A yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone, its preparation method and application

Abstract

The present invention provides a yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone, and its preparation method and application. The preparation method of the yttrium-based metal-organic framework material of the present invention includes the steps of: fully mixing and dispersing yttrium nitrate, tris(3'-F-4-carboxybiphenyl)amine, N,N-dimethylformamide, methanol, acetic acid and water evenly; carrying out a solvothermal reaction, and then filtering, washing and drying to obtain the yttrium-based metal-organic framework material. The yttrium-based metal-organic framework material obtained in the present invention has high sensitivity and selective recognition for nitrofurazone, and has potential application value in fluorescence recognition. The yttrium-based metal-organic framework material of the present invention has excellent photothermal stability and solvent stability, and its fluorescence effect is strong. The present invention uses polymethyl methacrylate and the yttrium-based metal-organic framework material to prepare a more convenient and rapid detection film, which can be used for visual and simple detection.

Description

Technical Field

[0001] The present invention relates to a yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone, a preparation method thereof, and applications thereof, belonging to the technical field of fluorescence recognition materials. Background Art

[0002] The increasingly severe environmental pollution seriously endangers the ecosystem and people's health, and human survival faces a severe challenge. As a broad-spectrum antibiotic, furan antibiotics can kill most Gram-positive and Gram-negative bacteria, fungi, and protozoa. Furan antibiotics are widely used as drugs and animal feed supplements, resulting in the abuse of antibiotics. The abuse of antibiotics has also been proven to cause potential carcinogenic and teratogenic effects on the human body. Therefore, the detection of antibiotics is crucial for regulating their use and evaluating the surrounding environmental levels nowadays.

[0003] Traditional methods for detecting antibiotics include Raman spectroscopy, gas ion mobility spectrometry (IMS), atomic mass spectrometry (MS), inductively coupled plasma atomic emission spectrometry (ICP-AES), etc., which have problems such as high cost, professional instruments, and cumbersome pretreatment. Metal-organic framework materials (MOFs) are a class of emerging highly ordered porous crystalline materials that can be used as fluorescence recognition probes. Fluorescence recognition, as a new detection and recognition technology based on fluorescent solid materials, has advantages such as high efficiency, high sensitivity, less time-consuming, and simplicity compared to traditional detection and recognition technologies, and has become a highly potential, highly sensitive, and time-saving fluorescence recognition technology. A series of metal-organic fluorescent sensing materials have been reported, and their detection ranges include inorganic metal ions, anions, explosives, etc. However, there are not many relevant reports on fluorescent probes with high sensitivity, high selectivity, visual detection of furan antibiotics, and high stability. Summary of the Invention

[0004] Aiming at the deficiencies of the existing technology, the present invention provides a yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone, a preparation method thereof, and applications thereof. The method of the present invention is based on the strong coordination ability of trivalent yttrium ions and the coordination of the organic ligand tris(3'-F-4-carboxybiphenyl)amine to prepare a yttrium-based metal-organic framework material, which points out a new direction for the preparation of metal-organic framework materials with selective fluorescence recognition for nitrofurazone. The yttrium-based metal-organic framework material obtained by the present invention has high sensitivity and selective recognition for nitrofurazone and has potential application value in fluorescence recognition. The yttrium-based metal-organic framework material of the present invention has excellent photothermal stability and solvent stability, and its fluorescence effect is strong. The present invention can prepare a more convenient and rapid detection film using polymethyl methacrylate and the yttrium-based metal-organic framework material, and can perform visual and simple detection.

[0005] The technical solution of the present invention is as follows:

[0006] A yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone, and the chemical formula of the yttrium-based metal-organic framework material is C 39 H 25 F3NO8Y.

[0007] Preferably according to the present invention, the yttrium-based metal-organic framework material is in a crystal structure, belonging to the triclinic system, space group P-1, and the unit cell parameters are: a = 8.7145(8), b = 13.0531(12), c = 21.3214(19), α = 73.3620(10), β = 87.314(3), γ = 76.025(2), V = 2254.4(4).

[0008] The preparation method of the above-mentioned yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone includes the steps of: fully mixing and dispersing yttrium nitrate, tris(3'-F-4-carboxybiphenyl)amine, N,N-dimethylformamide, methanol, acetic acid and water evenly; carrying out a solvothermal reaction, and then filtering, washing and drying to obtain the yttrium-based metal-organic framework material.

[0009] According to the present invention, the structure of tris(3'-F-4-carboxybiphenyl)amine is as follows, and it can be prepared by the prior art. For example, it can be prepared according to the reference "Journal of Solid State Chemistry, 2022, 307, 122820".

[0010]

[0011] Preferably according to the present invention, the molar ratio of yttrium nitrate to tris(3'-F-4-carboxybiphenyl)amine is 3-5:1, preferably 4:1.

[0012] Preferably according to the present invention, the volume ratio of the molar amount of yttrium nitrate to N,N-dimethylformamide is 0.05-0.08 mol / L.

[0013] Preferably according to the present invention, the volume ratio of N,N-dimethylformamide, methanol, acetic acid and water is 2-4:2-2.5:0.15-0.225:0-1; preferably, the volume ratio of N,N-dimethylformamide, methanol, acetic acid and water is 3:2:0.225:1.

[0014] According to the present invention, the mass concentration of acetic acid is 99.5%.

[0015] Preferably according to the present invention, the mixing and dispersion is carried out by ultrasonic wave at room temperature for 5-20 min.

[0016] Preferably according to the present invention, the solvothermal reaction temperature is 90-110 °C, and the solvothermal reaction time is 12-26 hours; preferably, the solvothermal reaction temperature is 100 °C, and the solvothermal reaction time is 14 hours.

[0017] Preferably according to the present invention, the washing is carried out by using water and methanol in sequence.

[0018] The application of the above yttrium-based metal-organic framework material with selective fluorescence recognition for furacilin is used for detecting furacilin.

[0019] Preferably according to the present invention, the yttrium-based metal-organic framework material can be used to prepare a mixed mechanism film for detecting furacilin; the mixed mechanism film is prepared by using polymethyl methacrylate, yttrium-based metal-organic framework material and a solvent as raw materials and volatilizing the solvent.

[0020] The technical features and beneficial effects of the present invention:

[0021] 1. The method of the present invention is based on the strong coordination ability of trivalent yttrium ions and the coordination of the organic ligand tris(3'-F-4-carboxybiphenyl)amine to prepare a yttrium-based metal-organic framework material, which points out a new direction for the preparation of metal-organic framework materials with selective fluorescence recognition for furacilin. The preparation method of the present invention is simple, with low cost; it is easy to implement and has strong repeatability.

[0022] 2. In the preparation method of the present invention, an organic ligand based on a photoactive center triarylamine moiety is selected. Triarylamine is a class of helical paddlewheel fluorescent molecules with a nitrogen atom center. The three benzene rings introduced by the ligand of the present invention increase the steric hindrance and hyperconjugated electron effect of the ligand. The large rigid skeleton and conjugated system can accelerate the internal electron transfer speed and conversion efficiency of the molecule; moreover, by modifying triarylamine with benzene rings (electron-rich conjugated groups), its light absorption range can be broadened and its optoelectronic properties can be enhanced. Among them, F has strong electronegativity and acidity (it can also enhance the acidity of the ligand), and the weak interaction of F will also produce an enhanced fluorescence effect. The coordination of tris(3'-F-4-carboxybiphenyl)amine of the present invention has better optical activity than other ligands. The trivalent yttrium ions of the present invention coordinate with an organic ligand with a specific structure, and the two play a synergistic role to prepare the material with the structure and excellent properties of the present invention.

[0023] 3. In the preparation method of the present invention, the preferred molar ratio of yttrium nitrate to tris(3'-F-4-carboxybiphenyl)amine is 4:1. If the molar ratio is too small, the ligand reaction will not form crystals, and crystals can still be formed by adding yttrium nitrate again. If the molar ratio is too large, the crystals will be smaller and the morphological regularity will be poor. N,N-dimethylformamide in the preparation method of the present invention plays the role of providing the main solvent; the addition of water and methanol can assist in crystal formation; the addition of acetic acid can control the reaction rate. N,N-dimethylformamide, methanol, and acetic acid are all indispensable, and their ratios directly affect whether crystals can be formed, the morphology of the formed crystals, and the yield. If water is not added or added in a small amount, the reaction will be slower and the yield will be lower; if more water is added, the reaction will be slower and the crystals will be smaller and more fragmented. In the preparation method of the present invention, the solvothermal reaction temperature is too low to react, and too high a temperature will cause the reaction to proceed but no crystals can be formed. Therefore, as a whole, the preparation method of the present invention can jointly prepare the yttrium-based metal-organic framework material with the structure and properties of the present invention.

[0024] 4. The chemical formula of the yttrium-based metal-organic framework material obtained in the present invention is C 39 H 25 F3NO8Y. Its crystal structure belongs to the triclinic system, P-1 space group; moreover, it has excellent photothermal stability and solvent stability and can still maintain its original structure after being soaked in water or DMF for three days.

[0025] 5. The yttrium-based metal-organic framework material obtained in the present invention has a strong fluorescence effect, high sensitivity and selectivity for the recognition of nitrofurazone. The fluorescence detection limit of nitrofurazone can be as low as 3.7×10 -6 mol / L, and it has potential application value in the fluorescence recognition of harmful substances. By using polymethyl methacrylate and the yttrium-based metal-organic framework material, a mixed mechanism membrane can be prepared, which can more conveniently and quickly detect nitrofurazone, achieve the purpose of visual and simple detection, and can be recycled. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is the crystal structure diagram of the yttrium-based metal-organic framework material prepared in Example 1;

[0027] Figure 2 It is the solid fluorescence spectrum of the yttrium-based metal-organic framework material prepared in Example 1;

[0028] Figure 3 It is the fluorescence spectrum of the yttrium-based metal-organic framework material prepared in Example 1 for antibiotic testing in water;

[0029] Figure 4 It is the furan titration fluorescence spectrum of the yttrium-based metal-organic framework material prepared in Example 1;

[0030] Figure 5Fluorescence recognition diagram of the yttrium-based metal-organic framework material prepared in Example 1 for the visual detection of furacilin;

[0031] Figure 6 XRD diagram of the stability test of the yttrium-based metal-organic framework material prepared in Example 1;

[0032] Figure 7 Thermal stability diagram of the yttrium-based metal-organic framework material prepared in Example 1;

[0033] Figure 8 Schematic diagram for the preparation of the mixed matrix membrane in the test example and the visual detection diagram under 365 nm ultraviolet light. Detailed implementation manners

[0034] The following combines specific examples to further elaborate on the present invention.

[0035] Reagents, materials, equipment, etc. involved in the examples can be obtained commercially without special instructions; the methods involved, without special instructions, are existing methods.

[0036] In the examples, tris(3'-F-4-carboxybiphenyl)amine can be prepared according to the existing technology; reference can be made to the literature "Journal of Solid State Chemistry 2022, 307, 122820." for preparation.

[0037] Example 1

[0038] A preparation method of a yttrium-based metal-organic framework material with selective fluorescence recognition for furacilin, comprising the steps:

[0039] Step 1: Add 0.4 mmol of yttrium nitrate hexahydrate, 0.1 mmol of tris(3'-F-4-carboxybiphenyl)amine, 6 ml of N,N-dimethylformamide, 4 ml of methanol, 0.45 ml of acetic acid with a mass concentration of 99.5%, and 2 ml of water into a reaction kettle, and ultrasonically treat at room temperature for 15 min to fully mix and disperse evenly. The reaction kettle contains a 20 ml polytetrafluoroethylene inner liner.

[0040] Step 2: Heat the above reaction kettle to 100 °C, carry out a solvothermal reaction for 14 hours, then cool down to 25 °C, and filter to obtain light yellow flaky crystals.

[0041] Step 3: Collect the above flaky crystals, wash them successively with water and methanol, and after vacuum drying, the target product: yttrium-based metal-organic framework material can be obtained.

[0042] Example 2

[0043] A preparation method of a yttrium-based metal-organic framework material with selective fluorescence recognition for furacilin, comprising the steps:

[0044] Step 1: Add 0.4 mmol of yttrium nitrate hexahydrate, 0.1 mmol of tris(3'-F-4-carboxybiphenyl)amine, 4 ml of N,N-dimethylformamide, 5 ml of methanol, 0.3 ml of acetic acid with a mass concentration of 99.5%, and 2 ml of water into a reaction kettle, and ultrasonically treat at room temperature for 15 min to make them fully mixed and dispersed evenly. The reaction kettle contains a 20-ml polytetrafluoroethylene inner liner.

[0045] Step 2: Heat the above reaction kettle to 100 °C, carry out a solvothermal reaction for 16 hours, then cool down to 25 °C, and filter to obtain light yellow flaky crystals.

[0046] Step 3: Collect the above flaky crystals, wash them successively with water and methanol, and after vacuum drying, the target product, the yttrium-based metal-organic framework material, can be obtained.

[0047] Example 3

[0048] A preferred preparation method of a yttrium-based metal-organic framework material with selective fluorescence recognition for furacilin, comprising the steps:

[0049] Step 1: Add 0.4 mmol of yttrium nitrate hexahydrate, 0.1 mmol of tris(3'-F-4-carboxybiphenyl)amine, 6 ml of N,N-dimethylformamide, 4 ml of methanol, 0.45 ml of acetic acid with a mass concentration of 99.5% into a reaction kettle, and ultrasonically treat at room temperature for 15 min to make them fully mixed and dispersed evenly. The reaction kettle contains a 20-ml polytetrafluoroethylene inner liner.

[0050] Step 2: Heat the above reaction kettle to 100 °C, carry out a solvothermal reaction for 20 hours, then cool down to 25 °C, and filter to obtain light yellow flaky crystals.

[0051] Step 3: Collect the above flaky crystals, wash them successively with water and methanol, and after vacuum drying, the target product, the yttrium-based metal-organic framework material, can be obtained.

[0052] Example 4

[0053] A preparation method of a yttrium-based metal-organic framework material with selective fluorescence recognition for furacilin, comprising the steps:

[0054] Step 1: Add 0.5 mmol of yttrium nitrate hexahydrate, 0.1 mmol of tris(3'-F-4-carboxybiphenyl)amine, 8 ml of N,N-dimethylformamide, 4 ml of methanol, 0.35 ml of acetic acid with a mass concentration of 99.5%, and 2 ml of water into a reaction kettle, and ultrasonically treat for 5 min at room temperature to fully mix and disperse evenly. The reaction kettle contains a 20-ml polytetrafluoroethylene liner.

[0055] Step 2: Heat the above reaction kettle to 105 °C, carry out a solvothermal reaction for 14 hours, then cool down to 25 °C, and filter to obtain light yellow flaky crystals.

[0056] Step 3: Collect the above flaky crystals, wash them successively with water and methanol, and after vacuum drying, the target product: yttrium-based metal-organic framework material can be obtained.

[0057] Test Example

[0058] [[ID=I2]]Characterize and visually detect the target product prepared in Example 1

[0059] 1. Single crystal diffraction data was collected on a diffractometer, and Mo-Kα radiation monochromatized by a graphite monochromator, 2.9° < 0s 22.8°, proved that this coordination polymer belongs to the triclinic system, P-1 space group, and its unit cell parameters are: a = 8.7145(8), b = 13.0531(12), c = 21.3214(19), α = 73.3620(10), β = 87.314(3), γ = 76.025(2), V = 2254.4(4), as shown in Table 1 for details. Figure 1 is the crystal structure diagram of this yttrium-based metal-organic framework material drawn by Diamond software.

[0060]

[0061] X-ray single crystal diffraction indicates that Y-MOF crystallizes in the P-1 space group. The asymmetric unit includes a single Y(III) center, a fully deprotonated tricarboxylic acid ligand, and two water molecules. Y(III) adopts an eight-coordinate single-capped square prism, surrounded by eight oxygen atoms for coordination, and the coordinating atoms are respectively from 4 oxygen atoms of 4 independent tricarboxylic acid ligands and 2 oxygen atoms of water molecules. The Y-O bond length range

[0062] 2. Use an F-7000 type fluorescence spectrometer to test the solid fluorescence data of the obtained metal-organic framework material. As Figure 2 shown, the yttrium-based metal-organic framework material emits fluorescence at 493 nm in the solid state.

[0063] 3. Suspend 2 mg of the yttrium-based metal-organic framework material prepared by the method of Example 1 in 2 ml of 1×10-3 In an aqueous solution of antibiotic X at a concentration of [[mol / L]], each abbreviation represents (X = ornidazole (ODZ), nitrofurazone (NFZ), furazolidone (FZD), sulfamethoxazole (SMX), sulfaguanidine (SG), sulfadiazine (SDZ), secnidazole (SCZ), levofloxacin (LVX)). The test was carried out using an F-7000 fluorescence spectrometer, and the fluorescence spectra of the yttrium-based metal-organic framework material for the recognition of the above antibiotics were plotted using Origin software. As Figure 3 shown, it can be seen that the yttrium-based metal-organic framework material only has a complete fluorescence quenching effect on nitrofurazone and has a high selective recognition performance for nitrofurazone.

[0064] 4. Suspend 2 mg of the yttrium-based metal-organic framework material prepared by the method of Example 1 in 2 ml of an aqueous solution, and titrate it with an aqueous solution of 1×10 -3 mol / L nitrofurazone (NFZ). The fluorescence titration spectrum of the yttrium-based metal-organic framework material for nitrofurazone (NFZ) plotted using Origin software is as Figure 4 shown, and the fluorescence detection limit of nitrofurazone can be obtained as 3.7×10 -6 mol / L through the formula 3σ / k.

[0065] 5. Prepare a mixed matrix membrane: Dissolve 2 g of polymethyl methacrylate in 15 ml of acetone, disperse 40 mg of the metal-organic framework material prepared by the method of Example 1 in 5 ml of acetone, and ultrasonicate for 15 min. Mix all the solutions evenly and volatilize to obtain a viscous mixture; spread the viscous mixture evenly on a glass dish with an area of 10 square centimeters, and let acetone evaporate naturally to form a shape. Demold to obtain the mixed matrix membrane.

[0066] Visual detection was carried out under a 365 nm ultraviolet lamp. The mixed matrix membrane emits blue-yellow light under a 365 nm ultraviolet lamp. Use a dropper to add 2 drops of an aqueous solution of 1×10 -3 mol / L nitrofurazone. The fluorescence of the part where nitrofurazone is added is quenched. After rinsing the mixed matrix membrane with pure water, the mixed matrix membrane resumes blue-yellow fluorescence and can be recycled. It should be noted that when 2 drops of an aqueous solution of 1×10 -3 mol / L of other antibiotics are added to the mixed matrix membrane with a dropper, there is no obvious fluorescence quenching.

[0067] 6. Stability test:

[0068] Soak 15 mg of the yttrium-based metal-organic framework material (Y-MOF) prepared in Example 1 in water or DMF at room temperature for three days, wash with methanol and dry, and then test the XRD pattern.

[0069] As Figure 6As shown, after the Y-MOF powder was soaked in water or DMF, its XRD data was consistent with that of the original Y-MOF powder, indicating good stability in water or DMF.

[0070] 7. Thermogravimetric analysis (TGA): The thermal stability curve of the yttrium-based metal-organic framework material (Y-MOF) prepared in Example 1 was tested from room temperature to 800 °C under a N2 atmosphere. As Figure 7 shown. The weight loss between approximately 30 - 200 °C was attributed to solvent molecules and coordinated water in the system. The framework structure of Y-MOF did not start to collapse until after 300 °C.

[0071] 8. As Figure 8 shown, 2 g of polymethyl methacrylate was dissolved in 15 ml of acetone, and 40 mg of the metal-organic framework material (MOF-1) was dispersed in 5 ml of acetone and sonicated for 15 min. All the solutions were mixed evenly and volatilized to obtain a viscous mixture; the viscous mixture was evenly spread on a 10-square-centimeter glass dish and the acetone was allowed to evaporate naturally to form it. The prepared mixed matrix membrane was peeled off, demolded, and cut before use. The prepared mixed matrix membrane emits blue-yellow light under a 365-nm ultraviolet lamp and can be used for visual detection of nitrofurazone.

[0072] In summary, the preparation method provided by the present invention is based on the strong coordination ability of trivalent yttrium ions and the coordination of tris(3'-F-4-carboxybiphenyl)amine organic ligands to prepare a yttrium-based metal-organic framework material, indicating a new direction for the preparation of metal-organic framework materials with selective fluorescence recognition for nitrofurazone; the yttrium-based metal-organic framework material has high sensitivity and selective recognition for nitrofurazone and has potential application value in the fluorescence recognition of harmful substances.

[0073] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone, characterized in that, The chemical formula of the yttrium-based metal-organic framework material is C 39 H 25 F3NO8Y; The preparation method of the yttrium-based metal-organic framework material includes the steps of: fully mixing and dispersing yttrium nitrate, tris(3'-F-4-carboxybiphenyl)amine, N,N-dimethylformamide, methanol, acetic acid and water evenly; carrying out a solvothermal reaction, and then filtering, washing and drying to obtain the yttrium-based metal-organic framework material.

2. The yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone according to claim 1, wherein, The yttrium-based metal-organic framework material has a crystal structure, belonging to the triclinic system, space group P-1, and the unit cell parameters are: a = 8.7145(8), b = 13.0531(12), c = 21.3214(19), α = 73.3620(10), β = 87.314(3), γ = 76.025(2), V = 2254.4(4).

3. The yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone according to claim 1, characterized in that, The molar ratio of yttrium nitrate to tris(3'-F-4-carboxybiphenyl)amine is 3-5:

1.

4. The yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone according to claim 1, characterized in that, The volume ratio of the molar amount of yttrium nitrate to N,N-dimethylformamide is 0.05-0.08 mol / L.

5. The yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone according to claim 1, characterized in that The volume ratio of N,N-dimethylformamide, methanol, acetic acid and water is 2-4:2-2.5:0.15-0.225:0-1.

6. The yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone according to claim 1, characterized in that, The mixing and dispersion is carried out by ultrasonic wave for 5-20 min at room temperature.

7. The yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone according to claim 1, characterized in that The solvothermal reaction temperature is 90-110 °C, and the solvothermal reaction time is 12-26 hours.

8. The application of the yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone according to any one of claims 1-7, characterized in that, It is applied to the detection of nitrofurazone.

9. Use of the yttrium-based metal-organic framework material with selective fluorescence recognition for nitrofurazone according to claim 8, characterized in that, The yttrium-based metal-organic framework material can be used to prepare a mixed matrix membrane for detecting nitrofurazone; the mixed matrix membrane is prepared by using polymethyl methacrylate, the yttrium-based metal-organic framework material and a solvent as raw materials and volatilizing the solvent.

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