonitrile, and then add 100 μL of ultrapure water, mix evenly by ultrasonication for 10 min, and obtain the diluted europium-based metal organic framework sensing reagent;

[0051] e. Select an area of ​​1cm 2A glass fiber sheet is immersed in the diluted europium-based metal organic framework sensing reagent obtained in step d, and taken out after 30 seconds to obtain a glass fiber sheet containing the europium-based metal organic framework sensing reagent; triacetone triperoxide particles are sprayed on the obtained glass fiber sheet of the europium-based metal organic framework sensing reagent, and the change of fluorescence color is observed with naked eyes under the condition of an excitation wavelength of 365nm, from colorless to green.

[0052] Example 6

[0053] Specific detection and recognition of triacetone triperoxide solid particles by europium-based metal organic framework sensing material reagents:

[0054] Take the diluted europium-based metal organic framework sensing reagent obtained in Example 5 and select an area of ​​1 cm 2 glass fiber sheet, immerse the glass fiber sheet in the obtained detection reagent, take it out after 30 seconds, and obtain the glass fiber containing europium-based metal organic framework fluorescent sensing material; triacetone triperoxide (TATP), 2,4,6-trinitrotoluene (TNT), dinitrotoluene (DNT), 2,4,6-trinitrophenol (PA), S, urea (Urea), NaClO4, KClO3, NaBrO3, NaNO3, NaNO2, KNO3, NH4NO3, NaCl, NH4Cl, KMnO4, K2Cr2O7, KBr, KI, microcrystalline cellulose (MCC), tea polyphenols (GTP), glucose (Glu), sucrose (Suc), starch (Starch), flour (Flour), monosodium glutamate (MSG), edible sugar (Sugar), rouge (Rouge), washing powder (Washing powder power) particles were sprayed onto the obtained glass fiber-based sensing material, and the change of fluorescence color was observed with naked eyes under the condition of excitation wavelength of 365nm, such as Figure 5 As shown, green fluorescence can be seen on the glass fiber with the naked eye only when the triacetone triperoxide solution is added, indicating that the europium-based metal organic framework sensing material reagent has good specificity for the detection of triacetone triperoxide.

[0055] The europium-based metal organic framework sensing material reagent provided in the present invention can realize highly sensitive, rapid, specific, and visualized fluorescence lighting detection of triacetone triperoxide in the environment, with a detection limit as low as 36.1nM, a response time of less than 1s, and excellent selectivity for more than 20 common interferences. Using glass fibers soaked in the europium-based metal organic framework sensing material reagent, solid particles of triacetone triperoxide can be identified with the naked eye.

Claims

1. A method for directly detecting triacetone triperoxide using a europium-based metal organic framework sensing reagent, characterized in that Follow these steps: Preparation of Europium-based Metal-Organic Framework Materials: a. Dissolve europium nitrate hexahydrate and 2,5-dihydroxyterephthalic acid in 7.3 mL N,N-dimethylformamide solution, add 2-fluorobenzoic acid, and mix the solution evenly by ultrasonication for 30 minutes; then add 0.6 mL of water and 0.2 mL of 3.5 mol / L nitric acid solution diluted with N,N-dimethylformamide, and mix evenly by ultrasonication for 30 minutes. After mixing evenly, put the mixture into a 50 mL reactor lined with polytetrafluoroethylene; b. Place the reactor in step a in an oven, react at 120°C for 48 hours, cool and centrifuge for 3 times with N,N-dimethylformamide and methanol at a speed of 10,000 rpm for 3 minutes; dry the product in a vacuum oven at 50°C for 12 hours to obtain a europium-based metal organic framework material; Preparation of Europium-based Metal-Organic Framework Sensing Reagents: c. Dissolve the europium-based metal organic framework material obtained in step b in acetonitrile, mix evenly by ultrasonication for 10 minutes, and obtain a europium-based metal organic framework sensing reagent, and encapsulate the detection reagent in a brown reagent bottle; Direct detection of triacetone triperoxide solution: d. Weigh the solid particles of triacetone triperoxide, add 2 mL of acetonitrile solvent to prepare a triacetone triperoxide solution with a concentration of 20 mmol / L, measure 0-40 μL of the 20 mmol / L triacetone triperoxide solution and add it to the europium-based metal organic framework sensing reagent obtained in step c, then add 20 μL of ultrapure water, dilute to 0.5 mL with acetonitrile, and measure the fluorescence spectrum under the condition of an excitation wavelength of 365 nm, and the fluorescence color gradually changes from colorless to green; e. Linearly fitting the fluorescence intensity at an emission wavelength of 533 nm with the corresponding concentration of triacetone triperoxide solution to obtain a standard curve for quantitative analysis of the content of triacetone triperoxide in the sample to be tested; Or directly detect triacetone triperoxide solid particles: d. Dissolve 0.0025 g of the europium-based metal organic framework sensing reagent obtained in step c in 3.9 mL of acetonitrile, mix evenly by ultrasonication for 10 min, take 1 mL of the evenly mixed europium-based metal organic framework sensing reagent, add 4 mL of acetonitrile, and then add 100 μL of ultrapure water, mix evenly by ultrasonication for 10 min, and obtain the diluted europium-based metal organic framework sensing reagent; e. Select an area of ​​1cm 2 A glass fiber sheet is immersed in the diluted europium-based metal organic framework sensing reagent obtained in step d, and taken out after 30 seconds to obtain a glass fiber sheet containing the europium-based metal organic framework sensing reagent; triacetone triperoxide particles are sprayed on the obtained glass fiber sheet of the europium-based metal organic framework sensing reagent, and the change of fluorescence color is observed with naked eyes under the condition of an excitation wavelength of 365nm, from colorless to green.

Images