Prochloraz ligand metal organic framework material as well as preparation method and application thereof

Abstract

The invention discloses a prochloraz ligand metal organic framework material as well as a preparation method and application thereof. The prochloraz ligand metal organic framework material is any one of the following Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3: Zn-PRO-1: the chemical formula of Zn-PRO-1 is [Zn (TPA) (PRO) 2] n, TPA represents terephthalic acid, PRO represents amidino-prochloraz, n represents 1, 2, 3, 4, 5, 6, 7, 8-tetramethyl-1, 3, 4, 5-tetramethyl-1, 3, 4, 5-tetramethyl-1, 3, 4, 5-tetramethyl-1, 3, 4, 5-tetramethyl-1, the chemical formula of Zn-PROO-2 is [Zn (1, 2, 4-BTC) (PRO) 2] n, 1, 2, 4-BTC represents 1, 2, 4-benzene tricarboxylic acid, and PRO represents 2, 3, 4-benzenetricarboxylic acid, and the chemical formula of Zn-PROO-2 is [Zn (1, 2, 4-BTC) (PRO) 2] n, the chemical formula of Zn-PROO-3 is [Zn (NTD) (PRO)] n, NTD represents 1, 4-naphthalenedicarboxylic acid, and PRO represents amidino-prochloraz. Compared with other sustained-release agents, the three materials provided by the invention have higher drug loading rates, all the materials can slowly release prochloraz pesticides, and Zn-PRO-3 has the characteristic of pH response release, has a remarkable antibacterial effect on two plant pathogenic fungi, namely, Colletotrichum gloeosporioides, of strawberry anthracnose pathogenic bacteria and Alternaria alternata of apple black spot pathogenic bacteria, and can be used for preparing the prochloraz sustained-release preparation for preventing and treating the prochloraz pesticides in the prochloraz sustained-release preparation of the prochloraz sustained-release preparation of the prochloraz sustained-release preparation of the prochloraz sustained-release preparation of the prochloraz sustained-release preparation of the prochloraz sustained-release preparation of the prochloraz sustained-release preparation of the prochloraz. A new thought can be provided for the MOF material slow-release bactericide.

Description

Technical Field

[0001] The invention belongs to the technical field of pesticides, and in particular relates to a prochloraz ligand metal organic framework material and a preparation method and application thereof. Background Art

[0002] In agricultural development, plant diseases are an important factor causing the decline of crop yield and safety. With the steady increase in the use of synthetic pesticides, the amount of active ingredients used has reached 3.5 billion kg / year, but the actual amount absorbed by biological targets is less than 0.1%. Most pesticides are directly lost to the environment through leaching, evaporation and drifting during spraying, or are degraded by light, temperature and microorganisms, which greatly reduces the efficiency of pesticide use (Yaghi OM, Li H. Hydrothermal synthesis of a metal-organic framework containing large rectangular channels. Journal of the American Chemical Society, 1995, 117, 10401−10402.). Therefore, in agricultural chemistry and environmental chemistry, it is very necessary to release pesticides slowly and transport them to the exact target location for release without losing their effectiveness.

[0003] The EU has also proposed the concept of encouraging precision agriculture, which is to develop tailored delivery systems to facilitate personalized pesticide application and ultimately minimize off-site pollution caused by spray drift, drainage and runoff. Therefore, the sustainable use of pesticides is of great significance to reducing the risks associated with human health and environmental pollution. At present, the research on slow-release pesticides is growing exponentially, such as microcapsule (MC) preparations, particles, hydrogels, new coatings, metal organic framework materials (MOFs), nano-enabled systems containing active ingredients (AI) and controlling their release.

[0004] Metal-organic framework materials (MOFs) are a type of coordination polymer that has developed rapidly in the past two decades. They are periodic materials with one-dimensional to three-dimensional structures. They generally use metal ions as connection points and organic ligands as support to form a 3D extension of space. They are another important new type of porous material besides zeolites and carbon nanotubes. CPs have become a dazzling "star" among porous materials due to their superior performance and potential applications in gas storage and separation, energy conversion and storage, water collection and cracking, heterogeneous catalysis, chemical sensors, environmental remediation, cancer treatment, and drug delivery. MOFs also show good activity in antibacterial properties, but there are few reports on MOFs in the prevention and control of plant diseases and pesticide delivery systems.

[0005] Prochloraz belongs to the imidazole fungicide class, which is a powerful fungicide that can inhibit sterol demethylation. It can be mainly used to control Ascomycetes, Basidiomycetes and Deuteromycetes, such as strawberry anthracnose, apple black spot and powdery mildew. It can destroy and prevent the biosynthesis of ergosterol, resulting in the inability to form cell membranes and the death of pathogens. However, due to its own shortcomings such as instability under ultraviolet (UV) and non-systemic characteristics, its effectiveness, utilization rate and duration are significantly reduced (Crist E, Mora C, Engeoman R. The Interaction of human population,food production, and biodiversity protection. Science, 2017, 356 (6335), 260−264.).

[0006] Therefore, the current technical difficulties mainly lie in how to process myclobutanil, and use the properties of MOF materials in water and their response characteristics to different pH values ​​to slowly release myclobutanil and transport it to the exact target location, thereby improving the utilization rate of pesticides and reducing the ineffective use of pesticides. Summary of the invention The purpose of the present invention is to provide a prochloraz ligand metal organic framework material and a preparation method and application thereof. The three materials can slowly release the prochloraz pesticide while ensuring the antibacterial effect, which can provide a new idea for the slow release of MOF materials fungicides.

[0007] To achieve the above object, the present invention adopts the following technical solution: In a first aspect, the present invention provides a prochloraz ligand metal organic framework material, which is any one of the following Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3: Zn-PRO-1: chemical formula is [Zn(TPA)(PRO)2] n , where TPA represents terephthalic acid, PRO represents amidine, and n represents the average number of repeating units contained in the polymer macromolecular chain; Zn-PRO-2: chemical formula is [Zn(1,2,4-BTC)(PRO)2] n , where 1,2,4-BTC represents 1,2,4-benzenetricarboxylic acid, PRO represents amidine, and n represents the average number of repeating units contained in the polymer macromolecular chain; Zn-PRO-3: chemical formula is [Zn(NTD)(PRO)] n , wherein NTD represents 1,4-naphthalene dicarboxylic acid, PRO represents amidine, and n represents the average number of repeating units contained in the polymer macromolecular chain.

[0008] Specifically, the chemical formula of Zn-PRO-1 is C 38 H 36 Cl6N6O8Zn; The chemical formula of Zn-PRO-2 is C 39 H 36 Cl6N6O 10 Zn; The chemical formula of Zn-PRO-3 is C 27 H 22 Cl3N3O6Zn.

[0009] In the above-mentioned prochloraz ligand metal organic framework material, the Zn-PRO-1 belongs to the monoclinic system, the P21 / c space group, and the unit cell parameters are as follows:

[0010] The Zn-PRO-2 belongs to the monoclinic system, P21 / c space group, and the unit cell parameters are as follows:

[0011] The Zn-PRO-3 belongs to the monoclinic system, C2 / c space group, and the unit cell parameters are as follows: .

[0012] In a second aspect, the present invention provides a method for preparing the prochloraz ligand metal organic framework material described in any one of the above items, which is any one of the following 1)-3): 1) The prochloraz ligand metal organic framework material is Zn-PRO-1, comprising the following steps: Dispersing zinc salt, amidine and terephthalic acid in a solvent, and heating in a closed system for reaction to obtain the Zn-PRO-1; 2) The prochloraz ligand metal organic framework material is Zn-PRO-2, comprising the following steps: Dispersing zinc salt, amidine and 1,2,4-benzenetricarboxylic acid in a solvent, and heating in a closed system for reaction to obtain the Zn-PRO-2; 3) The prochloraz ligand metal organic framework material is Zn-PRO-3, comprising the following steps: The zinc salt, amidine and 1,4-naphthalene dicarboxylic acid are dispersed in a solvent and heated in a closed system for reaction to obtain the Zn-PRO-3.

[0013] In the above-mentioned method for preparing the prochloraz ligand metal organic framework material, the molar ratio of the zinc salt, the prochloraz amine and the terephthalic acid is (1-2):1:(1-2), such as 1:1:1; The molar ratio of the zinc salt, the amidine and the 1,2,4-benzenetricarboxylic acid is (1-2):1:(1-2), such as 1:1:1; The molar ratio of the zinc salt, the amidine and the 1,4-naphthalene dicarboxylic acid is (1-2):1:(1-2), such as 1:1:1.

[0014] In the above-mentioned method for preparing the prochloraz ligand metal organic framework material, in methods 1)-3), the zinc salt is zinc chloride (ZnCl2), zinc sulfate (ZnSO4·7H2O) or zinc nitrate [Zn(NO3)2·6H2O]; The solvent consists of an organic solvent and water in a volume ratio of 1:1, and the organic solvent is N,N-dimethylformamide (DMA) or N,N-dimethylacetamide (DMF); The ratio of the zinc salt to the solvent is 0.5 mmol:8-80 mL, such as 0.5 mmol:80 mL.

[0015] In the above-mentioned method for preparing the prochloraz ligand metal organic framework material, the heating temperature is 80-120° C. and the heating time is 24-48 hours, such as heating at 80° C. for 48 hours.

[0016] In a third aspect, the present invention provides the use of the prochloraz ligand metal organic framework material described in any one of the above or the prochloraz ligand metal organic framework material obtained by the preparation method described in any one of the above in any of the following: A1) Inhibition of plant pathogenic fungi; A2) Inhibit the hyphae growth of plant pathogenic fungi; A3) Prevent and control plant diseases.

[0017] In the above application, the plant pathogenic fungi include Colletotrichum gloeosporioides ( Colletotrichum gloeosporioides ) or Alternaria interseptata ( Alternaria alternata ); The interspaced alternating spores can specifically be Alternaria alternata (Fr.) Keissl. YLPGl7092603-1; The Colletotrichum gloeosporioides ( Colletotrichum gloeosporioides ) may specifically be NRRL 45420; The plant diseases include strawberry anthracnose or apple black spot.

[0018] In a fourth aspect, the present invention provides a method for inhibiting plant pathogenic fungi, comprising the following steps: The prochloraz ligand metal organic framework material described in any one of the above items or the prochloraz ligand metal organic framework material obtained by any one of the above preparation methods is dispersed in water to prepare a suspension, and the suspension is used to treat a place that has been infected or is susceptible to infection by plant pathogenic fungi.

[0019] In the above method for inhibiting plant pathogenic fungi, the plant pathogenic fungi include Colletotrichum gloeosporioides ( Colletotrichum gloeosporioides ) or Alternaria interseptata ( Alternaria alternata ); The prochloraz ligand metal organic framework material is Zn-PRO-3, and the pH value of the suspension is controlled to be alkaline to accelerate the release of prochloraz, and the pH value of the suspension is controlled to be acidic to slow down the release of prochloraz.

[0020] Wherein, the alkalinity is preferably 7<pH≤9, more preferably pH 9; The acidity is preferably 5≤pH<7, more preferably pH 5.

[0021] The present invention has the following beneficial effects: (1) The present invention synthesized three new MOF materials (Zn-PRO-1, Zn-PRO-2, and Zn-PRO-3) with the nutrient element Zn as the metal and the pesticide prochloraz as the ligand. Zn-PRO-1, Zn-PRO-2, and Zn-PRO-3 have higher drug loading rates than other sustained-release agents, 76.6%, 73.4%, and 57.4%, respectively.

[0022] (2) Zn-PRO-1, Zn-PRO-2, and Zn-PRO-3 can all slowly release the pesticide prochloraz, and Zn-PRO-3 has the characteristic of pH-responsive release.

[0023] (3) Effects of Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3 on the pathogenic bacteria of strawberry anthracnose ( Colletotrichum gloeosporioides ) and apple black spot pathogen ( Alternaria alternata ) has a significant antibacterial effect and the carboxylic acid ligand has no effect on the antibacterial effect.

[0024] (4) Zn-PRO-1, Zn-PRO-2, and Zn-PRO-3 use Zn as a metal, which promotes plant growth and has a good inhibitory effect on bacteria, such as Escherichia coli ( Escherichia coli ), Staphylococcus aureus ( Staphylococcus aureus ) and other bacteria.

[0025] The present invention uses prochloraz, which has good bactericidal activity, as a ligand and Zn, which has good antibacterial activity and promotes plant growth, as a metal to synthesize three new MOF materials (Zn-PRO-1, Zn-PRO-2, and Zn-PRO-3) and characterize them in detail. Antibacterial experiments show that the three materials have good effects on the strawberry anthracnose pathogen ( Colletotrichum gloeosporioides ) and apple black spot pathogen ( Alternaria alternata ) have significant antibacterial effects, and their release conditions have been deeply explored. The metal organic coordination polymers synthesized by combining metal ions with bactericidal properties with pesticides have more comprehensive antibacterial properties than materials that release metal ions or antibacterial agent ligands, have a higher loading rate than loaded slow-release pesticides, and are easier to operate in terms of controlled release, more economical in price, and easier to operate, which can provide new ideas for the slow-release of fungicides from MOF materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] FIG1 is a schematic diagram of the synthesis of three MOF materials Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3 in Example 1 of the present invention (A), and an enlarged view of Zn-PRO-1 (B), Zn-PRO-2 (C) and Zn-PRO-3 (D).

[0027] Figure 2 This is the infrared spectrum (FT-IR) of the three MOF materials Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3 in Example 1 of the present invention.

[0028] Figure 3 Powder X-ray diffraction (PXRD) patterns of three MOF materials Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3 in Example 1 of the present invention.

[0029] Figure 4 This is a thermogravimetric analysis (TGA) curve diagram of three MOF materials Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3 in Example 1 of the present invention.

[0030] Figure 5 The release rate curves of the three MOF materials Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3 in ultrapure water in Example 2 of the present invention.

[0031] Figure 6 The release rate curve of the MOF material Zn-PRO-3 at different pH values ​​(pH=5, 7, 9) in Example 2 of the present invention.

[0032] Figure 7 The effects of PRO, Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3 on Colletotrichum gloeosporioides (Colletotrichum gloeosporioides ) (left) and Alternaria interseptata ( Alternaria alternata ) (right) The antibacterial effect of the concentrations from small to large: CK, 0.25, 0.5, 1, 2, 4, 8 mg / L.

[0033] Figure 8 The release concentration of PRO-1 prochloraz in Example 3 of the present invention is Colletotrichum gloeosporioides )'s antibacterial effect diagram. DETAILED DESCRIPTION

[0034] The present invention is further described in detail below in conjunction with specific embodiments, and the examples provided are only for illustrating the present invention, rather than for limiting the scope of the present invention. The examples provided below can be used as a guide for those of ordinary skill in the art to make improvements, and do not constitute a limitation of the present invention in any way.

[0035] The methods used in the following examples, unless otherwise specified, are all conventional methods, carried out according to the techniques or conditions described in the literature in the art or according to the product instructions. The materials, reagents, etc. used in the following examples, unless otherwise specified, can all be obtained from commercial sources.

[0036] Test strains Alternaria alternata Alternaria alternata (Fr.) Keissl. )YLPG17092603-1 is recorded in the literature "Wu Haiyan, Li Changshui, Ma Qingzhou, Yin Xinming, Geng Yuehua, Zhang Meng. Alternaria ( Alternaria alternata ) on jujube, pear and apple fruits. Tianjin Agricultural Science, 2023, 29(5): 47-50". The public can obtain it from Henan Agricultural University. The biological material is only used to repeat the relevant experiments of the present invention and cannot be used for other purposes.

[0037] Colletotrichum gloeosporioides Colletotrichum gloeosporioides ) NRRL 45420 is recorded in the literature "Zhou J, Wei HL, Li SM. Colletotriauxins AD, new plant growth inhibitors from thephytopathogenic fungus Colletotrichum gloeosporioides. Journal of AgriculturalandFoodChemistry. 2023, 71(29), 11104-11109." The public can obtain it from the applicant. The biological material is only used to repeat the relevant experiments of the present invention and cannot be used for other purposes.

[0038] Reagents All drugs were obtained commercially without further purification, and ZnCl2, prochloraz (PRO), terephthalic acid (TPA), 1,2,4-benzenetricarboxylic acid (1,2,4-BTC), 1,4-naphthalene dicarboxylic acid (NTD), N,N-dimethylacetamide (DMA), and N,N-dimethylformamide (DMF) were provided by Aladdin Holdings Group Co., Ltd.

[0039] Preparation of culture medium Solid PDA medium: 200 g potato, 20 g glucose, 20 g agar powder, adjust pH to 7.0, and make up to 1000 mL.

[0040] Example 1. Synthesis and characterization of prochloraz ligand metal organic framework materials 1. Synthesis According to the schematic diagram shown in Figure 1, three new MOF materials (Zn-PRO-1, Zn-PRO-2, Zn-PRO-3) were synthesized using the nutrient element Zn as the metal and PRO as the ligand. All three materials were synthesized using the hot solvent method. The specific steps are as follows: Zn-PRO-1: [Zn(TPA)(PRO)2] n First, ZnCl2 (6.8 mg, 0.05 mmol), PRO (18.8 mg, 0.05 mmol) and TPA (8.3 mg, 0.05 mmol) were fully dispersed in 8 mL of solvent ( N , N -dimethylacetamide: water = 1: 1). The mixture was placed in a high pressure reactor and heated at 80 ° C for 48 hours. After the reaction was completed, the formed white crystals were separated and filtered out, and repeatedly washed with deionized water. The obtained solid was dried at room temperature overnight to obtain 21 mg of the final product (yield: 53.4%).

[0041] Zn-PRO-2:[Zn(1,2,4-BTC)(PRO)2] n ZnCl2 (6.8 mg, 0.05 mmol), PRO (18.8 mg, 0.05 mmol) and 1,2,4-BTC (10.5 mg, 0.05 mmol) were fully dispersed in 8 mL of solvent ( N , N -dimethylacetamide: water = 1: 1). Then transferred to a high-pressure reactor and heated at 80 ° C for 48 hours. After the reaction, the formed white crystals were separated and filtered out, and repeatedly washed with deionized water and dried at room temperature overnight to obtain 24 mg of the final product (yield: 58.4%).

[0042] Zn-PRO-3: [Zn(NTD)(PRO)]n ZnCl2 (6.8 mg, 0.05 mmol), PRO (18.8 mg, 0.05 mmol) and NTD (10.8 mg, 0.05 mmol) were fully dispersed in 8 mL of solvent ( N , N -dimethylformamide: water = 1: 1). The mixture was placed in a high pressure reactor and heated at 80 ° C for 48 hours. After the reaction was completed, the formed light yellow crystals were separated and filtered out, and washed repeatedly with deionized water, and dried at room temperature overnight to obtain 30 mg of the final product (yield: 66.7%).

[0043] 2. Characterization The structure of the coordination polymer was characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). The crystal structure of the sample was determined by single crystal X-ray diffraction (SCXRD) method, and the single crystal data were recorded using a Bruker D8 Quest diffractometer equipped with a Mo-K α Photon III radiation detector (λ = 0.71073Å). The structure was solved by direct method, and all reflections on F2 were refined by full matrix least squares using SHELXL software. Non-hydrogen atoms were refined anisotropically. The experimentally measured structural information is shown in Table S1, and the bond length and angle information are shown in Tables S2, S3, and S4. The Cu-K α Powder X-ray diffraction analysis of the samples was performed using a 1000 nm (radiation) diffractometer and compared with the single crystal X-ray diffraction pattern to detect the presence of impurities in the samples. Thermogravimetric analysis (TGA) was performed using a synchronous thermal analyzer (STA449 F3 Jupiter) in nitrogen and air at a heating rate of 10 °C / min to 800 °C. Fourier transform infrared (FT-IR) spectroscopy was measured using a JASCO FT-IR-6300 spectrometer (JASCO International Co., Ltd., Tokyo, Japan). The spectral region is 4000–400 cm -1 , with a resolution of 4 cm -1 .

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051] Figure 2 Fourier transform infrared (FT-IR) spectra of three coordination polymers are shown.

[0052] In the infrared spectrum of Zn-PRO-1, 3129 cm -1 The absorption peak at 2970 cm-1 is mainly attributed to OH. The stretching vibration region of CH is located at 2970 cm-1 in the spectrum. -1 The C=O and CO stretching absorption peaks appear at 1703 and 1011 cm -1 Position. At 1554 cm -1 The stretching vibration peak of C=N is observed at 656 cm -1 The stronger signal at the position belongs to the C-Cl vibration of PRO.

[0053] In the infrared spectrum of Zn-PRO-2, 3132 cm -1 The absorption peak at 2965 cm is mainly attributed to OH. The stretching vibration region of CH is located at 2965 cm -1 The C=O and CO stretching absorption peaks appear at 1707 and 1028 cm -1 Position. At 1541 cm -1 The stretching vibration peak of C=N was observed at 652 cm-1, and the vibration peak of C-Cl on PRO appeared at 652 cm-1. -1 Place.

[0054] In the infrared spectrum of Zn-PRO-3, 3117 cm -1 The absorption peak at 2963 cm is mainly attributed to OH. The stretching vibration region of CH is located at 2963 cm -1 The C=O and CO stretching absorption peaks appear at 1705 and 1011 cm -1 Position. At 1550 cm -1 The stretching vibration peak of C=N was observed at 1513 cm -1 The stretching vibration of C=C is 656 cm -1 The absorption peak at is due to C-Cl.

[0055] Figure 3 Powder X-ray diffraction (PXRD) patterns of three coordination polymers are shown.

[0056] Figure 4 Thermogravimetric analysis (TGA) spectra of three coordination polymers are shown.

[0057] The structure and purity of Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3 were characterized by PXRD, FT-IR and TGA. The results showed that the three materials had good purity and thermal stability.

[0058] Example 2: Release Experiment 1. Release assay 8 mg of Zn-PRO-1, Zn-PRO-2, and Zn-PRO-3 were placed in 80 mL of ultrapure water and stirred at room temperature. 2 mL of the solution was removed periodically, centrifuged, and the supernatant was aspirated. The PRO release concentration was detected by high performance liquid chromatography (HPLC, Aglient-1200).

[0059] Chromatographic column: Lichrospher C18, 250 mm × 4.6 mm stainless steel column; Particle size: 5 µ m; column temperature: room temperature (28°C); mobile phase: methanol-water (volume ratio 80:20); Flow rate: 1.0 mL / min; Detection wavelength: 220 nm; Injection volume: 10 µ L; retention time: about 7.2 min.

[0060] The experimental results are as follows Figure 5 As shown. It can be seen that all three materials can slowly release PRO in water, and the release concentration can reach 5 mg / L within 2 hours, which is enough to inhibit Colletotrichum gloeosporioides The release concentration of Zn-PRO-3 is higher than that of Zn-PRO-1 and Zn-PRO-2. The three materials reach equilibrium at about 200 h and can maintain the concentration until 328 h.

[0061] The drug loading amounts of the three materials are as high as 76.6% (Zn-PRO-1), 73.4% (Zn-PRO-2), and 57.4% (Zn-PRO-3) (the relative molecular mass of PRO is 376.7, the relative molecular mass of Zn-PRO-1 is 982.82, the relative molecular mass of Zn-PRO-2 is 1026.83, and the relative molecular mass of Zn-PRO-3 is 656.22).

[0062] Drug loading rate = relative molecular mass of PRO / relative molecular mass of MOFs.

[0063] 2. pH responsive release HEPES sodium salt was added to ultrapure water to prepare a buffer solution. The pH was adjusted by adding NaOH and HCl. The pH value in the solution was detected by a pH analyzer. 8 mg of Zn-PRO-1 was weighed and added to 80 mL of three buffer solutions with different pH values ​​(pH = 5, 7, and 9). 2 mL of the solution was removed regularly, and the supernatant was aspirated after centrifugation. The PRO release concentration was detected by HPLC.

[0064] The experimental results are as follows Figure 6 As shown. It can be seen that the release rate of Zn-PRO-3 is different at different pH values, and the release rate is (pH=5<pH=7<pH=9). The release rate is fastest at pH 9 and slowest at pH 5, indicating that the material will accelerate decomposition under alkaline conditions and slow down decomposition under acidic conditions. Zn-PRO-3 itself has the characteristic of pH-responsive release.

[0065] Therefore, all three materials can slowly release PRO pesticides in water and then maintain a constant concentration for a long time. Zn-PRO-3 itself also has the property of pH-responsive release.

[0066] Example 3, antibacterial experiment 1. Material concentration and antibacterial effect The growth rate method was used to Colletotrichum gloeosporioides and Alternaria alternata For the antibacterial test, the three materials were prepared into a suspension with sterile water, and five concentration gradients (4mg / L, 2mg / L, 1mg / L, 0.5mg / L, 0.25mg / L) were diluted twice. The suspension was added to the melted PDA medium, and then poured into the culture dish to make a medicine plate and dried. A bacterial cake with a diameter of 0.5cm was punched out with a hole puncher and placed in the center of the medicine plate. The culture dish was sealed with a sealing film and placed in a constant temperature incubator at 28℃ for 3-5 days. The mycelium diameter was determined by the cross method, and then the daily data and photos were sorted and recorded. The data were analyzed to obtain the antibacterial efficiency of the material and EC 50 The culture medium without sample and PRO original drug was used as control, and the experiment was repeated 3 times in each group.

[0067] PRO, Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3 Colletotrichum gloeosporioides and Alternaria alternata The antibacterial effect of Figure 7 As shown, Colletotrichum gloeosporioides The antibacterial effect data of Alternaria alternata The antibacterial effects are shown in Table 2.

[0068] Table 1. Effects of Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3 on Colletotrichum gloeosporioides ( Colletotrichum gloeosporioides) Antibacterial effect data table

[0069] Table 2. Effects of Zn-PRO-1, Zn-PRO-2, and Zn-PRO-3 on the activity of Alternaria alternata ( Alternaria alternata ) Antibacterial effect data table

[0070] It can be seen that the three materials have certain antibacterial effects on Colletotrichum gloeosporioides and Alternariaalternata, and the effects of Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3 are better than PRO original drug.

[0071] 2. Release concentration and antibacterial effect In order to explore whether the organic acids and Zn ions released in the solution have inhibitory effects on PRO, antibacterial experiments were carried out according to the actual release concentration: Zn-PRO-3 was stirred in sterile water for a period of time using a magnetic stirrer, the supernatant was taken by centrifugation, the concentration of the supernatant was measured, and five concentration gradients (1, 0.5, 0.25, 0.125, 0.0625 mg / L) were configured according to the measured concentration for antibacterial experiments. The growth rate method was also used, and the specific method was as described above.

[0072] The experimental results are as follows Figure 8 As shown in Table 3, the half-inhibitory concentration (EC 50 ) is 0.13 mg / L, and the EC of Zn-PRO-3 50 The value was 0.12 mg / L, proving that the release concentration of Zn-PRO-3 was sufficient to inhibit Colletotrichum gloeosporioides The growth of the bacteria was inhibited, which was the same as that of PRO original drug. It also proved that the organic acid and Zn ions released in the solution did not inhibit PRO.

[0073] Table 3. Effect of Zn-PRO-3 release concentration on Colletotrichum gloeosporioides ( Colletotrichum loeosporioides ) Antibacterial effect data table

[0074] Therefore, the antibacterial experiments showed that the three materials Colletotrichum gloeosporioides , Alternaria alternata The two plant pathogenic fungi have significant antibacterial effects. The release concentration inhibition experiment proves that the released PRO concentration is sufficient to inhibit the growth of pathogens and the carboxylic acid ligand has no effect on the antibacterial effect.

[0075] The present invention has been described in detail above. For those skilled in the art, without departing from the purpose and scope of the present invention, can implement the present invention in a wider range under equivalent parameters, concentrations and conditions. Although the present invention provides specific embodiments, it should be understood that the present invention can be further improved. In a word, according to the principle of the present invention, the application is intended to include any changes, uses or improvements to the present invention, including departing from the disclosed scope in the application and the changes made with conventional techniques known in the art.

Claims

1. A prochloraz ligand metal organic framework material, It is characterized in that Any one of the following Zn-PRO-1, Zn-PRO-2 and Zn-PRO-3: Zn-PRO-1: chemical formula is [Zn(TPA)(PRO) 2 ] n , where TPA represents terephthalic acid, PRO represents amidine, and n represents the average number of repeating units contained in the polymer macromolecular chain; Zn-PRO-2: chemical formula is [Zn(1,2,4-BTC)(PRO) 2 ] n , where 1,2,4-BTC represents 1,2,4-benzenetricarboxylic acid, PRO represents amidine, and n represents the average number of repeating units contained in the polymer macromolecular chain; Zn-PRO-3: chemical formula is [Zn(NTD)(PRO)] n , wherein NTD represents 1,4-naphthalene dicarboxylic acid, PRO represents amidine, and n represents the average number of repeating units contained in the polymer macromolecular chain.

2. The prochloraz ligand metal organic framework material according to claim 1, Features: The Zn-PRO-1 belongs to the monoclinic system, P21 / c space group, and the unit cell parameters are as follows: The Zn-PRO-2 belongs to the monoclinic system, P21 / c space group, and the unit cell parameters are as follows: The Zn-PRO-3 belongs to the monoclinic system, C2 / c space group, and the unit cell parameters are as follows: 。 3. The method for preparing the prochloraz ligand metal organic framework material according to any one of claims 1 to 2, It is characterized in that Any one of the following 1)-3): 1) The prochloraz ligand metal organic framework material is Zn-PRO-1, comprising the following steps: Dispersing zinc salt, amidine and terephthalic acid in a solvent, and heating in a closed system for reaction to obtain the Zn-PRO-1; 2) The prochloraz ligand metal organic framework material is Zn-PRO-2, comprising the following steps: Dispersing zinc salt, amidine and 1,2,4-benzenetricarboxylic acid in a solvent, and heating in a closed system for reaction to obtain the Zn-PRO-2; 3) The prochloraz ligand metal organic framework material is Zn-PRO-3, comprising the following steps: The zinc salt, amidine and 1,4-naphthalene dicarboxylic acid are dispersed in a solvent and heated in a closed system for reaction to obtain the Zn-PRO-3.

4. The method for preparing the prochloraz ligand metal organic framework material according to claim 3, Features: The molar ratio of the zinc salt, the amidine and the terephthalic acid is (1-2):1:(1-2); The molar ratio of the zinc salt, the amidine and the 1,2,4-benzenetricarboxylic acid is (1-2):1:(1-2); The molar ratio of the zinc salt, the amidine and the 1,4-naphthalene dicarboxylic acid is (1-2):1:(1-2).

5. The method for preparing the prochloraz ligand metal organic framework material according to any one of claims 3 to 4, Features: In methods 1)-3), the zinc salt is zinc chloride, zinc sulfate or zinc nitrate; The solvent is composed of an organic solvent and water in a volume ratio of 1:1, and the organic solvent is N,N-dimethylformamide or N,N-dimethylacetamide; The ratio of the zinc salt to the solvent is 0.5 mmol:8-80 mL.

6. The method for preparing the prochloraz ligand metal organic framework material according to any one of claims 3 to 5, Features: The heating temperature is 80-120° C. and the heating time is 24-48 hours.

7. Use of the prochloraz ligand metal organic framework material according to any one of claims 1 to 2 or the prochloraz ligand metal organic framework material obtained by the preparation method according to any one of claims 3 to 6 in any of the following: A1) Inhibition of plant pathogenic fungi; A2) Inhibit the hyphae growth of plant pathogenic fungi; A3) Prevent and control plant diseases.

8. The use according to claim 7, Features: The plant pathogenic fungi include Colletotrichum gloeosporioides ( Colletotrichum gloeosporioides ) or Alternaria interseptata ( Alternaria alternata ); The plant diseases include strawberry anthracnose or apple black spot.

9. A method for inhibiting plant pathogenic fungi, It is characterized in that The steps include: The prochloraz ligand metal organic framework material according to any one of claims 1 to 2 or the prochloraz ligand metal organic framework material obtained by the preparation method according to any one of claims 3 to 6 is dispersed in water to prepare a suspension, and the suspension is used to treat a place that has been infected or is susceptible to infection by plant pathogenic fungi.

10. The method according to claim 9, Features: The plant pathogenic fungi include Colletotrichum gloeosporioides ( Colletotrichum gloeosporioides ) or Alternaria interseptata ( Alternaria alternata ); The prochloraz ligand metal organic framework material is Zn-PRO-3, and the pH value of the suspension is controlled to be alkaline to accelerate the release of prochloraz, and the pH value of the suspension is controlled to be acidic to slow down the release of prochloraz.

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