Preparation of metalloporphyrin-based porous organic polymer and application of metalloporphyrin-based porous organic polymer in solid-phase extraction adsorption
Synthesis of metalporphyrin-based porous organic polymers by solvothermal method solves the problem of bisphenol analog enrichment in food, and achieves efficient and rapid bisphenol analog enrichment and detection, which significantly improves the accuracy and efficiency of the detection results.
Patent Information
- Application Number
- CN202510525672.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-25
- Publication Date
- 2025-08-08
AI Technical Summary
The prior art is difficult to efficiently enrich the trace amount of bisphenol analogs in food, and the adsorption properties of existing adsorbent materials are limited by the material structure, resulting in inaccurate detection results.
The metalporphyrin-based porous organic polymer was synthesized by solvothermal method. Through the interaction of π-π conjugated structure and hydrogen bonds, an adsorbent was prepared with large specific surface area, adaptable pore size, high adsorption capacity and good stability, which was used to enrich bisphenol analogs for solid-phase extraction columns.
It achieves efficient and rapid enrichment of bisphenol analogs, combined with high-performance liquid chromatography-UV detection technology, significantly improves the accuracy and efficiency of food detection, and makes the materials easy to recycle and regenerate.
Smart Images
Figure CN120441794A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of material chemistry, and in particular relates to the preparation and application of a porous organic polymer. Background Art
[0002] The disclosure of this background information is intended to enhance understanding of the general background of the invention and should not necessarily be regarded as an acknowledgment or any form of suggestion that this information constitutes the prior art already known to a person skilled in the art.
[0003] In recent years, endocrine disrupting chemicals (EDCs), an emerging class of pollutants, have garnered widespread attention due to their potential harm to the environment and human health. Among these endocrine disrupting chemicals, bisphenol analogues (BPs) are the most common. These substances are aromatic compounds composed of two hydroxyphenyl functional groups connected by a bridging carbon or other chemical groups. BPAs are primarily used in the synthesis of polymers such as polycarbonate, polysulfone, epoxy resin, and polyester resin. They are widely used in the manufacturing of food containers, medical devices, automotive parts, and other materials. Due to their widespread use, BPs have been detected in a variety of environmental media and foods, including water, air, beverages, and canned foods.
[0004] However, these bisphenol analogs are present only in trace amounts in the environment and food, and the complex sample matrix can interfere with the accuracy of detection results. Therefore, direct analysis using large-scale instrumentation is impractical. Therefore, sample pretreatment techniques are generally required before analysis using high-performance liquid chromatography (HPLC), high-performance liquid chromatography-mass spectrometry (HPLC-MS), and gas chromatography-mass spectrometry (GC-MS). Sample pretreatment methods such as dispersive liquid-liquid microextraction (DLLME), dispersive solid-phase extraction (d-SPE), solid-phase microextraction (SPME), magnetic solid-phase extraction (MSPE), and solid-phase extraction (SPE) can effectively enrich bisphenol analogs. Among these methods, SPE, as a commonly used sample pretreatment method, has attracted considerable attention. It boasts significant advantages such as high efficiency, rapidity, automation, and resource conservation. Specifically, it achieves high sample enrichment efficiency, shortens analysis time, reduces labor investment, and minimizes the use of organic solvents. As a core element of SPE technology, the adsorbent has a crucial impact on SPE performance. Therefore, the research and development of new adsorbent materials with large specific surface area, high adsorption capacity and strong stability has become a research hotspot in this field.
[0005] Existing studies have shown that π-π conjugated structures show great potential in the efficient adsorption and activation of aromatic pollutants. Its mechanism of action is mainly based on the π-π stacking and hydrogen bonding interactions between molecules. With this characteristic, conjugated porous polymers with π-π conjugated structures have become ideal materials for removing aromatic pollutants. Porphyrin-based materials are widely used in many fields such as catalysis, photodynamic therapy and adsorption due to their high stability, unique macrocyclic structure and extensive π conjugated system. However, their adsorption performance is still limited by the structural characteristics of the material itself. When developing new adsorbents, adsorption performance is always a core consideration. At present, there are no reports on the synthesis of metalloporphyrin-based porous organic polymers for the adsorption of bisphenol analogs. Summary of the Invention
[0006] In response to the problem of difficulty in enriching bisphenol analogues in food in the existing technology, the present invention provides a metal porphyrin-based porous organic polymer with large specific surface area, adaptable pore size, high adsorption capacity, fast adsorption rate, easy recycling and regeneration, and good thermal stability.
[0007] Another object of the present invention is to provide a method for preparing the above-mentioned metalloporphyrin-based porous organic polymer, which adopts solvent thermal synthesis and has a simple process.
[0008] Another object of the present invention is to provide a use of the metalloporphyrin-based porous organic polymer in enriching bisphenol analogs.
[0009] To achieve the above objectives, the present invention adopts the following technical solutions.
[0010] A method for preparing a metalloporphyrin-based porous organic polymer comprises the following steps: Tetrakis(4-aminophenyl)porphyrin metal complex and 2,5-divinylterephthalaldehyde are dispersed in a mixed solvent and repeatedly frozen and thawed to obtain a precursor mixture; The mixed solution of the precursors is subjected to a solvent thermal reaction to obtain a metal porphyrin-based porous organic polymer.
[0011] The molar ratio of the tetrakis(4-aminophenyl)porphyrin metal complex to 2,5-divinylterephthalaldehyde is 1:2-1:4, and the metal is preferably copper.
[0012] The mixed solvent is a mixture of o-dichlorobenzene, n-butanol and acetic acid solution in a volume ratio of 2:2:1-10:10:1, and the concentration of the acetic acid solution is 6 M.
[0013] The temperature of the solvothermal reaction is 120°C-150°C, and the time of the solvothermal reaction is 60 h-84 h.
[0014] The number of freeze-thaw cycles is preferably 3 times.
[0015] A metalloporphyrin-based porous organic polymer obtained by the above preparation method and a solid phase extraction column prepared therefrom. The metalloporphyrin-based porous organic polymer and the solid phase extraction column can be used to adsorb bisphenol analogs.
[0016] The specific surface area of the metalloporphyrin-based porous organic polymer is 200 m 2 / g-800 m 2 / g; pore size 2 nm-3 nm.
[0017] The bisphenol analog is selected from bisphenol A (BPA), bisphenol F (BPF) and bisphenol S (BPS).
[0018] A method for detecting bisphenol analogues in food comprises the following steps: (1) Preparation of solid phase extraction columns using metalloporphyrin-based porous organic polymers as fillers; (2) Sample pretreatment to obtain a sample solution, filter to remove particles larger than 0.22 µm, and obtain a test solution; (3) After the solid phase extraction column is activated, the test solution is loaded, then rinsed with water, and then eluted with methanol to obtain the eluate; (4) Detection of bisphenol analogues in the eluate.
[0019] The detection method in step (4) is high performance liquid chromatography; preferably, the chromatographic column is a C18 column; the mobile phase is methanol-water with a volume ratio of 7:3; the detection wavelengths of BPA, BPF and BPS are 224 nm, 276 nm and 258 nm, respectively.
[0020] The mechanism of the present invention is as follows: The metalloporphyrin-based porous polymer material prepared by the present invention, in addition to physical confinement, primarily exhibits chemical interactions with bisphenol analogs, including π-π interactions, hydrogen bonding, and hydrophobic interactions. Due to its unique π-π conjugated structure, the porphyrin-based material is able to efficiently adsorb bisphenol analogs through the synergistic operation of intermolecular π-π stacking forces and hydrogen bonding. Furthermore, the metal ion-doped porphyrin not only optimizes the material's pore structure, making the internal pore distribution more rational, but also significantly enhances the adsorption material's performance in various aspects, such as thermal and chemical stability, through chemical interactions such as coordination.
[0021] The present invention has the following advantages: The metalloporphyrin-based porous polymer material provided by the present invention exhibits the outstanding characteristics of large specific surface area, adaptive pore size, high adsorption capacity, good stability, fast adsorption rate and easy recycling and regeneration. These advantages have laid a solid foundation for its in-depth application in the field of food testing. Based on the outstanding performance of this material, it was further loaded into a solid phase extraction column and organically combined with high performance liquid chromatography-ultraviolet detection technology (HPLC-DAD) to successfully construct an SPE-HPLC-DAD analysis method. After system optimization, the method achieved efficient operation under the conditions of a single adsorption dose of only 20 mg, a sample consumption of 20 mL, and an elution solvent of only 2 mL of methanol. When actually applied to the analysis and detection of food samples, the method demonstrated remarkable excellent performance, effectively verifying its practicality and reliability in the field of food testing. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 is a scanning electron microscope image of the copper porphyrin-based porous organic polymer prepared in Example 1; Figure 2 is the infrared spectrum of the copper porphyrin-based porous organic polymer and its monomer prepared in Example 1; Figure 3 is a N2 adsorption-desorption isotherm diagram of the copper porphyrin-based porous organic polymer prepared in Example 1; Figure 4 is a pore size distribution diagram of the copper porphyrin-based porous organic polymer prepared in Example 1; Figure 5 is a thermogravimetric analysis graph of the copper porphyrin-based porous organic polymer prepared in Example 1; Figure 6 is a scanning electron microscope image of the porphyrin-based porous organic polymer prepared in Comparative Example 1; Figure 7 This is a thermogravimetric analysis diagram of the porphyrin-based porous organic polymer prepared in Comparative Example 1; Figure 8 is the recovery rate of the solid phase extraction column prepared by copper porphyrin-based porous organic polymer at different cycle numbers; Figure 9 is the recovery rate of the solid phase extraction column prepared by porphyrin-based porous organic polymer at different cycle times. DETAILED DESCRIPTION
[0023] The present invention will be further described below with reference to the embodiments and drawings, but the present invention is not limited to the following embodiments.
[0024] Example 1 Preparation of Copper Porphyrin-Based Porous Organic Polymer (CuTAPP-Dva) (1) preparing a mixed solvent consisting of o-dichlorobenzene, n-butanol, and 6M acetic acid in a volume ratio of 10:10:1; (2) Copper tetraphenylaminoporphyrin (0.12 mmol, 88.36 mg) and 2,5-divinylterephthalaldehyde (0.24 mmol, 44.69 mg) were added to 6 mL of mixed solvent and ultrasonicated for 15 min to disperse uniformly; then three freeze-pump-thaw cycles were performed; (3) After the solvent was completely thawed, the mixed system was placed at 120°C for a solvothermal reaction for 72 h. After the reaction was completed, the powder was washed three times with THF, then Soxhlet extracted with THF for 24 h, and the residue was dried in a vacuum dryer at 60°C for 12 h to obtain a copper porphyrin-based porous polymer material (CuTAPP-Dva).
[0025] The scanning electron microscopy image of CuTAPP-Dva is as follows Figure 1 As shown in the figure, the surface of the material is rough and presents irregular aggregated particles. Figure 2 ) It can be seen that the amino characteristic peak of CuTAPP is in the range of 3200-3400 cm⁻¹, and the C=O characteristic peak of Dva is located at 1680 cm⁻¹. When CuTAPP-Dva was synthesized, significant changes occurred: the intensity of the amino characteristic peak of the CuTAPP monomer was significantly weakened, and the intensity of the aldehyde characteristic peak of the Dva monomer also decreased synchronously. At the same time, the intensity of the stretching vibration peak of C=N at 1602 cm⁻¹ was significantly enhanced. The changes in these characteristic peaks strongly confirmed the successful synthesis of the copper porphyrin conjugated polymer CuTAPP-Dva, indicating that during the reaction, a chemical reaction occurred between CuTAPP and Dva to generate a target product with new structural characteristics. The N2 adsorption-desorption isotherm of CuTAPP-Dva is shown in the figure. Figure 3 As shown in the figure, its isotherm shows a typical type I feature, indicating that the material has a rich microporous structure. By calculation, its specific surface area is 578.77 m² / g. The pore size distribution diagram is shown in the figure. Figure 4 As shown in the figure, the average pore size is 2.21 nm. Figure 5 As shown in Figure 2, the material has good thermal stability below 385°C.
[0026] Comparative Example 1 Preparation of porous organic polymer (TAPP-Dva) (1) preparing a mixed solvent consisting of o-dichlorobenzene, n-butanol, and 6M acetic acid in a volume ratio of 10:10:1; (2) Tetraphenylaminoporphyrin (0.12 mmol, 88.36 mg) and 2,5-divinylterephthalaldehyde (0.24 mmol, 44.69 mg) were added to 6 mL of mixed solvent and ultrasonicated for 15 min to disperse uniformly; then three freeze-pump-thaw cycles were performed; (3) After the solvent is completely thawed, the mixed system is placed at 120°C for 72 hours of solvent thermal reaction. After the reaction is completed, the powder is washed three times with THF, then Soxhlet extraction is performed with THF for 24 hours, and the residue is dried in a vacuum dryer at 60°C for 12 hours to obtain a porphyrin-based porous polymer material (TAPP-Dva). The scanning electron microscopy of the material is shown in FIG. Figure 6 As shown, it appears as irregular clusters and flocculents. The specific surface area calculated by N2 adsorption-desorption is 686 m 2 / g, the average pore size is 2.60 nm. Figure 7 As shown, it has good thermal stability below 62 °C, which indicates that the thermal stability of this material is poor.
[0027] Compared with the material obtained in Example 1, it can be seen that the addition of metal ions to the porphyrin-based conjugated organic polymer can significantly improve the thermal stability of the material.
[0028] Example 2 Preparation of Copper Porphyrin-Based Porous Organic Polymer (CuTAPP-Dva) (1) preparing a mixed solvent consisting of o-dichlorobenzene, n-butanol, and 6M acetic acid in a volume ratio of 5:5:1; (2) Copper tetraphenylaminoporphyrin (0.12 mmol, 88.36 mg) and 2,5-divinylterephthalaldehyde (0.24 mmol, 44.69 mg) were added to 6 mL of mixed solvent and ultrasonicated for 15 min to disperse uniformly; then three freeze-pump-thaw cycles were performed; (3) After the solvent was completely thawed, the mixed system was placed at 120°C for a solvothermal reaction for 72 h. After the reaction was completed, the powder was washed three times with THF, then Soxhlet extracted with THF for 24 h, and the residue was dried in a vacuum dryer at 60°C for 12 h to obtain a copper porphyrin-based porous polymer material (CuTAPP-Dva). Its adsorption capacity for BPA was 62.87 mg / g.
[0029] A mixed solvent consisting of mesitylene, dioxane, and 6M acetic acid in a volume ratio of 5:5:1 was prepared, and a copper porphyrin-based porous polymer material (CuTAPP-Dva) was prepared according to the above method; its adsorption capacity for BPA was 42.73 mg / g.
[0030] A mixed solvent consisting of o-dichlorobenzene, n-butanol, and 6M acetic acid in a volume ratio of 2:2:1 was prepared, and a copper porphyrin-based porous polymer material (CuTAPP-Dva) was prepared according to the above method; its adsorption capacity for BPA was 105 mg / g.
[0031] It can be seen that the type and proportion of solvents have a great influence on the material's ability to adsorb BPA.
[0032] Example 3 Preparation of Copper Porphyrin-Based Porous Organic Polymer (CuTAPP-Dva) (1) preparing a mixed solvent consisting of o-dichlorobenzene, n-butanol, and 6M acetic acid in a volume ratio of 10:10:1; (2) Copper tetraphenylaminoporphyrin (0.12 mmol, 88.36 mg) and 2,5-divinylterephthalaldehyde (0.24 mmol, 44.69 mg) were added to 6 mL of mixed solvent and ultrasonicated for 15 min to disperse uniformly; then three freeze-pump-thaw cycles were performed; (3) After the solvent was completely thawed, the mixed system was placed at 150°C for a solvothermal reaction for 72 h. After the reaction was completed, the powder was washed three times with THF, then subjected to Soxhlet extraction with THF for 24 h. The residue was then dried in a vacuum dryer at 60°C for 12 h to obtain a copper porphyrin-based porous polymer material (CuTAPP-Dva). The adsorption capacity of CuTAPP-Dva for BPA was 343.96 mg / g.
[0033] After the solvent was completely thawed, the mixed system was placed at 120°C for a solvothermal reaction for 72 hours. A copper porphyrin-based porous polymer material (CuTAPP-Dva) was prepared according to the above method. Its adsorption capacity for BPA was 348.98 mg / g.
[0034] It can be seen that the solvothermal temperature has a limited effect on the material's ability to adsorb BPA.
[0035] Application Example 1 Adsorption of Bisphenol Analogs by Copper Porphyrin-Based Porous Organic Polymers The porous organic polymers prepared in Example 1 and Comparative Example 1 were used as adsorbents to conduct adsorption performance experiments on BPA, BPF, and BPS.
[0036] 1. Static adsorption 5 mg of adsorbent material was added to 20 mL of a single bisphenol analogue working standard solution with a concentration range of 20-200 mg / L. Subsequently, the system was ultrasonically treated for 10 min to ensure uniform dispersion of the material. The system was then placed in a thermostatic oscillator at 298.15 K and oscillated until adsorption equilibrium was reached. After adsorption, the supernatant was filtered through a 0.22 μm polytetrafluoroethylene (PTFE) microfiltration membrane, and the filtrate was analyzed by Agilent 1260 high-performance liquid chromatography (HPLC) to quantitatively determine the concentration of residual bisphenol analogues. HPLC conditions: The chromatographic column was an Agilent 5 TC-C18 (2) column (4.6×250 mm, 5 μm); the mobile phase was 70% methanol (A) and 30% ultrapure water (B); the flow rate was set at 1 mL / min; the column oven temperature was 30°C; the injection volume was 50 μL; the detection wavelengths for BPA, BPF, and BPS were 224 nm, 276 nm, and 258 nm, respectively.
[0037] Table 1 Maximum adsorption capacity of three bisphenol analogues by different porous organic polymers Analysis of the isothermal adsorption curves reveals that the adsorption behavior of both the metalloporphyrin and the non-metal-based porous organic polymer conforms to the Langmuir model, with the adsorption of bisphenol analogs occurring as a monolayer with uniform adsorption sites. Furthermore, metal ion doping has little effect on the adsorption of bisphenol analogs.
[0038] 2. Dynamic adsorption 5 mg of each copper-porphyrin-based porous organic polymer was added to a 20 mL solution containing 80 mg / L of bisphenol analogs (BPA, BPF, and BPS). The system was sonicated for 10 minutes and then placed in a thermostatic oscillator at 298.15 K for 24 hours. At specific time points, the solution was centrifuged, and the resulting supernatant was filtered through a 0.22 μm polytetrafluoroethylene (PTFE) membrane. The quantitative analysis of residual bisphenol analogs was performed using the same procedure as in the static adsorption experiment.
[0039] Analysis of the kinetic adsorption curves of BPA, BPF, and BPS by the copper-porphyrin-based porous organic polymer revealed a significant increase in the adsorption of bisphenol analogs within the first 20 minutes, reaching equilibrium after approximately 30 minutes. The adsorption behavior of the adsorbent material closely conforms to a pseudo-second-order kinetic model, indicating that chemical adsorption is a key interaction mechanism between the copper-porphyrin-based porous organic polymer and BPA, BPF, and BPS.
[0040] Example 4 Preparation of solid phase extraction column The adsorption material is loaded into an empty solid phase extraction column using a dry method. The specific operation is as follows: 20 mg of the porous organic polymer prepared in Example 1 or Comparative Example 1 was loaded into a 3 mL solid-phase extraction column with a sieve plate at the bottom. The column was gently shaken to ensure uniform filling of the metalloporphyrin-based porous organic polymer. A porous polyethylene sieve plate was then placed above the material to securely hold the adsorbent between the two sieve plates. This successfully completed the solid-phase extraction column.
[0041] The SPE cartridge was regenerated as follows: After one SPE run, 3 mL of methanol and 3 mL of water were added to the cartridge to remove any remaining bisphenol analogs. The cartridge was then placed in a 60°C drying oven for further drying. After the next extraction, 3 mL of methanol and 3 mL of water were added to reactivate the cartridge.
[0042] Depend on Figure 8 and Figure 9 The results show that after 20 cycles of regeneration, the copper porphyrin-based porous organic polymer SPE column showed no significant change in the recovery rate of the three bisphenol analogs. However, after 10 cycles of regeneration, the recovery rate of the porphyrin-based porous organic polymer SPE column decreased significantly. This shows that the addition of metal ions not only does not lead to a decrease in the recovery of bisphenol analogs, but also enhances the thermal stability of the adsorption material and improves the utilization rate of the material.
[0043] Example 5 Detection of bisphenol analogues in milk (1) Sample preparation: Take 15 mL of milk sample and add 0.15 mL of trifluoroacetic acid to it; to ensure thorough mixing, vortex the sample for 1.5 min and then centrifuge it at 8000 rpm for 10 min; transfer the supernatant to a conical flask, and vortex the remaining precipitate with 7.5 mL of methanol for 3 min to facilitate the extraction of bisphenol analogues, and then collect the supernatant after another round of centrifugation; finally, combine all the supernatants, dilute with water to a final volume of 150 mL, filter with a 0.22 µm polytetrafluoroethylene (PTFE) membrane, and store in a refrigerator at 4°C; (2) Solid phase extraction: The loaded CuTAPP-Dva (Example 1) solid phase extraction column was connected to the solid phase extraction instrument, and 3 mL of methanol and 3 mL of ultrapure water were used to activate and clean the solid phase extraction column in sequence; then, 20 mL of spiked solution or sample solution was taken and passed through the solid phase extraction column at 1.5 mL / min with the assistance of a vacuum pump to ensure that it can fully contact with the adsorption material so that the target substance is adsorbed on the solid phase extraction column; after the sample loading is completed, the adsorption material is washed with 1 mL of ultrapure water to completely remove the impurities remaining in the adsorption process; finally, 2 mL of methanol was used to elute the bisphenol analogues enriched on the adsorption material of the solid phase extraction column at a flow rate of 1 mL / min to obtain an eluate, thereby achieving separation and enrichment of the target substance; (3) Analysis and detection: The eluate obtained in step (2) was subjected to nitrogen purge to remove the solvent, and the residue was then redissolved in an aqueous solution containing 4% methanol for subsequent high performance liquid chromatography (HPLC) analysis and detection. The HPLC detection method was the same as that in Application Example 1.
[0044] Table 2 Recovery rates of spiked bisphenol analogues in milk The spiked recoveries of bisphenol analogs in milk are shown in Table 2. As can be seen from Table 2, the spiked recoveries of the three bisphenol analogs (BPA, BPF, and BPS) ranged from 83.86% to 99.93%. This result demonstrates that the adsorbent prepared in this invention performs well in recovering bisphenol analogs from milk, with high recovery efficiency.
[0045] Example 6 Detection of bisphenol analogs in tea beverages (1) Sample preparation: The tea beverage was centrifuged at 10,000 rpm for 10 min at 4°C to remove impurities and a small amount of precipitate. The supernatant was then collected and filtered through a 0.22 μm polytetrafluoroethylene (PTFE) membrane and stored in a refrigerator at 4°C. (2) Solid phase extraction: The loaded CuTAPP-Dva (Example 1) solid phase extraction column was connected to the solid phase extraction instrument, and 3 mL of methanol and 3 mL of ultrapure water were used to activate and clean the solid phase extraction column in sequence; then, 20 mL of spiked solution or sample solution was taken and passed through the solid phase extraction column at 1.5 mL / min with the assistance of a vacuum pump to ensure that it can fully contact with the adsorption material so that the target substance is adsorbed on the solid phase extraction column; after the sample loading is completed, the adsorption material is washed with 1 mL of ultrapure water to completely remove the impurities remaining in the adsorption process; finally, 2 mL of methanol was used to elute the bisphenol analogues enriched on the adsorption material of the solid phase extraction column at a flow rate of 1 mL / min to obtain an eluate, thereby achieving separation and enrichment of the target substance; (3) Analysis and detection: The eluate obtained in step (2) was subjected to nitrogen purge to remove the solvent, and the residue was then redissolved in an aqueous solution containing 4% methanol for subsequent high performance liquid chromatography (HPLC) analysis and detection. The HPLC detection method was the same as that in Application Example 1.
[0046] Table 3 Recovery rates of spiked bisphenol analogues in tea beverages The results of the spiked recoveries of bisphenol analogs in tea beverages are shown in Table 3. As can be seen from Table 3, the spiked recoveries of the three bisphenol analogs (BPA, BPF, and BPS) ranged from 89.96% to 104.22%. This result demonstrates that the adsorbent prepared in this invention performs well in recovering bisphenol analogs from tea beverages, with high recovery efficiency.
[0047] Example 7 Detection of Bisphenol Analogs in Fruit Juice Beverages (1) Sample preparation: The juice beverage was centrifuged at 10,000 rpm for 10 min at 4°C to remove impurities and a small amount of precipitate. The supernatant was then collected and filtered through a 0.22 μm polytetrafluoroethylene (PTFE) membrane and stored in a refrigerator at 4°C. (2) Solid phase extraction: The loaded CuTAPP-Dva (Example 1) solid phase extraction column was connected to the solid phase extraction instrument, and 3 mL of methanol and 3 mL of ultrapure water were used to activate and clean the solid phase extraction column in sequence; then, 20 mL of spiked solution or sample solution was taken and passed through the solid phase extraction column at 1.5 mL / min with the assistance of a vacuum pump to ensure that it can fully contact with the adsorption material so that the target substance is adsorbed on the solid phase extraction column; after the sample loading is completed, the adsorption material is washed with 1 mL of ultrapure water to completely remove the impurities remaining in the adsorption process; finally, 2 mL of methanol was used to elute the bisphenol analogues enriched on the adsorption material of the solid phase extraction column at a flow rate of 1 mL / min to obtain an eluate, thereby achieving separation and enrichment of the target substance; (3) Analysis and detection: The eluate obtained in step (2) was subjected to nitrogen purge to remove the solvent, and the residue was then redissolved in an aqueous solution containing 4% methanol for subsequent high performance liquid chromatography (HPLC) analysis and detection. The HPLC detection method was the same as that in Application Example 1.
[0048] Table 4 Recovery rates of spiked bisphenol analogues in fruit juice beverages The results of the spiked recoveries of bisphenol analogs in juice are shown in Table 4. As can be seen from Table 4, the spiked recoveries of the three bisphenol analogs (BPA, BPF, and BPS) ranged from 82.66% to 105.97%. This result demonstrates that the adsorbent prepared in this invention performs well in recovering bisphenol analogs from juice, with high recovery efficiency.
[0049] The above Examples 5-7 not only verify the adsorbent's ability to efficiently capture the target compounds, but also illustrate its applicability and reliability in complex matrices (such as milk, tea beverages, and fruit juices).
[0050] The foregoing is merely an embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various changes and variations. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application should all be included within the scope of the claims of the present application.
Claims
1. A method for preparing a metalloporphyrin-based porous organic polymer, characterized in that: The following steps are involved: Tetrakis(4-aminophenyl)porphyrin metal complex and 2,5-divinylterephthalaldehyde are dispersed in a mixed solvent and repeatedly frozen and thawed to obtain a precursor mixture; The mixed solution of the precursors is subjected to a solvent thermal reaction to obtain a metal porphyrin-based porous organic polymer.
2. The preparation method according to claim 1, characterized in that The molar ratio of the tetrakis(4-aminophenyl)porphyrin metal complex to 2,5-divinylterephthalaldehyde is 1:2-1:
4.
3. The preparation method according to claim 1, characterized in that The mixed solvent is a mixture of o-dichlorobenzene, n-butanol and acetic acid solution in a volume ratio of 2:2:1-10:10:1, and the concentration of the acetic acid solution is 6 M; The temperature of the solvothermal reaction is 120°C-150°C.
4. The preparation method according to claim 1, characterized in that The solvent thermal reaction time is 60 h-84 h; the number of freeze-thaw cycles is preferably 3 times; The tetrakis(4-aminophenyl)porphyrin metal complex is tetrakis(4-aminophenyl)porphyrin copper.
5. A metalloporphyrin-based porous organic polymer obtained by the preparation method according to any one of claims 1 to 4 and a solid phase extraction column prepared therefrom.
6. The method according to claim 5, characterized in that The specific surface area of the metalloporphyrin-based porous organic polymer is 200 m 2 / g-800 m 2 / g; pore size 2 nm-3 nm.
7. Use of the metalloporphyrin-based porous organic polymer and solid phase extraction column according to claim 5 or 6 in adsorbing bisphenol analogs.
8. The use according to claim 7, characterized in that The bisphenol analog is selected from bisphenol A, bisphenol F and bisphenol S.
9. A method for detecting bisphenol analogues in food, characterized in that: The following steps are involved: (1) Preparing a solid phase extraction column using the metalloporphyrin-based porous organic polymer according to claim 5 or 6 as a filler; (2) Sample pretreatment to obtain sample solution, filter to remove particles larger than 0.22 µm, and obtain the test solution; (3) After the solid phase extraction column is activated, the test solution is loaded, then rinsed with water, and then eluted with methanol to obtain the eluate; (4) Detection of bisphenol analogues in the eluate.
10. The method according to claim 9, characterized in that The detection method in step (4) is high performance liquid chromatography; preferably, the chromatographic column is a C18 column; the mobile phase is methanol-water with a volume ratio of 7:3; the detection wavelengths of BPA, BPF and BPS are 224 nm, 276 nm and 258 nm, respectively.