Organic framework material with high adsorption of non-steroidal drugs, preparation method and application thereof
Organic framework materials prepared by hydrothermal synthesis introduce guanidine groups and π-π stacking mechanisms, solving the problem of poor adsorption of nonsteroidal anti-inflammatory drugs by covalent organic framework materials and achieving efficient adsorption of drugs such as ibuprofen.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUANGDONG UNIV OF TECH
- Filing Date
- 2023-07-25
- Publication Date
- 2026-06-05
AI Technical Summary
Existing covalent organic framework materials do not show good adsorption performance for nonsteroidal anti-inflammatory drugs.
Organic framework materials were prepared by hydrothermal synthesis using 1,2,4,5-tetra(4-formylphenyl)benzene and 1,3-diaminoguanidine hydrochloride as precursors. Guanidine groups were introduced to enhance the adsorption effect through electrostatic interactions and π-π stacking.
It achieved highly efficient adsorption of a variety of nonsteroidal drugs, especially significantly improved adsorption of drugs such as ibuprofen, with an adsorption capacity of 313.99 mg/g.
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Figure CN116970137B_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the field of organic framework materials technology, and particularly relates to organic framework materials for efficient adsorption of nonsteroidal drugs, their preparation methods and applications. Background Technology
[0002] Nonsteroidal anti-inflammatory drugs (NSAIDs) are used as analgesics to treat various diseases, including fever, rheumatoid arthritis, and other inflammations. For example, ibuprofen is widely used to treat symptoms such as acne, pain, inflammation, and fever. However, NSAIDs such as ibuprofen have the characteristics of resistance to degradation, accumulation, and migration. After entering water bodies through human or animal urine, ibuprofen is metabolized into carboxyl and hydroxyibuprofen in the aquatic medium. With accumulation, it has a significant impact on human health and related ecosystems. Therefore, it is necessary to eliminate NSAID pollution in water bodies.
[0003] Covalent organic frameworks (COFs) are a novel type of crystalline mesh with permanent channels, consisting of lightweight elements (C, O, N, B, etc.) linked by covalent bonds. They have low density, high specific surface area, and good chemical stability, which bring rich application prospects to COFs. However, the adsorption effect of COFs on nonsteroidal anti-inflammatory drugs is currently poor. Summary of the Invention
[0004] In view of this, this application provides an organic framework material for the efficient adsorption of nonsteroidal drugs, its preparation method and application, to solve the technical problem that the adsorption effect of covalent organic framework materials for nonsteroidal anti-inflammatory drugs in the prior art needs to be improved.
[0005] The first aspect of this application provides a method for preparing an organic framework material that efficiently adsorbs nonsteroidal drugs. The preparation method includes the following steps:
[0006] Step S1: The precursor monomers 1,2,4,5-tetratetra(4-formylphenyl)benzene and 1,3-diaminoguanidine hydrochloride are mixed in 1,4-dioxane and deionized water and then sealed for reaction to obtain an organic framework material.
[0007] Step S2: The organic framework material precursor is washed and dried sequentially to obtain an organic framework material that can efficiently adsorb nonsteroidal drugs.
[0008] Preferably, in step S1, the 1,2,4,5-tetratetra(4-formylphenyl)benzene and 1,3-diaminoguanidine hydrochloride are 117.7 parts by mass and 45.2 parts by mass, respectively, calculated in parts by mass.
[0009] Preferably, in step S1, the sealing reaction is carried out at a temperature of 120°C for 24 hours.
[0010] Preferably, in step S2, the washing process involves sequentially washing with methanol, acetone, and ultrapure water.
[0011] Preferably, in step S2, the vacuum drying temperature is 70°C and the time is 12 hours.
[0012] The second aspect of this application provides an organic framework material for the efficient adsorption of nonsteroidal drugs, which is prepared by the preparation method described in the first aspect.
[0013] Preferably, the organic framework material is a spherical organic framework material.
[0014] Preferably, the particle size of the spherical organic framework material is 300~500nm.
[0015] The third aspect of this application provides the application of highly efficient adsorption of nonsteroidal drugs in the treatment of water bodies contaminated by nonsteroidal drugs.
[0016] Preferably, the nonsteroidal drug polluting the water body is ibuprofen, diclofenac, indomethacin, ketoprofen, or naproxen.
[0017] In summary, this application provides an organic framework material for highly efficient adsorption of nonsteroidal drugs, its preparation method, and its application. The preparation method of the organic framework material for highly efficient adsorption of nonsteroidal drugs includes mixing 1,2,4,5-tetra(4-formylphenyl)benzene, 1,3-diaminoguanidine hydrochloride, 1,4-dioxane, and deionized water, followed by a sealed reaction to obtain an organic framework material precursor. The precursor is then washed and dried to obtain the organic framework material. This preparation method employs a simple hydrothermal synthesis method, where the monomers 1,2,4,5-tetra(4-formylphenyl)benzene and 1,3-diaminoguanidine hydrochloride undergo a Schiff base reaction. The synthesis process is simple. Furthermore, the organic framework material incorporates guanidine groups. When the organic framework material with positively charged guanidine fragments exists in aqueous solution in ionic form and adsorbs nonsteroidal drugs (NSAIDs), the NSAIDs rapidly enter the ordered pore channels and generate electrostatic interactions with the organic framework material containing ionic sites. This results in good adsorption performance for a variety of NSAIDs. Moreover, NSAIDs containing phenyl groups, such as ibuprofen, have abundant π-π sites, which can generate π-π stacking with the organic framework material, synergistically significantly improving the adsorption effect of IBP. This solves the technical problem that the adsorption effect of covalent organic framework materials for NSAIDs in the prior art needs to be improved. Attached Figure Description
[0018] To more clearly illustrate the technical solutions in the specific embodiments of this application or the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0019] Figure 1 Infrared spectrum of the organic framework material for high-efficiency adsorption of nonsteroidal drugs prepared by the preparation method provided in Example 1 of this application;
[0020] Figure 2 X-ray diffraction pattern of the organic framework material for high-efficiency adsorption of nonsteroidal drugs prepared by the preparation method provided in Example 1 of this application;
[0021] Figure 3 X-ray photoelectron spectroscopy (XPS) of the organic framework material for high-efficiency adsorption of nonsteroidal drugs prepared by the preparation method provided in Example 1 of this application;
[0022] Figure 4 Scanning electron microscope (SEM) and transmission electron microscope (TEM) images of the organic framework material for highly efficient adsorption of nonsteroidal drugs prepared by the preparation method provided in Example 1 of this application;
[0023] Figure 5 Specific surface area test diagram of the organic framework material for high-efficiency adsorption of nonsteroidal drugs prepared by the preparation method provided in Example 1 of this application;
[0024] Figure 6 A schematic diagram illustrating the removal rate of nonsteroidal drugs by the organic framework material for high-efficiency adsorption of nonsteroidal drugs prepared by the preparation method provided in Example 1 of this application.
[0025] Figure 7 This is a schematic diagram of the adsorption kinetics of ibuprofen on the organic framework material for high-efficiency adsorption of nonsteroidal drugs prepared by the preparation method provided in Example 1 of this application. Detailed Implementation
[0026] This application provides an organic framework material for the efficient adsorption of nonsteroidal drugs, its preparation method, and its application, in order to solve the technical problem that the adsorption effect of covalent organic framework materials for nonsteroidal anti-inflammatory drugs in the prior art needs to be improved.
[0027] The technical solutions of this application will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0028] Example 1
[0029] In view of the shortcomings of existing covalent organic framework materials in terms of low adsorption efficiency for nonsteroidal anti-inflammatory drugs, Example 1 of this application provides a method for preparing an organic framework material with high efficiency for adsorbing nonsteroidal drugs; the preparation method includes preparing an organic framework material precursor and preparing an organic framework material with high efficiency for adsorbing nonsteroidal drugs.
[0030] The preparation of the organic framework material precursor involves: weighing 235.4 mg (0.48 mmol) of 1,2,4,5-tetra(4-formylphenyl)benzene and 90.4 mg (0.72 mmol) of 1,3-diaminoguanidine hydrochloride and placing them in a 25 mL standard glass gate reaction tube, adding 4 mL of ultrapure water and 12 mL of 1,4-dioxane, sealing the tube, and heating it in an oil bath at 120 °C for 24 h. After the reaction is completed, the tube is cooled completely to obtain the organic framework material precursor.
[0031] The preparation of an organic framework material for highly efficient adsorption of nonsteroidal drugs includes: thoroughly washing the organic framework material precursor with methanol, acetone, and ultrapure water sequentially, and then drying it in a vacuum drying oven at 70°C for 12 hours to obtain the final product, a covalent organic framework material (TFPB-DG). Cl -COF).
[0032] Comparative Example 1
[0033] Comparative Example 1 of this application provides another method for preparing organic framework materials, the method including the preparation of TPB-DMTP-COF and the preparation of organic framework material COF-NO2.
[0034] The preparation of TPB-DMTP-COF involves: ultrasonically dispersing, condensing, centrifuging, and purifying a mixture of (TAPB, 1,3,5-Tris(4-AminoPhenyl)Benzene, 1,3,5-tris(4-aminophenyl)benzene, 168 mg, 0.48 mmol) and (DMTA, 2,5-Dimethoxyterephthalaldehyde, 2,5-dimethoxyterephthalaldehyde, 138 mg, 0.72 mmol) in o-dichlorobenzene / n-butanol / acetic acid (2 ml / 2 ml / (0.4 ml, 6 M)) to obtain TPB-DMTP-COF.
[0035] The preparation of the organic framework material COF-NO2 involved adding TPB-DMTP-COF (19.6 mg), 4-nitrophenylacetylene (22.05 mg, 0.15 mmol), Lewis acid-base adduct (BF3·OEt2, 20 μL, 0.15 mmol), tetrachloro-1,4-benzoquinone (40 mg, 0.15 mmol), and toluene (2 ml) into a Pyrex tube and mixing thoroughly with ultrasound. The tube was then flash-frozen in a liquid nitrogen bath, evacuated, flame-sealed, and placed in an oven at 110 °C for 3 days. Afterward, the mixture was filtered, washed with THF, saturated NaHCO3 solution, and H2O. The collected solid was purified with tetrahydrofuran in a Soxhlet extractor for 1 day and dried overnight at 80 °C to obtain an organic framework material COF-NO2 powder (approximately 25 mg).
[0036] Comparative Example 2
[0037] Comparative Example 2 of this application provides another method for preparing an organic framework material, the method comprising:
[0038] Preparation of heterogeneous core solutions and preparation of organic framework material MICOF@SiO2.
[0039] The preparation of the heterogeneous core solution involved dissolving (TFB, 1,3,5-Tris(4-formylphenyl)benzene, 1,3,5-tris(4-formylphenyl)benzene, 83.98 mg) in 13 ml of NH₂-silica suspension (100 mg / ml, in dioxane) and stirring at room temperature for 1 hour. After reacting for 10 minutes, a heterogeneous core was formed, which was then diluted with dioxane to 50 mg / ml.
[0040] The preparation of the organic framework material MICOF@SiO2 includes: dissolving (TFB, 1,3,5-Tris(4-formylphenyl)benzene, 1,3,5-tris(4-formylphenyl)benzene, 210.6 mg) and 1,6-diaminopyrene (BD, 484.3 mg) in 13 ml of heterogeneous core solution (50 mg / ml), mixing the two solutions, adding 1.17 ml of acetic acid and 268.2 mg of ibuprofen, transferring the reaction mixture to a 50 ml round flask, and refluxing at 120 °C for 3 hours. The template molecules in the obtained nanocomposite material are removed by washing several times with an ethanol / acetic acid mixture (98 / 2, v / v), and then drying in the atmosphere to obtain the organic framework material MICOF@SiO2 nanocomposite material.
[0041] Experimental Example 1
[0042] Example 1 of this experiment tested the performance of the organic framework materials prepared in the examples and comparative examples, including infrared spectroscopy, X-ray diffraction, X-ray energy dispersive spectroscopy, scanning electron microscopy, transmission electron microscopy, specific surface area, and adsorption of nonsteroidal drugs.
[0043] Among them, the organic framework material (TFPB-DG) prepared in Example 1 Cl The infrared spectrum, X-ray diffraction, and X-ray energy dispersive spectroscopy results of -COF are as follows: Figure 1-3 As shown, from Figure 1 It can be seen that, compared with the control monomers 1,2,4,5-tetratetra(4-formylphenyl)benzene (TFPB) and 1,3-diaminoguanidine hydrochloride (DG), Cl Compared to the infrared spectrum of the original sample, the synthesized organic framework material (TFPB-DGCl-COF) exhibits a characteristic C=N peak at 1626 cm⁻¹, indicating that the preparation method provided in Example 1 of this application uses a simple hydrothermal synthesis method to induce a Schiff base reaction between the amino and aldehyde groups, forming an imine bond, thus preparing the organic framework material. Meanwhile, Figure 3 The X-ray energy dispersive spectroscopy test also showed the same results. The N1s measurement results show that the characteristic peak at 398.31 eV represents the C=N peak, which further confirms that the organic framework material was synthesized by simple hydrothermal synthesis.
[0044] and Figure 2 The X-ray diffraction pattern shown indicates that the organic framework material has a broad peak in the range of 20.5° to 26.7°. This is due to the repulsive interaction between the layers of the organic framework material. The inherently positively charged guanidine units may cause weak π-π stacking between the layers. The presence of loosely bonded chloride ions and the positive charge of guanidine units can reduce crystallinity by interfering with π-π stacking.
[0045] The organic framework material (TFPB-DG) prepared in Example 1 Cl The scanning electron microscope (SEM) and transmission electron microscope (TEM) images of COF are shown below. Figure 4 a, Figure 4 As shown in b, from Figure 4 a and Figure 4 b. As can be seen, the organic framework material (TFPB-DG) prepared by the hydrothermal synthesis method provided in Example 1 of this application is... Cl The -COF structure is a relatively regular sphere with a particle size of about 300-500 nanometers. The porous structure of organic framework materials can be designed to increase the density of loaded functional sites and facilitate the accessibility of ion binding sites.
[0046] Meanwhile, the organic framework material (TFPB-DG) prepared in Example 1 Cl Specific surface area test of COF (as shown in the figure) Figure 5 As shown, from Figure 5 It can be seen that the specific surface area of the organic framework material is 7.5797 m² / g. The relatively low surface area may be due to the weak directional control of the guanidine units between layers or the presence of chloride ion disturbance layers within the pores. Despite the small surface area, the organic framework material can effectively adsorb non-steroidal drugs through electrostatic adsorption and other mechanisms.
[0047] The organic framework material provided in Example 1 was subjected to adsorption tests for the nonsteroidal drugs ibuprofen (IBP), diclofenac (DCF), indomethacin (IDM), ketoprofen (KT), and naproxen (NPX). The test process included:
[0048] (1) 5 mg of the organic framework material prepared in Example 1 was added to 40 ml of ibuprofen, diclofenac, indomethacin, ketoprofen and naproxen solutions with a concentration of 20 mg / L, and the mixture was placed on a magnetic stirrer for 3 hours to adsorb.
[0049] (2) After adsorption was complete, stirring was stopped, 1 ml of sample solution was collected using a syringe, and filtered through a 0.45 μm polyethersulfone membrane. The concentration of the nonsteroidal drug in the collected solution was measured by high performance liquid chromatography (HPLC). Two parallel experiments were set up for each drug.
[0050] Test results are as follows Figure 6 As shown, the organic framework material prepared in Example 1 has good adsorption capacity for ibuprofen, diclofenac, and indomethacin. This indicates that the organic framework material prepared in Example 1 has a good removal effect on nonsteroidal drugs and is a reliable and selective nonsteroidal drug adsorbent.
[0051] Further adsorption tests were conducted on the organic framework materials provided in Example 1 and Comparative Examples 1-2 to compare the adsorption capacity of the nonsteroidal drug ibuprofen (IBP). The test procedure included:
[0052] (1) At 25°C, prepare 120 mL of ibuprofen solution with a concentration of 100 mg / L, add 15 mg of the organic framework material prepared in Example 1, and add it to the rotor placed on a magnetic stirrer for adsorption.
[0053] (2) Collect 1 mL of sample solution at regular time intervals using a syringe and filter it using a 0.45 μm polyethersulfone membrane (which has no effect on IBP concentration).
[0054] (3) Stop stirring after the reaction has proceeded for exactly 3 hours;
[0055] (4) The concentration of IBP in the collected solution was measured by high performance liquid chromatography (HPLC).
[0056] Test results are as follows Figure 7 As shown, after 180 min of adsorption, the adsorption capacity of the organic framework material prepared in Example 1 for ibuprofen was 313.99 mg / g; while the adsorption test results of the organic framework materials provided in Comparative Examples 1-2 for the nonsteroidal drug ibuprofen (IBP) showed that the adsorption capacities for ibuprofen were 94 mg / g and 50 mg / g, respectively, indicating that the organic framework material provided in Example 1 has a good adsorption effect on ibuprofen.
[0057] In summary, the organic framework material provided in Example 1 of this application introduces guanidine groups. When the organic framework material with positively charged guanidine fragments exists in aqueous solution in ionic form, nonsteroidal drugs (NSAIDs) rapidly enter the ordered pore channels and generate electrostatic interactions with the organic framework material having ionic sites. This results in good adsorption performance for a variety of NSAIDs. Furthermore, NSAIDs such as ibuprofen containing phenyl groups have abundant π-π sites, which can generate π-π stacking with the organic framework material, synergistically significantly improving the adsorption effect of IBP. This solves the technical problem that the adsorption effect of covalent organic framework materials for NSAIDs in the prior art needs to be improved.
[0058] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.
Claims
1. A method for preparing an organic framework material for efficiently adsorbing nonsteroidal drugs, characterized in that, Including the following steps: Step S1: The precursor monomers 1,2,4,5-tetra(4-formylphenyl)benzene, 1,3-diaminoguanidine hydrochloride, 1,4-dioxane, and deionized water are mixed and then reacted in a sealed manner to obtain an organic framework material precursor. The temperature of the sealed reaction is 120°C and the time is 24 hours. Step S2: The organic framework material precursor is washed and dried sequentially to obtain an organic framework material that can efficiently adsorb nonsteroidal drugs.
2. The method for preparing an organic framework material for highly efficient adsorption of nonsteroidal drugs according to claim 1, characterized in that, In step S1, the 1,2,4,5-tetratetra(4-formylphenyl)benzene and 1,3-diaminoguanidine hydrochloride are 117.7 parts by mass and 45.2 parts by mass, respectively, calculated in parts by mass.
3. The method for preparing an organic framework material for highly efficient adsorption of nonsteroidal drugs according to claim 1, characterized in that, In step S2, the washing process involves sequentially washing with methanol, acetone, and ultrapure water.
4. The method for preparing an organic framework material for highly efficient adsorption of nonsteroidal drugs according to claim 1, characterized in that, In step S2, the vacuum drying temperature is 70℃ and the time is 12h.
5. An organic framework material for efficiently adsorbing nonsteroidal drugs, characterized in that, It is prepared by the preparation method described in any one of claims 1-4.
6. The organic framework material for efficiently adsorbing nonsteroidal drugs according to claim 5, characterized in that, The organic framework material is a spherical organic framework material.
7. The organic framework material for efficiently adsorbing nonsteroidal drugs according to claim 6, characterized in that, The particle size of the spherical organic framework material is 300~500nm.
8. The application of the organic framework material for efficiently adsorbing nonsteroidal drugs as described in any one of claims 5-7 in the treatment of water bodies polluted by nonsteroidal drugs.
9. The application according to claim 8, characterized in that, The nonsteroidal drugs polluting the water bodies are ibuprofen, diclofenac, indomethacin, ketoprofen, or naproxen.