Preparation method and application of enhanced hydrolytic nanoenzyme for organophosphorus pesticide degradation

Abstract

The present invention discloses a preparation method of an enhanced hydrolytic nanozyme for the degradation of organophosphorus pesticides. The broad-spectrum nucleic acid aptamer BSAPT is modified on the surface of a metal zirconium organic framework MOF-808 in various ways to form a MOF-808 / BSAPT or MOF-808-BSAPT enhanced hydrolytic nanozyme for selective and efficient degradation of organophosphorus pesticides. The enhanced hydrolytic nanozyme prepared by the present invention can simulate phosphatase activity and broadly identify a variety of highly toxic organophosphorus pesticides. The organophosphorus pesticide broad-spectrum nucleic acid aptamer BSAPT actively recognizes and captures organophosphorus compounds, enriches the target molecule to the Lewis acidic Zr(IV) active site center of MOF-808, and achieves selective and efficient degradation of organophosphorus pesticides by nucleophilic attack on the electrophilic group of the phosphorus atom center of the organophosphorus compound substrate. It can effectively degrade a variety of highly toxic organophosphorus pesticides such as chlorpyrifos, profenofos, and methyl parathion. The invention has simple preparation materials, low cost, fast degradation rate and broad spectrum, and can be applied to the degradation of various organophosphorus pesticides in water bodies.

Description

Technical Field

[0001] The present invention relates to the field of pesticide degradation, and in particular to a preparation method and application of an enhanced hydrolytic nanoenzyme for degrading organophosphorus pesticides. Background Art

[0002] Organophosphorus pesticides, with their high efficacy, broad spectrum, and strong insecticide capacity, are currently among the most widely used pesticides in agricultural production. However, their increasing use poses a significant threat to both the ecological environment and human health. Organophosphorus pesticides can enter the environment through various pathways, including production, transportation, and application. They can remain and accumulate in various environmental media. Once transmitted through the food chain and into animals and humans, they can interfere with the normal functioning of the nervous system, leading to a range of health problems such as nerve damage, liver dysfunction, and a weakened immune system, and can even induce cancer and genetic diseases. Therefore, achieving the effective degradation of organophosphorus pesticides is crucial for protecting ecosystems and human health.

[0003] Currently, pesticide residue degradation is categorized into biodegradation and non-biodegradation. Biodegradation primarily utilizes bacteria, fungi, and the enzymes they produce as degradation agents. While this method offers advantages such as environmental friendliness and the ability to be used for in-situ remediation, it also suffers from drawbacks such as difficulty in enzyme preparation, high production costs, and harsh reaction conditions. Meanwhile, non-biodegradation primarily utilizes non-living entities present in the environment or uses adsorbents to extract and decompose organophosphorus pesticides. While these methods offer high adsorption degradation efficiency and rapid speed, they are relatively cumbersome and cannot achieve in-situ degradation of organophosphorus pesticides.

[0004] As existing degradation technologies still have many problems such as complex processes and high costs, there is an urgent need to build an efficient, stable, and low-cost system to achieve the degradation of organophosphorus pesticides in complex environments. Summary of the Invention

[0005] Purpose of the invention: In order to solve the problems existing in the prior art, the present invention proposes a preparation method and application of an enhanced hydrolytic nanoenzyme for organophosphorus pesticide degradation, which has low cost, fast degradation rate, broad spectrum, and can be applied to the degradation of various organophosphorus pesticides in water.

[0006] Technical solution: To achieve the above objectives, the present invention adopts the following technical solution: a method for preparing an enhanced hydrolytic nanozyme for the degradation of organophosphorus pesticides, specifically modifying the broad-spectrum nucleic acid aptamer BSAPT on the surface of the metal zirconium organic framework MOF-808 to form MOF-808 / BSAPT or MOF-808-BSAPT enhanced hydrolytic nanozyme.

[0007] Furthermore, the method of modifying the broad-spectrum nucleic acid aptamer BSAPT on the surface of MOF-808 is a combination of one or more of electrostatic adsorption and covalent bonding.

[0008] In some embodiments, the preparation method of the enhanced hydrolytic nanozyme MOF-808 / BSAPT by adsorbing the broad-spectrum nucleic acid aptamer BSAPT on the surface of the metal zirconium organic framework MOF-808 by electrostatic adsorption is as follows:

[0009] (1) adding zirconium oxychloride octahydrate ZrOCl2·8H2O and 1,3,5-benzenetricarboxylic acid H3BTC in a weight ratio of 3 to 5:1 to N,N-dimethylformamide DMF and formic acid FA to obtain a mixed solution; the volume ratio of the N,N-dimethylformamide DMF and formic acid FA mixed solution is 1:1; the concentration of the 1,3,5-benzenetricarboxylic acid H3BTC in the mixed solution is 0.1-0.2 M;

[0010] (2) After ultrasonic treatment, the mixed solution was transferred to a reactor and placed in an electric constant temperature drying oven at 70-90 o C reaction time: 48-96 h;

[0011] (3) After the reaction, the precipitate was washed with DMF and acetone several times and placed in a vacuum oven for 25-120 o C and dried at 60-120 o After activation at high temperature for 4-8 h, a white dry powder was obtained;

[0012] (4) The above white dry powder was dispersed in deionized water to obtain a suspension with a concentration of 0.5-5 g / L, and the broad-spectrum nucleic acid aptamer BSAPT for organophosphorus pesticides was added to the suspension at 4-37 o C mixed reaction for 0.5-2 h, and 0.1-0.6 mmol of the broad-spectrum nucleic acid aptamer BSAPT was modified on each 1 g of white dry powder. The suspension was then centrifuged, washed several times with saline at pH 7-8 and redispersed to obtain an enhanced hydrolytic nanozyme MOF-808 / BSAPT suspension.

[0013] In some embodiments, the preparation method of the enhanced hydrolytic nanozyme MOF-808-BSAPT by covalently adsorbing the broad-spectrum nucleic acid aptamer BSAPT on the surface of the metal zirconium organic framework MOF-808 is as follows:

[0014] (1) adding zirconium oxychloride octahydrate ZrOCl2·8H2O, 1,3,5-benzenetricarboxylic acid H3BTC and 5-aminoisophthalic acid H2BTC-NH2 in a weight ratio of 15-25:3-5:1 to N,N-dimethylformamide DMF and formic acid FA to obtain a mixed solution; the volume ratio of the N,N-dimethylformamide DMF and formic acid FA mixed solution is 1:1; the concentration of the 1,3,5-benzenetricarboxylic acid H3BTC in the mixed solution is 0.1-0.2 M;

[0015] (2) After ultrasonic treatment, the mixed solution was transferred to a reactor and placed in an electric constant temperature drying oven at 70-90 o C reaction time: 48-96 h;

[0016] (3) After the reaction, the precipitate was washed with DMF and acetone several times and placed in a vacuum oven for 25-120 o C and dried at 60-120 o After activation at high temperature for 4-8 h, a white dry powder was obtained;

[0017] (4) The white dry powder was dispersed in deionized water to obtain a suspension with a concentration of 0.1-1 g / L, and 2-3 wt% glutaraldehyde solution was added for reaction. After centrifugation to remove the supernatant, amino-modified organophosphorus pesticide broad-spectrum nucleic acid aptamer BSAPT-NH2 was added and the reaction was continued at 35-40 o C for 12-36 h, and 0.1-0.6 mmol of the broad-spectrum nucleic acid aptamer BSAPT for organophosphorus pesticides was modified on each 1 g of white dry powder. The suspension was then centrifuged, washed several times with saline at pH 7-8 and redispersed to obtain an enhanced hydrolytic nanozyme MOF-808-BSAPT suspension.

[0018] Furthermore, the pH of the brine in step (4) is 7-8, and contains 40-60 mM NaCl, 5-15 mM KCl, and 5-15 mM MgCl2.

[0019] The application of the enhanced hydrolytic nanozyme for organophosphorus pesticide degradation prepared by the above method is that the enhanced hydrolytic nanozyme simulates phosphatase activity and broadly recognizes a variety of highly toxic organophosphorus pesticides, and is used for the selective and efficient degradation of organophosphorus pesticides.

[0020] Furthermore, the enhanced hydrolytic nanozyme suspension was added to a Tris-HCl buffer with a pH of 9 and a concentration of 0.1 M containing chlorpyrifos. The concentration of the enhanced hydrolytic nanozyme suspension in the system was 0.5 g / L, and the Tris-HCl buffer specifically contained NaCl 40-60 mM; KCl 5-15 mM; MgCl25-15 mM; the reaction was carried out at 37°C for 48 hours, and then the chlorpyrifos content before and after degradation was determined by high-performance liquid chromatography-mass spectrometry to calculate the degradation rate of chlorpyrifos.

[0021] Furthermore, the enhanced hydrolytic nanozyme suspension was added to a Tris-HCl buffer with a pH of 7.4 and a concentration of 0.1 M containing bromophos. The concentration of the enhanced hydrolytic nanozyme suspension in the system was 0.5 g / L, and the Tris-HCl buffer contained NaCl 40-60 mM; KCl 5-15 mM; MgCl25-15 mM; the reaction was carried out at 37°C for 2 h, and then the bromophos content before and after degradation was determined by high-performance liquid chromatography-mass spectrometry to calculate the degradation rate of bromophos.

[0022] Furthermore, the enhanced hydrolytic nanozyme suspension was added to a NEM buffer solution with a pH of 9 and a concentration of 1.5 M containing methyl parathion. The concentration of the enhanced hydrolytic nanozyme suspension in the system was 0.5 g / L, and the NEM buffer solution specifically contained NaCl 40-60 mM; KCl 5-15 mM; MgCl25-15 mM; the reaction was carried out at 37°C for 2 h, and then the methyl parathion content before and after degradation was determined by high-performance liquid chromatography-mass spectrometry to calculate the degradation rate of methyl parathion.

[0023] Beneficial effects: Compared with the existing technology, the present invention has the following advantages: 1) Compared with traditional pesticide degradation methods, the enhanced hydrolytic nanozyme prepared by the present invention can simulate phosphatase activity and broadly identify a variety of highly toxic organophosphorus pesticides. It actively identifies and captures organophosphorus compounds through the organophosphorus pesticide broad-spectrum nucleic acid aptamer BSAPT, enriches the target molecules to the Lewis acidic Zr(IV) active site center of MOF-808, and achieves selective and efficient degradation of a variety of highly toxic organophosphorus pesticides including chlorpyrifos, profenofos, and methyl parathion through nucleophilic attack on the electrophilic group at the phosphorus atom center of the organophosphorus compound substrate. It avoids the use of natural biomass such as bacteria, fungi and the enzymes they produce, which greatly reduces the degradation cost and achieves low-cost, selective and efficient degradation of a variety of highly toxic organophosphorus pesticides. 2) The preparation method of the present invention is simple in materials and low in cost. The prepared enhanced hydrolytic nanozyme has a fast degradation rate and a broad spectrum, and can be applied to the degradation of a variety of organophosphorus pesticides in water bodies. 3) The catalytic activities of the enhanced hydrolytic nanozymes MOF-808 / BSAPT and MOF-808-BSAPT simulated phosphatase prepared by the present invention were significantly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 Schematic diagram of the degradation of organophosphorus pesticides by enhanced hydrolytic nanoenzymes modified with broad-spectrum nucleic acid aptamers;

[0025] Figure 2 This is a scanning electron micrograph of the enhanced hydrolytic nanozyme MOF-808 / BSAPT prepared in Example 1 based on the organophosphorus pesticide broad-spectrum nucleic acid aptamer BSAPT adsorbed on the surface of the metal zirconium organic framework MOF-808;

[0026] Figure 3 This is a scanning electron micrograph of the enhanced hydrolytic nanozyme MOF-808-BSAPT prepared in Example 2, in which the broad-spectrum nucleic acid aptamer BSAPT for organophosphorus pesticides is covalently linked to the surface of the metal zirconium organic framework MOF-808;

[0027] Figure 4 This is a comparison chart of the simulated phosphatase catalytic activity of the nanozyme in Example 3;

[0028] Figure 5 4 is a comparison of the high performance liquid chromatography-mass spectrometry (LC-MS) and degradation efficiency of chlorpyrifos degradation by the organophosphorus pesticide broad-spectrum aptamer-enhanced hydrolysis nanozyme in Example 4;

[0029] Figure 6 The figure shows the comparison of high performance liquid chromatography-mass spectrometry (LC-MS) and degradation efficiency of profenofos degradation by the organophosphorus pesticide broad-spectrum aptamer-enhanced hydrolysis nanozyme in Example 5;

[0030] Figure 7 This is a comparison of the high-performance liquid chromatography-mass spectrometry (LC-MS) and degradation efficiency of the degradation of methyl parathion by the organophosphorus pesticide broad-spectrum aptamer-enhanced hydrolysis nanozyme in Example 6; DETAILED DESCRIPTION

[0031] The present invention will be further described below with reference to specific embodiments.

[0032] Example 1: Preparation of enhanced hydrolytic nanozyme MOF-808 / BSAPT based on the adsorption of broad-spectrum organophosphorus pesticide aptamers (BSAPT) on the surface of metal zirconium organic framework (MOF-808)

[0033] 0.54 g zirconium oxychloride octahydrate (ZrOCl2·8H2O) and 0.12 g 1,3,5-benzenetricarboxylic acid (H3BTC) were added to 25 mL each of N,N-dimethylformamide (DMF) and formic acid (FA) to obtain a mixed solution. After ultrasonic treatment, the mixed solution was transferred to a 100 mL polytetrafluoroethylene reactor and placed in an electric constant temperature drying oven at 80°C for 72 h. After the reaction, the precipitate was washed three times with DMF and acetone, dried in a vacuum oven at 120°C, and activated for 5 h to obtain a white dry powder. 0.5 mg of the white dry powder was dispersed in 1 mL of deionized water, and 15 μL of a broad-spectrum organophosphorus pesticide aptamer (BSAPT) (100 μM) was added. The mixture was mixed and reacted at 4°C for 1 h. The suspension was centrifuged and washed with saline (pH 7.4, containing 50 mM NaCl, 10 mM KCl, and 10 mM MgCl2). mM) were washed three times and redispersed to obtain the enhanced hydrolytic nanozyme MOF-808 / BSAPT suspension.

[0034] Figure 2 This is a scanning electron micrograph of the enhanced hydrolytic nanoenzyme MOF-808 / BSAPT prepared based on the adsorption of organophosphorus pesticide broad-spectrum nucleic acid aptamer (BSAPT) on the surface of metal zirconium organic framework (MOF-808). Figure 2 It can be seen that the prepared enhanced hydrolytic nanozyme MOF-808 / BSAPT has a regular octahedral structure, proving its successful synthesis.

[0035] Example 2: Preparation of enhanced hydrolytic nanozyme MOF-808-BSAPT based on amino-modified organophosphorus pesticide broad-spectrum nucleic acid aptamer (BSAPT-NH2) covalently linked to the surface of metal zirconium organic framework (MOF-808)

[0036] 0.54 g zirconium oxychloride octahydrate (ZrOCl2·8H2O), 0.09 g 1,3,5-benzenetricarboxylic acid (H3BTC) and 0.026 g 5-aminoisophthalic acid (H2BTC-NH2) were taken, and 25 mL each of N,N-dimethylformamide (DMF) and formic acid (FA) were added to obtain a mixed solution. After ultrasonic treatment, the mixed solution was transferred to a 100 mL polytetrafluoroethylene reactor and placed in an electric constant temperature drying oven at 80°C for 72 h. After the reaction, the precipitate was washed three times with DMF and acetone respectively and dried in a vacuum oven at 120°C for 5 h to obtain a white dry powder. 0.5 mg of the white dry powder was dispersed in 500 μL deionized water, and glutaraldehyde solution (2.5 wt%) was added to react for 2 h. After centrifugation to remove the supernatant, 400 μL HEPES buffer (20 mM, pH 7.4) and 100 μL amino-modified broad-spectrum organophosphorus pesticide aptamer (BSAPT-NH2) (15 μM), the reaction continued at 37 °C for 24 h, the suspension was centrifuged, washed three times with saline (pH 7.4, containing NaCl 50 mM; KCl 10 mM; MgCl210 mM) and redispersed to obtain the enhanced hydrolytic nanozyme MOF-808-BSAPT suspension.

[0037] Figure 3 This is a scanning electron micrograph of the enhanced hydrolytic nanoenzyme MOF-808-BSAPT prepared based on the covalent attachment of the broad-spectrum nucleic acid aptamer for organophosphorus pesticides (BSAPT-NH2) to the surface of the metal zirconium organic framework (MOF-808-NH2). Figure 3 It can be seen that the prepared enhanced hydrolytic nanozyme MOF-808-BSAPT has a regular octahedral structure, proving its successful synthesis.

[0038] Example 3: Comparative test of simulated phosphatase catalytic activity of enhanced hydrolytic nanozymes:

[0039] Take 50 μL of the phosphatase assay chromogenic substrate p-nitrophenyl phosphate disodium pNPP (100 μM), 50 μL of the enhanced hydrolytic nanozymes MOF-808 / BSAPT and MOF-808-BSAPT solution (0.5 mg / mL), and 400 μL of NEM buffer (1.5 mM, pH 9, containing NaCl 50 mM; KCl 10 mM; MgCl2 10 mM), react at 37°C for 10 min, and after centrifugation, take 400 μL of the supernatant. The absorbance value at a wavelength of 400 nm was analyzed by UV spectrophotometer to quantitatively detect paraoxon.

[0040] Two control experiments were also conducted: in one control experiment, unmodified organophosphorus pesticide broad-spectrum nucleic acid aptamer materials MOF-808 and MOF-808-NH2 were used as nanozymes in the catalytic reaction system, and the absorbance value was detected after 10 minutes of reaction under the same conditions; in the other control experiment, no nanozyme material was used in the catalytic reaction system, and the absorbance value was detected after standing for 10 minutes under the same conditions as the above experimental system.

[0041] like Figure 4 As shown, the reaction system after adding the nanozyme with simulated phosphatase activity showed a clear ultraviolet absorption peak at 400 nm, indicating that the prepared nanozymes can efficiently hydrolyze the chromogenic substrate pNPP for phosphatase assay to generate p-nitrophenol (p-NP) product, and have simulated phosphatase activity. At the same time, the enhanced hydrolysis nanozyme modified with the broad-spectrum nucleic acid aptamer for organophosphorus pesticides showed an increased ultraviolet absorption peak at 400 nm, indicating that the simulated phosphatase catalytic activity of the material after modification with the broad-spectrum nucleic acid aptamer for organophosphorus pesticides was significantly enhanced.

[0042] Example 4: Verification test of the effect of degradation of chlorpyrifos:

[0043] 100 μL of the enhanced hydrolytic nanozyme MOF-808-BSAPT suspension was added to 900 μL of Tris-HCl buffer (0.1 M, pH 9, containing 50 mM NaCl, 10 mM KCl, and 10 mM MgCl2) containing 100 μM chlorpyrifos. The reaction was incubated at 25°C for 48 h, followed by centrifugation. 800 μL of the supernatant was collected and the chlorpyrifos content before and after degradation was determined by high-performance liquid chromatography-mass spectrometry (LC-MS). The degradation rate of chlorpyrifos was calculated.

[0044] Figure 5 The high-performance liquid chromatography-mass spectrometry (LC-MS) determination of the degradation of chlorpyrifos by the enhanced hydrolytic nanozyme based on the broad-spectrum nucleic acid aptamer of organophosphorus pesticides showed that the degradation efficiency of the enhanced hydrolytic nanozyme on chlorpyrifos was 96.75% and 99.98% respectively within 48 h.

[0045] Example 5: Degradation of Profenofos

[0046] 100 μL of the enhanced hydrolytic nanozyme MOF-808-BSAPT suspension was added to 900 μL of Tris-HCl buffer (0.1 M, pH 7.4, containing 50 mM NaCl, 10 mM KCl, and 10 mM MgCl₂) containing 100 μM profenofos. The reaction was incubated at 37°C for 2 h, followed by centrifugation. 800 μL of the supernatant was collected and the profenofos content before and after degradation was determined by high-performance liquid chromatography-mass spectrometry (LC-MS). The profenofos degradation rate was then calculated.

[0047] Figure 6 The degradation efficiency of profenofos by the enhanced hydrolytic nanozyme based on the broad-spectrum nucleic acid aptamer of organophosphorus pesticides was 98.63% and 99.29% respectively within 2 h.

[0048] Example 6: Degradation of methyl parathion

[0049] 100 μL of the enhanced hydrolytic nanoenzyme MOF-808-BSAPT suspension was added to 900 μL of NEM buffer containing 100 μM methyl parathion. The NEM buffer was 1.5 mM, pH 9, and contained 50 mM NaCl, 10 mM KCl, and 10 mM MgCl2. The reaction was carried out at 37°C for 2 h, followed by centrifugation and 800 μL of the supernatant was taken. The methyl parathion content before and after degradation was determined by high-performance liquid chromatography-mass spectrometry (LC-MS) to calculate the degradation rate of methyl parathion.

[0050] Figure 7 The degradation efficiency of methyl parathion by the enhanced hydrolytic nanozyme based on the broad-spectrum nucleic acid aptamer of organophosphorus pesticides was 60.72% and 95.19% respectively within 2 h.

Claims

1. An application of an enhanced hydrolytic nanozyme for the degradation of organophosphorus pesticides, characterized by: The enhanced hydrolytic nanozyme simulates phosphatase activity and broadly recognizes highly toxic organophosphorus pesticides such as chlorpyrifos and methyl parathion, and is applied to the selective and efficient degradation of organophosphorus pesticides. The broad-spectrum nucleic acid aptamer BSAPT for organophosphorus pesticides actively recognizes and captures organophosphorus compounds, enriches the target molecules at the Lewis acidic Zr(IV) active site center of MOF-808, and achieves selective and efficient degradation of highly toxic organophosphorus pesticides including chlorpyrifos and methyl parathion by nucleophilic attack on the electrophilic group at the phosphorus atom center of the organophosphorus compound substrate. The preparation method of the enhanced hydrolytic nanozyme for organophosphorus pesticide degradation is as follows: a broad-spectrum nucleic acid aptamer BSAPT is modified on the surface of a metal zirconium organic framework MOF-808 to form a MOF-808 / BSAPT or MOF-808-BSAPT enhanced hydrolytic nanozyme; the broad-spectrum nucleic acid aptamer BSAPT is modified on the surface of MOF-808 by electrostatic adsorption, covalent bonding or a combination of one or more of the two methods; The preparation method of the enhanced hydrolytic nanozyme MOF-808 / BSAPT, in which the broad-spectrum nucleic acid aptamer BSAPT is adsorbed on the surface of the metal zirconium organic framework MOF-808 by electrostatic adsorption, is as follows: (1) adding zirconium oxychloride octahydrate ZrOCl2·8H2O and 1,3,5-benzenetricarboxylic acid H3BTC in a weight ratio of 3-5:1 to N,N-dimethylformamide DMF and formic acid FA to obtain a mixed solution; the volume ratio of the N,N-dimethylformamide DMF and formic acid FA mixed solution is 1:1; the concentration of the 1,3,5-benzenetricarboxylic acid H3BTC in the mixed solution is 0.1-0.2 M; (2) After ultrasonic treatment, the mixed solution was transferred to a reactor and placed in an electric constant temperature drying oven at 70-90°C for 48-96 hours; (3) After the reaction is completed, the precipitate is washed several times with DMF and acetone and placed in a vacuum oven for drying at 25-120°C. After activation at 60-120°C for 4-8 h, a white dry powder is obtained. (4) The above white dry powder was dispersed in deionized water to obtain a suspension with a concentration of 0.5-5 g / L, and the broad-spectrum nucleic acid aptamer BSAPT for organophosphorus pesticides was added to the suspension at 4-37 o The mixture was reacted for 0.5-2 h, and 0.1-0.6 mmol of broad-spectrum nucleic acid aptamers for organophosphorus pesticides was modified on each 1 g of white dry powder. The suspension was then centrifuged, washed several times with saline at a pH of 7-8, and redispersed to obtain an enhanced hydrolytic nanozyme MOF-808 / BSAPT suspension; the saline had a pH of 7-8 and contained 40-60 mM NaCl, 5-15 mM KCl, and 5-15 mM MgCl2. The preparation method of the enhanced hydrolytic nanozyme MOF-808-BSAPT in which the broad-spectrum nucleic acid aptamer BSAPT is covalently linked to the surface of the metal zirconium organic framework MOF-808 is as follows: (1) adding zirconium oxychloride octahydrate ZrOCl2·8H2O, 1,3,5-benzenetricarboxylic acid H3BTC and 5-aminoisophthalic acid H2BDC-NH2 in a weight ratio of 15-25:3-5:1 to N,N-dimethylformamide DMF and formic acid FA to obtain a mixed solution; the volume ratio of the N,N-dimethylformamide DMF and formic acid FA mixed solution is 1:1; the concentration of the 1,3,5-benzenetricarboxylic acid H3BTC in the mixed solution is 0.1-0.2 M; (2) After ultrasonic treatment, the mixed solution was transferred to a reactor and placed in an electric constant temperature drying oven at 70-90 o C reaction time: 48-96 h; (3) After the reaction, the precipitate was washed with DMF and acetone several times and placed in a vacuum oven for 25-120 o C and dried at 60-120 o After activation at high temperature for 4-8 h, a white dry powder was obtained; (4) The white dry powder was dispersed in deionized water to obtain a suspension with a concentration of 0.1-1 g / L, and 2-3 wt% glutaraldehyde solution was added for reaction. After centrifugation to remove the supernatant, amino-modified organophosphorus pesticide broad-spectrum nucleic acid aptamer BSAPT-NH2 was added and the reaction was continued at 35-40 o C for 12-36 h, and 0.1-0.6 mmol of broad-spectrum nucleic acid aptamers for organophosphorus pesticides were modified on each 1 g of white dry powder. The suspension was then centrifuged, washed several times with saline at a pH of 7-8, and redispersed to obtain an enhanced hydrolytic nanoenzyme MOF-808-BSAPT suspension; the saline had a pH of 7-8 and contained 40-60 mM NaCl, 5-15 mM KCl, and 5-15 mM MgCl2.

2. The use of an enhanced hydrolytic nanozyme for organophosphorus pesticide degradation according to claim 1, characterized in that: An enhanced hydrolytic nanozyme suspension was added to a Tris-HCl buffer with a pH of 9 and a concentration of 0.1 M containing chlorpyrifos. The concentration of the enhanced hydrolytic nanozyme suspension in the system was 0.5 g / L. The Tris-HCl buffer specifically contained NaCl 40-60 mM; KCl 5-15 mM; MgCl2 5-15 mM. The reaction was carried out at 37°C for 48 hours, and then the chlorpyrifos content before and after degradation was determined by high-performance liquid chromatography-mass spectrometry to calculate the degradation rate of chlorpyrifos.

3. The use of an enhanced hydrolytic nanozyme for organophosphorus pesticide degradation according to claim 1, characterized in that: An enhanced hydrolytic nanozyme suspension was added to a NEM buffer with a pH of 9 and a concentration of 1.5 M containing methyl parathion. The concentration of the enhanced hydrolytic nanozyme suspension in the system was 0.5 g / L. The NEM buffer specifically contained NaCl 40-60 mM; KCl 5-15 mM; MgCl2 5-15 mM. The reaction was carried out at 37°C for 2 h, and then the methyl parathion content before and after degradation was determined by high-performance liquid chromatography-mass spectrometry to calculate the degradation rate of methyl parathion.

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