A cobalt-based metal-organic framework material, preparation method, and application in the detection and degradation of sulfonamide drugs

Abstract

The present invention provides a cobalt-based metal organic framework material, a preparation method and its application in the detection and degradation of sulfonamides, belonging to the technical field of detection and degradation of sulfonamides. Co66% / ZIF‑8 is a composite material synthesized from Co(CH3COO)2·4H2O, Zn(CH3COO)2·2H2O and 2‑MIM as main components. The ratio of Co(CH3COO)2·4H2O and Zn(CH3COO)2·2H2O is 2:1. The defect coordination on the outer surface of Co66% / ZIF‑8 bimetallic crystals is used to simulate the catalytic active center of natural carbonic anhydrase (CA). By introducing cobalt ions, the parameters of the synthesis process are regulated, and a biomimetic CA with high stability and catalytic ability is successfully prepared. This material quantifies sulfonamides (SAAs) in the environment and food by inhibiting human carbonic anhydrase II (hCAII)-like activity. The synergistic effect between the bimetallic Co66% / ZIF-8 nanozymes enhances diffusion and mass transfer in the reactant solution, enabling rapid visual detection and adsorption degradation of SAAs. The prepared Co66% / ZIF-8 nanozymes can achieve rapid analysis and effective removal of SAAs in the environment and food.

Description

Technical Field

[0001] The present invention relates to the technical field of sulfonamide drug detection and degradation, and in particular to a cobalt-based metal organic framework material, a preparation method and application thereof in sulfonamide drug detection and degradation. Background Art

[0002] Sulfonamides are a class of antimicrobial drugs widely used in human medicine and animal husbandry. Due to their extensive use and inappropriate discharge, sulfonamide residues in the environment are becoming increasingly serious, posing a potential threat to the ecological environment and human health.

[0003] Currently, methods for detecting sulfonamides primarily include high-performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometry (LC-MS). While these methods offer high accuracy and sensitivity, they often require expensive instrumentation, complex sample pretreatment procedures, and specialized personnel, making rapid on-site detection difficult. Traditional treatment methods for residual sulfonamides in the environment, such as physical adsorption and biodegradation, are inefficient, costly, and prone to secondary contamination. Therefore, developing a simple, efficient, and economical method for detecting and treating sulfonamides is of great practical significance.

[0004] In recent years, rapid advances in materials science have provided new insights into addressing this problem. New functional materials, such as layered double hydroxides, ceria, manganese dioxide, carbon nanomaterials, and metal-organic frameworks, have shown great potential for drug detection and degradation due to their unique physicochemical properties. However, most existing materials only possess a single detection or degradation function, making it difficult to simultaneously meet the requirements for rapid detection and effective degradation of sulfonamides. To achieve efficient detection and degradation of sulfonamides, the development of a novel material with both colorimetric detection and degradation capabilities is imperative.

[0005] Materials with both colorimetric detection and degradation capabilities have broad application prospects in environmental monitoring, food safety, healthcare, and other fields. For example, in environmental monitoring, they can be used to monitor pollutant concentrations in water, soil, and air in real time, and to degrade pollutants that exceed standards on-site. In food safety, they can detect pesticide residues, heavy metals, and other harmful substances in food and degrade them to ensure food safety. In healthcare, they can be used to detect and degrade toxins and harmful substances in organisms, providing new tools for disease diagnosis and treatment.

[0006] As an emerging technology, materials with both colorimetric detection and degradation capabilities offer new insights and approaches to addressing environmental monitoring and pollution control. With continued in-depth research, we believe these materials will play a significant role in even more areas. Summary of the Invention

[0007] The purpose of the present invention is to provide a cobalt-based metal-organic framework material, a preparation method and its application in the detection and degradation of sulfonamide drugs, aiming to solve the problems of the singleness, limitations and low efficiency of the existing methods for detecting and treating sulfonamide drugs.

[0008] Specific purposes include:

[0009] 1. Develop a material that can simultaneously achieve efficient and sensitive colorimetric detection of sulfonamides, so as to quickly and intuitively determine the presence and content of sulfonamides in samples.

[0010] 2. Provide a material that can effectively degrade sulfonamides, reduce the residues and hazards of such drugs in the environment, and protect the ecological environment and human health.

[0011] 3. Overcoming the shortcomings of traditional detection methods such as complex operation, expensive instruments, and the need for professional equipment and technicians, the material of this invention has the characteristics of simple operation, low cost, and easy promotion and application.

[0012] 4. By realizing the dual-functional integration of detection and degradation, the processing process and time can be reduced, the processing efficiency can be improved, and the processing cost can be reduced.

[0013] 5. Provide an innovative, efficient and convenient comprehensive solution for the monitoring and management of sulfonamides, and promote technological progress and development in related fields.

[0014] In order to achieve the above-mentioned purpose, the present invention adopts the following technical scheme: a cobalt-based metal organic framework material, which is a composite material synthesized with Co(CH3COO)2·4H2O, Zn(CH3COO)2·2H2O and 2-MIM as main components.

[0015] Further preferably, the molar ratio of Co(CH3COO)2·4H2O and Zn(CH3COO)2·2H2O is 2:1;

[0016] Another technical solution of the present invention is: a method for preparing a cobalt-based metal organic framework material, comprising the following steps:

[0017] Step 1: Weigh a certain amount of Co(CH3COO)2·4H2O and dissolve it in deionized water. Stir the mixture evenly under magnetic stirring to obtain solution A.

[0018] Step 2: Dissolve a certain amount of Zn(CH3COO)2·2H2O in deionized water and stir evenly to obtain solution B;

[0019] Step 3: Dissolve a certain amount of 2-MIM in deionized water and stir evenly to obtain solution C;

[0020] Step 4: Slowly add solution B to solution A while stirring. After the addition is complete, continue stirring and react for 5 minutes.

[0021] Step 5: While stirring, slowly add solution C dropwise to the mixture obtained in step 4. After the addition is complete, continue stirring and react for 5 minutes;

[0022] Step 6: While continuing to stir, slowly add the methanol solution dropwise to the mixture obtained in step 5. After the addition is complete, continue stirring and react for 2 hours;

[0023] Step 7: Transfer the mixed solution after the reaction into a centrifuge tube, centrifuge it at room temperature, collect the precipitate, and obtain a preliminary product;

[0024] Step 8: washing the precipitate with methanol to remove unreacted substances and impurities;

[0025] Step 9: Dry the washed precipitate in a vacuum drying oven overnight to obtain a material with dual functions of colorimetric detection and degradation of sulfonamides.

[0026] The molar ratio of Co(CH3COO)2·4H2O added in step 1 to Zn(CH3COO)2·2H2O added in step 2 is 2:1.

[0027] In the step 1, in a 50 mL beaker, 1.317 g of Co(CH3COO)2·4H2O was dissolved in 15 mL of deionized water to obtain solution A; in the step 2, in a 50 mL beaker, 0.6585 g of Zn(CH3COO)2·2H2O was dissolved in 15 mL of deionized water to obtain solution B.

[0028] The temperature set in steps 4 and 5 is room temperature, and the stirring speed is maintained at 5000 r / min.

[0029] The amount of methanol added in step 6 was 15 mL, and the stirring temperature was maintained the same as that in steps 4 and 5.

[0030] In step 7, the reaction solution was transferred to a 15 mL centrifuge tube and centrifuged at a speed of 8000 rpm for 5 min.

[0031] The product in step 8 was washed with methanol three times.

[0032] The drying temperature in step 9 is 70°C.

[0033] Another technical solution of the present invention is: application of the above-mentioned cobalt-doped organic framework material in the efficient detection and degradation of sulfonamides.

[0034] Surface modification and functionalization:

[0035] The present invention uses a chemical grafting method to introduce cobalt ions as dopants on the material surface to replace the original zinc ions, successfully designing a bimetallic active center, thereby obtaining a biomimetic CA nanozyme with excellent stability and catalytic activity.

[0036] Further reaction of functional groups revealed that Co66% / ZIF-8 has a geometric structure similar to the active center of human carbonic anhydrase II (hCAII), where the active site Co 2+ Coordinated by three histidine residues, it can hydrolyze p-nitrophenyl acetate (pNPA) to p-nitrophenol (pNP).

[0037] Material characterization:

[0038] The prepared materials were characterized by characterization method 1, such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), etc., to determine the composition and structure of the materials.

[0039] The morphology and size of the material were observed by characterization methods 2, such as scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

[0040] Establishment of detection mechanism:

[0041] The catalytic mechanism of the studied material is Co 2+ As a nucleophilic Lewis acid, it lowers the pKa of bound water molecules, thereby forming reactive hydroxide ions that catalyze ester hydrolysis. Sulfonamides, on the other hand, inhibit the hydrolysis of hCAII. In the presence of sulfonamides, Co66% / ZIF-8 weakens its ability to hydrolyze p-nitrophenyl acetate (pNPA) to p-nitrophenol (pNP), resulting in a change in its optical properties from yellow to colorless and a decrease in absorbance at 405 nm.

[0042] A standard curve was established to determine the linear relationship between SAAs concentration and product absorbance (pNP), and the quantitative relationship between sulfonamide concentration and optical signal was indirectly determined.

[0043] Performance testing:

[0044] Colorimetric detection performance test of sulfonamides: The prepared material was dispersed in solutions containing sulfonamides at different concentrations, the absorbance value was measured by spectrophotometer, and a concentration-absorbance standard curve was established to evaluate the detection sensitivity and linear range of the material.

[0045] Degradation performance test of sulfonamides: A certain amount of material is added to a solution containing sulfonamides, and the reaction is carried out under specific conditions (such as avoiding light, room temperature, etc.). Samples are taken regularly, and the concentration changes of sulfonamides are measured by ultraviolet spectrophotometer. The degradation rate is calculated to evaluate the degradation effect of the material.

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] The Co66% / ZIF-8 material of the present invention has the dual functions of colorimetric detection and degradation, and combines the dual functions of detection and treatment, and has the following significant advantages:

[0048] 1. Integrated solution: It can detect and degrade pollutants in the same material system, reducing operation steps and time, and improving work efficiency.

[0049] 2. Real-time monitoring capability: During the degradation process, the concentration changes of pollutants can be monitored in real time by color changes, which helps to optimize degradation conditions and evaluate degradation effects.

[0050] 3. High selectivity and sensitivity: By rationally designing the structure and composition of the material, highly selective detection and efficient degradation of specific pollutants can be achieved.

[0051] 4. Reusability: After completing a detection and degradation process, some dual-functional materials can be regenerated and reused through simple processing, reducing costs.

[0052] 5. By doping ZIF-8 with transition metals, this invention achieves a high-performance structure without altering its original framework. This is because the presence of multiple metals in the structure not only produces a cumulative effect but also promotes synergistic interactions, thus providing a new method for the detection and degradation of sulfonamides.

[0053] 6. Among various transition metal ions, cobalt ions prefer a tetrahedral coordination structure, similar to zinc ions under the same conditions. This property makes cobalt ions an excellent alternative to the primary metal cofactor in natural CA. Therefore, cobalt ions are a promising candidate for doping ZIF-8. Here, we focused on utilizing ZIF-8, which has a similar structure to the catalytic active center of CA. By incorporating cobalt ions as dopants into the ZIF-8 framework to replace the original zinc ions, we successfully designed a bimetallic active center, resulting in a bimetallic Co66% / ZIF-8 biomimetic CA nanozyme with excellent stability and catalytic activity. The development of this bimetallic Co66% / ZIF-8 biomimetic CA nanozyme holds great promise for the detection of sulfonamides and the degradation of pollutants. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] For ease of explanation, the present invention is described in detail with reference to the following specific embodiments and accompanying drawings.

[0055] Figure 1 TEM spectra of Co66% / ZIF-8(a) and ZIF-8(b), ZIF-67(c);

[0056] Figure 2 SEM images of Co66% / ZIF-8 (a) and ZIF-8 (b), ZIF-67 (c);

[0057] Figure 3 XRD patterns of Co66% / ZIF-8 (a) and ZIF-8 (b), ZIF-67 (c);

[0058] Figure 4 The absorbance graphs of Co66% / ZIF-8, ZIF-67, and ZIF-8 for SD detection under optimized conditions;

[0059] Figure 5 This is the adsorption degradation equilibrium curve of Co66% / ZIF-8, ZIF-67 and ZIF-8 under optimized conditions. DETAILED DESCRIPTION

[0060] The following are specific embodiments of the present invention, which, in conjunction with the accompanying drawings, further describe the technical solutions of the present invention, but the present invention is not limited to these embodiments; in the following description, specific details such as specific configurations are provided only to help fully understand the embodiments of the present invention. Therefore, it should be clear to those skilled in the art that various changes and modifications can be made to the embodiments described herein without departing from the scope and spirit of the present invention. It should be clear to those skilled in the art that various changes and modifications can be made to the embodiments described herein without departing from the scope and spirit of the present invention.

[0061] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments of the present invention can be combined with each other.

[0062] Unless otherwise specified, the materials, practices, and experimental equipment involved in the implementation cases of the present invention are in line with the commercially available standard products in the relevant chemical and biotechnology fields.

[0063] Example 1

[0064] A cobalt-based metal-organic framework material is prepared by setting appropriate process parameters, mixing Co(CH3COO)2·4H2O and Zn(CH3COO)2·2H2O in a ratio of 2:1, and then mixing with a 2-MIM solution to obtain Co66% / ZIF-8. The specific preparation method is as follows:

[0065] Step 1: Weigh a certain amount of Co(CH3COO)2·4H2O and dissolve it in deionized water. Stir the mixture evenly under magnetic stirring to obtain solution A.

[0066] Step 2: Dissolve a certain amount of Zn(CH3COO)2·2H2O in deionized water and stir evenly to obtain solution B;

[0067] Step 3: Dissolve a certain amount of 2-MIM in deionized water and stir evenly to obtain solution C;

[0068] Step 4: While stirring continuously, slowly add solution B to solution A. After the addition is complete, continue stirring and react for 5 minutes.

[0069] Step 5: While stirring continuously, slowly add solution C dropwise to the mixture obtained in step 4. After the addition is complete, continue stirring and react for 5 minutes.

[0070] Step 6: Slowly add the methanol solution dropwise to the mixture obtained in step 5 while stirring continuously. After the addition is complete, continue stirring and reacting for 2 hours.

[0071] Step 7: Transfer the mixed solution after the reaction into a centrifuge tube, centrifuge it at room temperature, collect the precipitate, and obtain a preliminary product;

[0072] Step 8: washing the precipitate with methanol to remove unreacted substances and impurities;

[0073] Step 9: Dry the washed precipitate in a vacuum drying oven overnight to obtain a material with dual functions of colorimetric detection and degradation of sulfonamides.

[0074] In the step 1, 1.317 g of Co(CH3COO)2·4H2O was dissolved in 15 mL of deionized water to obtain solution A; in the step 2, 0.6585 g of Zn(CH3COO)2·2H2O was dissolved in 15 mL of deionized water to obtain solution B.

[0075] The temperature set in steps 4 and 5 is room temperature, and the stirring speed is maintained at 5000 r / min.

[0076] The amount of methanol added in step 6 was 15 mL, and the stirring temperature was maintained the same as that in steps 4 and 5.

[0077] In step 7, the reaction solution was transferred to a 15 mL centrifuge tube and centrifuged at a speed of 8000 rpm for 5 min.

[0078] In step 8, methanol was used for washing 3 times.

[0079] The drying temperature in step 9 is 70°C.

[0080] Comparative Example 1:

[0081] Co(CH3COO)2·4H2O and Zn(CH3COO)2·2H2O were mixed in a ratio of 0:1 and then mixed with 2-MIM solution to obtain ZIF-8. The other preparation steps were the same as in Example 1.

[0082] Comparative Example 2:

[0083] Co(CH3COO)2·4H2O and Zn(CH3COO)2·2H2O were mixed in a ratio of 1:0 and then mixed with 2-MIM solution to obtain ZIF-67 (zinc-free). The other preparation steps were the same as in Example 1.

[0084] Co66% / ZIF-8, ZIF-8 and ZIF-67 were prepared under the same conditions, and the three nanomaterials were characterized by TEM. Figure 1 As shown in the figure, they all maintain their unique rhombic dodecahedron structure. Co66% / ZIF-8 presents a uniform nanoparticle morphology with a narrow particle size distribution. This may be due to the precise control during the synthesis process, which allows the cobalt element to be uniformly incorporated into ZIF-8 ( Figure 1 a). The irregular morphology of ZIF-67 particles may be due to the influence of its own structural characteristics ( Figure 1 b). Compared with ZIF-67, ZIF-8 may have particle agglomeration or uneven particle size, which may be due to the fluctuation of reaction conditions during the synthesis process, resulting in inconsistent crystal growth rate ( Figure 1 c).

[0085] The surface morphology and microstructure of the samples were characterized by SEM. Figure 2 As shown, the surface of Co66% ZIF-8 is smooth and flat, and the pores are evenly distributed and of moderate size ( Figure 2 a). Comparing the surfaces of ZIF-8 and ZIF-67, the surface of ZIF-8 has more defects or is rougher ( Figure 2 b); The pore distribution of ZIF-67 is not as uniform as that of Co66% / ZIF-8 ( Figure 2 c) These results suggest that the incorporation of cobalt may have altered the chemical properties of the material surface, promoting surface smoothness and uniform pore distribution, which facilitates the diffusion of reactants and products, thereby improving catalytic efficiency. Appropriate pore size and uniform distribution contribute to enhanced adsorption capacity.

[0086] Under the same conditions, the obtained samples were subjected to X-ray diffraction analysis, such as Figure 3As shown in the figure, compared with ZIF-67 and ZIF-8, Co66% / ZIF-8 has no impurity peaks or amorphous material peaks, and has good crystallinity, indicating that the introduction of cobalt has led to changes in the crystal structure or improved performance. In addition, the increase in the cobalt ion doping ratio leads to a decrease in the half-maximum width of the XRD, which is due to the change in diffraction caused by the increase in crystal size.

[0087] Co66% / ZIF-8, ZIF-8, and ZIF-67 samples were prepared under the same conditions, and the samples were dispersed in a sulfonamide solvent to prepare sample solutions for colorimetric detection. The appropriate colorimetric detection method was selected based on the specific experimental requirements and sample characteristics. The absorbance of different samples at specific wavelengths was measured using a UV spectrophotometer. The UV spectra of Co66% / ZIF-8, ZIF-67, and ZIF-8 are shown in Figure 1. Figure 4 As shown, the absorbance of Co66% / ZIF-8 is significantly higher than that of ZIF-8 and ZIF-67 within a specific wavelength range, indicating that Co66% / ZIF-8 has a stronger UV absorption capacity at this wavelength and better UV shielding properties. Furthermore, the absorbance variation trend with wavelength was observed to understand the absorption characteristics of the samples at different wavelengths. The results show that when detecting sulfonamides, the absorbance of Co66% / ZIF-8 is significantly higher than that of ZIF-8 and ZIF-67, suggesting that Co66% / ZIF-8 may have better performance under these detection conditions.

[0088] Co66% / ZIF-8, ZIF-8, and ZIF-67 were synthesized and prepared under identical conditions. A representative sulfonamide was selected as the target pollutant for adsorption degradation experiments. A series of sulfonamide solutions with varying concentrations were prepared, and equal amounts of Co66% / ZIF-8, ZIF-8, and ZIF-67 were added to the sulfonamide solutions. At regular intervals, a certain amount of the solution was withdrawn and the sulfonamide concentration was measured. The adsorption capacity and adsorption efficiency were calculated based on the change in sulfonamide concentration before and after adsorption.

[0089] The adsorption and degradation reactions were monitored using a UV spectrophotometer. Samples were taken out regularly to determine the concentration of sulfonamides and to observe the degradation effects. The differences in adsorption and degradation performance of Co66% / ZIF-8, ZIF-8, and ZIF-67 were compared. The differences in their performance could be demonstrated by plotting adsorption kinetic curves and degradation kinetic curves. Figure 5 As shown in the figure, the absorbance of Co66% / ZIF-8 was significantly lower than that of ZIF-8 and ZIF-67 when adsorbing and degrading sulfonamides, indicating that Co66% / ZIF-8 may have better performance in adsorption and degradation.

[0090] Those skilled in the art to which this application relates may make various modifications or additions to the described specific embodiments or replace them with similar methods, but they will not deviate from the inventive concept of this application or exceed the scope defined by the appended claims.

Claims

1. Application of a cobalt-based metal-organic framework material in the efficient detection and degradation of sulfonamides, characterized in that: The material is a composite material synthesized with Co(CH3COO)2·4H2O, Zn(CH3COO)2·2H2O and 2-MIM as main components.

2. The use according to claim 1, characterized in that The molar ratio of Co(CH3COO)2·4H2O to Zn(CH3COO)2·2H2O is 2:

1.

3. The use according to claim 1 or 2, characterized in that The preparation method of the cobalt-based metal organic framework material comprises the following steps: Step 1: Weigh a certain amount of Co(CH3COO)2·4H2O and dissolve it in deionized water. Stir the mixture under magnetic stirring until homogeneous to obtain solution A. Step 2: Dissolve a certain amount of Zn(CH3COO)2·2H2O in deionized water and stir until homogeneous to obtain solution B; Step 3: Dissolve a certain amount of 2-MIM in deionized water and stir until uniform to obtain solution C; Step 4: While stirring continuously, slowly add solution B to solution A. After the addition is complete, continue stirring and react for 5 minutes. Step 5: While stirring continuously, slowly add solution C dropwise to the mixture obtained in step 4. After the addition is complete, continue stirring and react for 5 minutes. Step 6: While stirring continuously, slowly add the methanol solution dropwise to the mixture obtained in step 5. After the addition is complete, continue stirring and reacting for 2 h. Step 7: Transfer the mixed solution after the reaction into a centrifuge tube, centrifuge it at room temperature, collect the precipitate, and obtain a preliminary product; Step 8: washing the precipitate with methanol to remove unreacted substances and impurities; Step 9: Dry the washed precipitate in a vacuum drying oven overnight to obtain a material with dual functions of colorimetric detection and degradation of sulfonamides.

4. The use according to claim 3, characterized in that The molar ratio of Co(CH3COO)2·4H2O added in step 1 to Zn(CH3COO)2·2H2O added in step 2 is 2:

1.

5. The use according to claim 4, characterized in that In the step 1, 1.317 g of Co(CH3COO)2·4 H2O was dissolved in 15 mL of deionized water to obtain solution A. In the step 2, 0.6585 g of Zn(CH3COO)2·2 H2O was dissolved in 15 mL of deionized water to obtain solution B.

6. The use according to claim 5, characterized in that The temperature set in steps 4 and 5 is room temperature, and the stirring speed is maintained at 5000 r / min.

7. The use according to claim 6, characterized in that In step 6, 15 mL of methanol was added, and the stirring temperature was maintained the same as in steps 4 and 5.

8. The use according to claim 7, characterized in that In step 7, the reaction solution was transferred to a 15 mL centrifuge tube and centrifuged at 8000 rpm for 5 min.

9. The use according to claim 8, characterized in that The step 8 is to wash with methanol three times; the drying temperature of the step 9 is 70°C.

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