CN116730770B - Intelligent degradable silicon-based nano-pesticide-fertilizer and preparation method and application thereof - Google Patents
Intelligent degradable silicon-based nano-pesticide-fertilizer and preparation method and application thereof Download PDFInfo
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- CN116730770B CN116730770B CN202310441220.7A CN202310441220A CN116730770B CN 116730770 B CN116730770 B CN 116730770B CN 202310441220 A CN202310441220 A CN 202310441220A CN 116730770 B CN116730770 B CN 116730770B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 35
- 239000010703 silicon Substances 0.000 title claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000003337 fertilizer Substances 0.000 title claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 83
- 239000005820 Prochloraz Substances 0.000 claims abstract description 51
- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000575 pesticide Substances 0.000 claims abstract description 46
- 239000005794 Hymexazol Substances 0.000 claims abstract description 40
- KGVPNLBXJKTABS-UHFFFAOYSA-N hymexazol Chemical compound CC1=CC(O)=NO1 KGVPNLBXJKTABS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 175
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 107
- 239000000243 solution Substances 0.000 claims description 83
- 239000011787 zinc oxide Substances 0.000 claims description 79
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 235000019441 ethanol Nutrition 0.000 claims description 51
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 42
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 21
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 18
- 239000004246 zinc acetate Substances 0.000 claims description 18
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 claims description 16
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 15
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 15
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 15
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 15
- 239000011654 magnesium acetate Substances 0.000 claims description 15
- 235000011285 magnesium acetate Nutrition 0.000 claims description 15
- 229940069446 magnesium acetate Drugs 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 150000001299 aldehydes Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000007037 hydroformylation reaction Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 8
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 claims description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 7
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 6
- 230000008635 plant growth Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 20
- 229940079593 drug Drugs 0.000 abstract description 19
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 2
- 238000000338 in vitro Methods 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 235000016709 nutrition Nutrition 0.000 abstract description 2
- 230000035764 nutrition Effects 0.000 abstract description 2
- 238000005576 amination reaction Methods 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 238000001000 micrograph Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000011056 performance test Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002096 quantum dot Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 241000813090 Rhizoctonia solani Species 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- GVJXGCIPWAVXJP-UHFFFAOYSA-N 2,5-dioxo-1-oxoniopyrrolidine-3-sulfonate Chemical compound ON1C(=O)CC(S(O)(=O)=O)C1=O GVJXGCIPWAVXJP-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 241001361634 Rhizoctonia Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- -1 aldehyde zinc oxide Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002539 nanocarrier Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NASVITFAUKYCPM-UHFFFAOYSA-N ethanol;tetraethyl silicate Chemical compound CCO.CCO[Si](OCC)(OCC)OCC NASVITFAUKYCPM-UHFFFAOYSA-N 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 244000000004 fungal plant pathogen Species 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 230000008636 plant growth process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P21/00—Plant growth regulators
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
- C05G5/27—Dispersions, e.g. suspensions or emulsions
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical & Material Sciences (AREA)
- Plant Pathology (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Toxicology (AREA)
- Microbiology (AREA)
- Mycology (AREA)
- Botany (AREA)
- Fertilizers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to the technical field of nano materials, and discloses an intelligent degradable silicon-based nano pesticide fertilizer and a preparation method and application thereof. The preparation method of the intelligent degradable silicon-based nano-pesticide fertilizer comprises the following steps: amination of Cu-MSNs to Cu-MSNs-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the Then, prochloraz is adsorbed to obtain Pro@Cu-MSNs; then grafting aldehyde ZnOQDs, pro@Cu-MSNs-ZnO; mixing hymexazol, water and Pro@Cu-MSNs-ZnO to obtain Pro@Cu-MSNs-ZnO/Hym, namely the intelligent degradable silicon-based nano-pesticide fertilizer. The invention constructs a degradable bimetal bi-pesticide nano composite system with pH response, effectively controls the slow release of the drug through the in vitro environment, improves the bactericidal activity, reduces the pollution to the environment possibly caused by excessive accumulation of the pesticide and the carrier and provides good nutrition function for plants.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to an intelligent degradable silicon-based nano medical fertilizer and a preparation method and application thereof.
Background
Plant pathogenic fungi have serious influence on the growth and yield of crops, and become an important bottleneck for sustainable agricultural development. The pesticide plays an important role in resisting biological disasters, ensuring crop yield and promoting continuous and stable growth of agricultural production. However, the effective utilization of pesticides is less than 1% due to runoff, spray drift, evaporation or volatilization, etc. during field application. The inefficient use of pesticides causes a series of problems of ecological environmental pollution, eutrophication of water bodies, soil degradation and the like. With the sustainable development of agriculture, ecological environment protection, food safety and other problems, the problems become a focus of attention. There is a strong need for a safer, more effective new pesticide.
In recent years, the development of nano technology is rapid, and nano materials are popularized and applied in the field of pesticide preparations due to the characteristics of small size, special structure and the like, so that the sustainable development of pesticides is greatly promoted. The novel multifunctional nano delivery system can obviously improve the biological activity of the effective components of the pesticide, increase the utilization rate, prolong the lasting effect, reduce the pesticide loss and effectively control the environmental pollution.
Silica nanomaterials have been widely used in material science, are special members for manufacturing various valuable materials, and are attracting attention in various fields such as medicine, food, agriculture, and the like. In recent years, a variety of stimuli-responsive nano pesticide delivery systems have been developed for the efficient control of target organisms. The traditional response mesoporous silicon nanomaterial has large specific surface area, good water dispersibility and stability and can be widely applied. However, in the application, the nano-carrier is not easy to degrade in structure, so that a certain pesticide residue problem exists, and the utilization rate of the pesticide active ingredients cannot be maximized.
Therefore, the pesticide taking the degradable nano material as the carrier has important significance for the application of the nano material in pesticides.
Disclosure of Invention
The invention aims to provide an intelligent degradable silicon-based nano-pesticide fertilizer and a preparation method and application thereof, and solves the problems in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an intelligent degradable silicon-based nano-pesticide fertilizer, which comprises the following steps:
(1) Preparation of Cu-MSNs: mixing cetyl trimethyl ammonium bromide, ammonia water solution and ethanol solution of tetraethoxysilane, adding ethanol solution of copper nitrate and ethanol solution of tetraethoxysilane after mixing, and performing hydrothermal reaction to obtain Cu-MSNs;
(2) Preparation of aminated Cu-MSNs: mixing Cu-MSNs, methanol and 3-aminopropyl triethoxysilane to obtain Cu-MSNs-NH 2 Namely, the aminated Cu-MSNs;
(3) Preparation of Pro@Cu-MSNs: n-hexane solution of prochloraz, cu-MSNs-NH 2 Mixing and drying to obtain Pro@Cu-MSNs;
(4) Preparation of ZnOQDs: heating absolute ethyl alcohol, then adding zinc acetate and magnesium acetate, and mixing to obtain a mixed solution of zinc acetate and magnesium acetate;
adding a mixed solution of zinc acetate and magnesium acetate into an absolute ethyl alcohol solution of sodium hydroxide to react to obtain zinc oxide quantum dots, namely ZnOQDs;
(5) Preparation of aminated ZnOQDs: mixing and dispersing ZnOQDs and N, N-dimethylformamide, heating to a reaction temperature, and adding 3-aminopropyl triethoxysilane for reaction to obtain aminated ZnOQDs;
(6) Preparation of the hydroformylation ZnOQDs: mixing 4-formylbenzoic acid, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide, N-dimethylformamide and aminated ZnOQDs to obtain aldehyde ZnOQDs;
(7) Preparation of Pro@Cu-MSNs-ZnO: mixing aldehyde ZnOQDs, tris buffer solution and Pro@Cu-MSNs to obtain Pro@Cu-MSNs-ZnO;
(8) Preparation of Pro@Cu-MSNs-ZnO/Hym: mixing hymexazol, water and Pro@Cu-MSNs-ZnO to obtain Pro@Cu-MSNs-ZnO/Hym, namely the intelligent degradable silicon-based nano-pesticide fertilizer.
Preferably, in the preparation method of the intelligent degradable silicon-based nano-pesticide fertilizer, the mass volume ratio of tetraethoxysilane in the ethanol solution of cetyltrimethylammonium bromide, ammonia water solution and tetraethoxysilane added for the first time in the step (1) is 400-700 mg: 100-500 mL: 0.1-0.4 mL, wherein the volume ratio of tetraethoxysilane to ethanol in the ethanol solution of the tetraethoxysilane added for the first time is 0.1-0.4: 3 to 6;
the mass volume ratio of the hexadecyl trimethyl ammonium bromide in the step (1), the copper nitrate in the ethanol solution of the copper nitrate, the ethanol in the ethanol solution of the copper nitrate and the tetraethoxysilane in the ethanol solution of the tetraethoxysilane added for the second time is 400-700 mg: 35-42 mg: 3-7 mL: 0.5-2.5 mL, wherein the volume ratio of tetraethoxysilane to ethanol in the ethanol solution of the tetraethoxysilane added for the second time is 0.5-2.5: 4 to 8.
Preferably, in the preparation method of the intelligent degradable silicon-based nano-pesticide fertilizer, the mass-volume ratio of the Cu-MSNs, the methanol and the 3-aminopropyl triethoxysilane in the step (2) is 300-700 mg: 30-80 mL: 0.1-0.4 mL;
the prochloraz and Cu-MSNs-NH in the n-hexane solution of prochloraz in the step (3) 2 The mass ratio of the prochloraz to the n-hexane is 2-4:0.5-2, and the concentration of the prochloraz to the n-hexane solution is 1-20 mg/mL.
The mass volume ratio of the absolute ethyl alcohol to the zinc acetate to the magnesium acetate in the step (4) is 2-4 mL: 40-60 mg: 4-6 mg, wherein the mass ratio of the sodium hydroxide in the anhydrous ethanol solution of the zinc acetate and the sodium hydroxide is 3-6: 0.5-2, wherein the mass volume ratio of the sodium hydroxide to the absolute ethyl alcohol in the absolute ethyl alcohol solution of the sodium hydroxide is 100-120 mg:1 to 1.2mL.
Preferably, in the preparation method of the intelligent degradable silicon-based nano-pesticide fertilizer, the volume ratio of ZnOQDs, N-dimethylformamide and 3-aminopropyl triethoxysilane in the step (5) is 90-115 mg: 10-20 mL: 40-60 mu L;
the mass volume ratio of the 4-formylbenzoic acid, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the N-hydroxysuccinimide, the N, N-dimethylformamide and the aminated ZnOQDs in the step (6) is 50-70 mg: 65-80 mg: 60-70 mg: 3-7 mL: 120-160 mg;
the mass volume ratio of the hydroformylation ZnOQDs, the Tris buffer solution and the Pro@Cu-MSNs in the step (7) is 0.5-2 mg: 0.05-0.25 mL: 0.5-2 mg;
in the step (8), the mass ratio of the hymexazol to the water to the Pro@Cu-MSNs-ZnO is 10-30:1:5-20.
Preferably, in the method for preparing the intelligent degradable silicon-based nano-pesticide fertilizer, the hydrothermal reaction condition in the step (1) is as follows: the temperature is 30-60 ℃ and the time is 12-24 h;
the mixing conditions in step (2): mixing for 15-24 h at 20-30 ℃;
the mixing conditions in step (3): mixing for 15-24 h at 25-35 ℃;
the drying temperature in the step (3) is 40-60 ℃, and the drying time is 8-12 h;
the heating temperature in the step (4) is 70-90 ℃;
the reaction conditions in step (4): reacting for 6-12 h under the dark condition;
the reaction temperature in the step (5) is 100-130 ℃, and the reaction time is 15-25 min.
Preferably, in the preparation method of the intelligent degradable silicon-based nano-pesticide fertilizer, the mixing condition in the step (6) is as follows: mixing for 15-24 h at 20-30 ℃;
the mixing conditions in step (7): mixing for 10-15 h at 20-30 ℃ under the condition of avoiding light;
the mixing conditions in step (8): mixing for 20-25 h at 20-30 ℃ under the condition of avoiding light.
The invention also provides the intelligent degradable silicon-based nano-pesticide fertilizer prepared by the preparation method of the intelligent degradable silicon-based nano-pesticide fertilizer.
The invention also provides application of the intelligent degradable silicon-based nano-pesticide fertilizer in plant growth.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention is realized byMethod of introducing Cu into silica framework 2+ Forming a Cu-O-bond which is easy to break under an acidic condition, and constructing a biodegradable mesoporous silica carrier Cu-MSNs; the surface of the mesoporous silica and the surface of the zinc oxide quantum dot are modified, so that the zinc oxide quantum dot is grafted on the surface of the mesoporous silica as a pore plugging agent; the compound medicines prochloraz and hymexazol are used as mode medicines, and prochloraz is loaded in a silicon dioxide pore canal through adsorption; on the other hand, zinc oxide provides a conjugation site, so that the other drug hymexazol is loaded on the surface of the zinc oxide through a coordination bond; the bactericidal activity of the silicon-based nano-pesticide fertilizer is greatly improved due to the loading of the two compound medicines, and the growth of plants is promoted along with the regulation of the two metal ions and the green pesticide hymexazol in the plant growth process.
(2) The invention constructs a degradable bimetal bi-pesticide nano composite system with pH response, effectively controls the slow release of the drug through the in vitro environment, improves the bactericidal activity, reduces the pollution to the environment possibly caused by excessive accumulation of the pesticide and the carrier, and provides good nutrition function for plants.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a scanning electron microscope image of MSNs and Cu-MSNs, pro@Cu-MSNs-ZnO/Hym of example 1; wherein A is a scanning electron microscope image of MSNs, B is a scanning electron microscope image of Cu-MSNs, C is a scanning electron microscope image of Pro@Cu-MSNs-ZnO/Hym;
FIG. 2 is an X-ray diffraction pattern of Cu-MSNs, pro@Cu-MSNs-ZnO/Hym in example 1;
FIG. 3 is a chart of FT-IR spectroscopy for Cu-MSNs, pro@Cu-MSNs-ZnO/Hym in example 1;
FIG. 4 is a graph showing cumulative release at different pH values for Pro@Cu-MSNs, pro@Cu-MSNs-ZnO/Hym in example 1; wherein A is an accumulated release curve graph of Pro@Cu-MSNs under different pH conditions, and B is an accumulated release curve graph of Pro@Cu-MSNs-ZnO/Hym under different pH conditions;
FIG. 5 is a scanning electron microscope image of Pro@Cu-MSNs-ZnO/Hym of example 1 at different times at pH 4.0; wherein, A is Pro@Cu-MSNs-ZnO/Hym scanning electron microscope image at 0h, B is Pro@Cu-MSNs-ZnO/Hym scanning electron microscope image at 24h, C is Pro@Cu-MSNs-ZnO/Hym scanning electron microscope image at 48h, D is Pro@Cu-MSNs-ZnO/Hym scanning electron microscope image at 72 h;
fig. 6 is a graph showing the sterilizing effect of prochloraz, hymexazol, and mixtures of prochloraz and hymexazol on 14 days against rhizoctonia solani of pro@cu-MSNs-ZnO/Hym prepared in example 1.
Detailed Description
The invention provides a preparation method of an intelligent degradable silicon-based nano-pesticide fertilizer, which comprises the following steps:
(1) Preparation of Cu-MSNs: mixing cetyl trimethyl ammonium bromide, ammonia water solution and ethanol solution of tetraethoxysilane, adding ethanol solution of copper nitrate and ethanol solution of tetraethoxysilane after mixing, and performing hydrothermal reaction to obtain Cu-MSNs;
(2) Preparation of aminated Cu-MSNs: mixing Cu-MSNs, methanol and 3-aminopropyl triethoxysilane to obtain Cu-MSNs-NH 2 Namely, the aminated Cu-MSNs;
(3) Preparation of Pro@Cu-MSNs: n-hexane solution of prochloraz, cu-MSNs-NH 2 Mixing and drying to obtain Pro@Cu-MSNs;
(4) Preparation of ZnOQDs: heating absolute ethyl alcohol, then adding zinc acetate and magnesium acetate, and mixing to obtain a mixed solution of zinc acetate and magnesium acetate;
adding a mixed solution of zinc acetate and magnesium acetate into an absolute ethyl alcohol solution of sodium hydroxide to react to obtain zinc oxide quantum dots, namely ZnOQDs;
(5) Preparation of aminated ZnOQDs: mixing and dispersing ZnOQDs and N, N-dimethylformamide, heating to a reaction temperature, and adding 3-aminopropyl triethoxysilane for reaction to obtain aminated ZnOQDs;
(6) Preparation of the hydroformylation ZnOQDs: mixing 4-formylbenzoic acid, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide, N-dimethylformamide and aminated ZnOQDs to obtain aldehyde ZnOQDs;
(7) Preparation of Pro@Cu-MSNs-ZnO: mixing aldehyde ZnOQDs, tris buffer solution and Pro@Cu-MSNs to obtain Pro@Cu-MSNs-ZnO;
(8) Preparation of Pro@Cu-MSNs-ZnO/Hym: mixing hymexazol, water and Pro@Cu-MSNs-ZnO to obtain Pro@Cu-MSNs-ZnO/Hym, namely the intelligent degradable silicon-based nano-pesticide fertilizer.
In the invention, the specific mixing process in the step (1) is as follows:
cetyl trimethyl ammonium bromide is dissolved in ammonia water solution at 40 ℃, and then tetraethoxysilane ethanol solution is added to be mixed and stirred for 4 hours.
In the present invention, the step (1) further comprises the steps of: stirring for 2h.
In the present invention, the hydrothermal reaction conditions in the step (1) are as follows: the temperature is preferably 30 to 60 ℃, more preferably 35 to 55 ℃, still more preferably 40 to 50 ℃; the time is preferably 12 to 24 hours, more preferably 15 to 22 hours, and still more preferably 18 to 20 hours.
In the present invention, after the hydrothermal reaction in the step (1) is finished, the method further comprises: 0.3g of ammonium nitrate is dissolved in 50mL of isopropanol, the product of the hydrothermal reaction is added, the cetyl trimethyl ammonium bromide as a surfactant template in the product of the hydrothermal reaction is extracted, and the mixture is stirred at 85 ℃ overnight, collected, washed and dried.
In the invention, the mass volume ratio of tetraethoxysilane in the ethanol solution of the cetyltrimethylammonium bromide, the ammonia water solution and the tetraethoxysilane added for the first time in the step (1) is preferably 400-700 mg: 100-500 mL:0.1 to 0.4mL, more preferably 455 to 640mg: 210-400 mL:0.15 to 0.32mL, more preferably 495 to 575mg: 280-365 mL: 0.22-0.29 mL;
the volume ratio of tetraethoxysilane and ethanol in the ethanol solution of the tetraethoxysilane added for the first time is preferably 0.1-0.4: 3 to 6, more preferably 0.15 to 0.35:3.5 to 5.5, more preferably 0.22 to 0.29:4.2 to 5.
In the present invention, the mass volume ratio of cetyl trimethyl ammonium bromide, copper nitrate in the ethanol solution of copper nitrate, ethanol in the ethanol solution of copper nitrate, tetraethoxysilane in the ethanol solution of tetraethoxysilane added for the second time in the step (1) is preferably 400-700 mg: 35-42 mg: 3-7 mL:0.5 to 2.5mL, more preferably 445 to 655mg: 36-41 mg: 3.5-6.5 mL:0.75 to 2.05mL, more preferably 500 to 590mg: 37-39 mg: 4-5 mL: 1.25-1.9 mL;
the volume ratio of tetraethoxysilane and ethanol in the ethanol solution of the tetraethoxysilane added for the second time is preferably 0.5-2.5: 4 to 8, more preferably 0.9 to 2.3:4.5 to 7, more preferably 1.3 to 1.9:5 to 6.3.
In the invention, the specific process of the step (2) is as follows:
dissolving Cu-MSNs in methanol, performing ultrasonic dispersion, adding 3-aminopropyl triethoxysilane, mixing, washing, and centrifuging to obtain Cu-MSNs-NH 2 。
In the present invention, the mixing conditions in the step (2) are preferably a mixing at a temperature of 20 to 30℃for 15 to 24 hours, more preferably a mixing at a temperature of 22 to 28℃for 17 to 23 hours, and still more preferably a mixing at a temperature of 24 to 27℃for 20 to 22 hours.
In the invention, the mass-volume ratio of the Cu-MSNs, the methanol and the 3-aminopropyl triethoxysilane in the step (2) is preferably 300-700 mg: 30-80 mL:0.1 to 0.4mL, more preferably 340 to 620mg: 43-72 mL:0.13 to 0.37mL, more preferably 420 to 570mg: 50-63 mL: 0.23-0.31 mL.
In the present invention, the mixing in the step (3) further includes: centrifuging and washing with n-hexane for 2-3 times.
In the present invention, the mixing conditions in the step (3) are preferably a mixing at a temperature of 25 to 35℃for 15 to 24 hours, more preferably a mixing at a temperature of 26 to 32℃for 16 to 22 hours, and still more preferably a mixing at a temperature of 28 to 30℃for 18 to 20 hours.
In the present invention, the drying temperature in the step (3) is preferably 40 to 60 ℃, more preferably 42 to 58 ℃, and even more preferably 45 to 53 ℃; the drying time is preferably 8 to 12 hours, more preferably 9 to 11 hours, and still more preferably 9 to 10 hours.
In the invention, the prochloraz and Cu-MSNs-NH in the n-hexane solution of prochloraz in the step (3) 2 The mass ratio of (2) to (4) is preferably: 0.5 to 2, more preferably 2.3 to 3.7:0.95 to 2.1, more preferably 2.5 to 3.2:1.3 to 1.8;
the concentration of the prochloraz in the n-hexane solution is preferably 1 to 20mg/mL, more preferably 5 to 17mg/mL, and even more preferably 9 to 13mg/mL.
In the present invention, the heating temperature in the step (4) is preferably 70 to 90 ℃, more preferably 75 to 86 ℃, and still more preferably 76 to 80 ℃.
In the present invention, the mixing condition in the step (4) is stirring at 80℃for 1 hour.
In the present invention, the reaction conditions in the step (4) are as follows: the reaction is carried out under the dark condition for 6 to 12 hours, more preferably 7 to 10 hours, still more preferably 8 to 9 hours.
In the present invention, after the reaction in the step (4), the method further comprises: adding n-hexane into the reacted solution, precipitating overnight and centrifuging; the volume ratio of the reacted solution to the normal hexane is 1:1 to 5.
In the invention, the mass-volume ratio of the absolute ethyl alcohol, the zinc acetate and the magnesium acetate in the step (4) is preferably 2-4 mL: 40-60 mg:4 to 6mg, more preferably 2.3 to 3.7mL: 43-55 mg:4.3 to 5.5mg, more preferably 2.5 to 3.2mL: 45-50 mg: 4.5-5 mg;
the mass ratio of the sodium hydroxide in the anhydrous ethanol solution of the zinc acetate and the sodium hydroxide is preferably 3-6: 0.5 to 2, more preferably 3.5 to 5.5:0.7 to 1.5, more preferably 4 to 4.5:0.9 to 1.3;
the mass volume ratio of the sodium hydroxide and the absolute ethyl alcohol in the absolute ethyl alcohol solution of the sodium hydroxide is preferably 100-120 mg:1 to 1.2mL, more preferably 103 to 117mg:1.03 to 1.17mL, more preferably 105 to 113mg: 1.05-1.13 mL.
In the present invention, after the reaction in the step (5), the method further comprises: after cooling, the mixture was centrifuged at 7800rpm for 3min, and then washed with N, N-dimethylformamide 2 times to remove impurities.
In the present invention, the temperature of the reaction in step (5) is preferably 100 to 130 ℃, more preferably 105 to 125 ℃, still more preferably 110 to 120 ℃; the reaction time is preferably 15 to 25 minutes, more preferably 16 to 24 minutes, and still more preferably 17 to 23 minutes.
In the invention, the mass-volume ratio of the ZnOQDs, the N, N-dimethylformamide and the 3-aminopropyl triethoxysilane in the step (5) is preferably 90-115 mg: 10-20 mL:40 to 60. Mu.L, more preferably 95 to 110mg: 13-19 mL:43 to 55. Mu.L, more preferably 97 to 107mg: 15-17 mL: 48-53 mu L.
In the invention, the specific mixing process in the step (6) is as follows:
dissolving 4-formylbenzoic acid, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysulfosuccinimide in N, N-dimethylformamide, and adding aminated ZnOQDs for mixing.
In the present invention, the mixing conditions in step (6) are preferably mixing at a temperature of 20 to 30℃for 15 to 24 hours; more preferably, the mixture is mixed at a temperature of 22 to 28℃for 17 to 23 hours, still more preferably, at a temperature of 24 to 27℃for 20 to 22 hours.
In the present invention, after the mixing in the step (6), the method further includes: and (5) centrifuging.
In the present invention, the mass-to-volume ratio of 4-formylbenzoic acid, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide, N-dimethylformamide, and aminated ZnOQDs in the step (6) is preferably 50 to 70mg: 65-80 mg: 60-70 mg: 3-7 mL:120 to 160mg, more preferably 56 to 64mg: 67-76 mg: 63-67 mg: 4-6 mL:130 to 150mg, more preferably 58 to 62mg: 70-73 mg: 65-66 mg: 5-5.5 mL: 135-145 mg.
In the invention, the specific mixing process in the step (7) is as follows:
the aldehyde ZnOQDs are dissolved in Tris buffer solution, and then Pro@Cu-MSNs are added for mixing.
In the present invention, the mixing condition in the step (7) is preferably mixing at 20 to 30℃for 10 to 15 hours under the light-shielding condition, more preferably mixing at 22 to 27℃for 11 to 14 hours under the light-shielding condition, and even more preferably mixing at 23 to 26℃for 12 to 13 hours under the light-shielding condition.
In the invention, the mass-volume ratio of the aldehyde ZnOQDs, the Tris buffer and the Pro@Cu-MSNs in the step (7) is preferably 0.5-2 mg: 0.05-0.25 mL:0.5 to 2mg, more preferably 0.9 to 1.7mg:0.07 to 0.23mL:0.7 to 1.6mg, more preferably 1.2 to 1.5mg: 0.1-0.2 mL:1 to 1.3mg.
In the invention, the specific mixing process in the step (8) is as follows:
the hymexazol is dissolved in water, and then Pro@Cu-MSNs-ZnO is added for mixing.
In the present invention, the mixing condition in the step (8) is preferably mixing at 20 to 30℃for 20 to 25 hours under the light-shielding condition, more preferably mixing at 22 to 27℃for 21 to 24 hours under the light-shielding condition, and even more preferably mixing at 23 to 26℃for 22 to 23 hours under the light-shielding condition.
In the invention, the ratio by mass of the hymexazol, the water and the Pro@Cu-MSNs-ZnO in the step (8) is preferably 10-30: 1:5 to 20, more preferably 12 to 25:1:8 to 17, more preferably 15 to 20:1:10 to 15.
The invention also provides the intelligent degradable silicon-based nano-pesticide fertilizer prepared by the preparation method of the intelligent degradable silicon-based nano-pesticide fertilizer.
The invention also provides application of the intelligent degradable silicon-based nano-pesticide fertilizer in plant growth.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The invention provides a preparation method of an intelligent degradable silicon-based nano-pesticide fertilizer, which comprises the following steps:
(1) Preparation of Cu-MSNs: 600mg of hexadecyl trimethyl ammonium bromide is dissolved in 300mL of ammonia water solution at 40 ℃, and then ethanol solution of tetraethoxysilane is added to be mixed and stirred for 4 hours; wherein the volume of tetraethoxysilane in the ethanol solution of tetraethoxysilane is 0.23mL, and the volume of ethanol is 5mL;
adding an ethanol solution of copper nitrate and an ethanol solution of tetraethoxysilane after mixing, mixing and stirring for 2 hours, transferring to a high-pressure reaction kettle, carrying out hydrothermal reaction at 40 ℃ for 16 hours, dissolving 0.3g of ammonium nitrate in 50mL of isopropanol after the reaction is finished, adding a hydrothermal reaction product, extracting a surfactant template cetyl trimethyl ammonium bromide, stirring overnight at 85 ℃, collecting the product, washing and drying to obtain Cu-MSNs; wherein the mass of copper nitrate in the ethanol solution of copper nitrate is 40.6mg, the volume of ethanol is 5mL, the volume of tetraethoxysilane in the ethanol solution of tetraethoxysilane is 1.144mL, and the volume of ethanol is 5mL;
(2) Preparation of aminated Cu-MSNs: dissolving 500mgCu-MSNs in 50mL of methanol, performing ultrasonic dispersion, adding 250 μl of 3-aminopropyl triethoxysilane, stirring at room temperature for 24 hr, washing, and centrifuging to obtain Cu-MSNs-NH 2 Namely, the aminated Cu-MSNs;
(3) Preparation of Pro@Cu-MSNs: 50mgCu-MSNs-NH 2 Mixing with 10mg/mL of prochloraz in n-hexane solution, magnetically stirring at 35deg.C for 24 hr, centrifuging, washing with n-hexane for 3 times, and vacuum drying at 50deg.C for 10 hr to obtain Pro@Cu-MSNs, wherein prochloraz and Cu-MSNs-NH are contained in prochloraz in n-hexane solution 2 The mass ratio of (3): 1, a step of;
(4) Preparation of ZnOQDs: heating 50mL of absolute ethyl alcohol to 80 ℃, then adding 500mg of zinc acetate and 50mg of magnesium acetate, and magnetically stirring for 1 hour at 80 ℃ to obtain a mixed solution of zinc acetate and magnesium acetate;
adding a mixed solution of zinc acetate and magnesium acetate into an absolute ethanol solution of sodium hydroxide, carrying out light-proof reaction for 8 hours at 80 ℃, then adding 200ml of n-hexane, precipitating overnight, and centrifuging to obtain zinc oxide quantum dots, namely ZnOQDs; wherein the mass of sodium hydroxide in the absolute ethyl alcohol solution of sodium hydroxide is 114mg, and the volume of the absolute ethyl alcohol is 1.14mL;
(5) Preparation of aminated ZnOQDs: mixing 100mgZnOQDs with 15mLN, N-dimethylformamide, heating to 120 ℃ after ultrasonic dispersion, adding 50 mu L of 3-aminopropyl triethoxysilane, stirring for 15min, cooling after the reaction is finished, centrifuging for 3min under the condition of 7800rpm, and washing for 2 times by adopting N, N-dimethylformamide to remove impurities to obtain the aminated ZnOQDs;
(6) Preparation of the hydroformylation ZnOQDs: dissolving 60mg of 4-formylbenzoic acid, 76mg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 64mg of N-hydroxysulfosuccinimide in 6mL of N, N-dimethylformamide solution, adding 150mg of aminated ZnOQDs, magnetically stirring at room temperature for 24 hours, and centrifuging to obtain aldehyde ZnOQDs;
(7) Preparation of Pro@Cu-MSNs-ZnO: 100mg of the hydroformylation ZnOQDs are dissolved in 10mLTris buffer (PH=8.0), then 100mgPro@Cu-MSNs are added, and stirring is carried out in the dark for 12 hours, so that Pro@Cu-MSNs-ZnO is obtained;
(8) Preparation of Pro@Cu-MSNs-ZnO/Hym: 300mg of hymexazol is dissolved in 20mL of deionized water, then 100mgPro@Cu-MSNs-ZnO is added for mixing, and after stirring for 24 hours in the dark, pro@Cu-MSNs-ZnO/Hym is obtained by centrifugation.
Comparative example 1
The preparation method of the MSNs comprises the following steps: 600mg of hexadecyl trimethyl ammonium bromide is dissolved in 300mL of ammonia water solution at 40 ℃, and then ethanol solution of tetraethoxysilane is added to be mixed and stirred for 4 hours; wherein the volume of tetraethoxysilane in the ethanol solution of tetraethoxysilane is 0.23mL, and the volume of ethanol is 5mL;
adding ethanol solution of tetraethoxysilane after mixing, mixing and stirring for 2 hours, transferring to a high-pressure reaction kettle, carrying out hydrothermal reaction at 40 ℃ for 16 hours, dissolving 0.3g of ammonium nitrate in 50mL of isopropanol after the reaction is finished, adding a product of the hydrothermal reaction, extracting hexadecyl trimethyl ammonium bromide serving as a surfactant template, stirring overnight at 85 ℃, collecting a product, washing and drying to obtain MSNs; wherein the tetraethoxysilane in the ethanol solution of tetraethoxysilane has a volume of 1.144mL and ethanol has a volume of 5mL.
Performance test 1
The Scanning Electron Microscope (SEM) images of the Cu-MSNs, pro@Cu-MSNs-ZnO/Hym and MSNs prepared in example 1 are shown in FIG. 1. As can be seen from FIG. 1, the Cu-MSNs have no obvious change in shape, are rod-like, have smaller size of 385.9nm and have smoother surface compared with the MSNs; the Pro@Cu-MSNs-ZnO/Hym still maintains the morphology after ZnO modification and drug loading, has nanoscale size of 467.9nm, but the surface becomes rough and has obvious granular feel, which indicates that zinc oxide is successfully grafted on the surface of a silicon dioxide nanosphere (MSNs).
Performance test 2
The Zeta potential parameter tables of Cu-MSNs, pro@Cu-MSNs-ZnO/Hym prepared in example 1 are shown in Table 1. As can be seen from Table 1, in aqueous solution, the Cu-MSNs charge is-14.0 mV, because of the influence of the surface silicon hydroxyl groups of the Cu-MSNs; after the surface is modified by amino, the value of Zeta potential is increased to some extent because the amino has positive charges, but the potential is still negative and is minus 0.55mV; after the prochloraz serving as a model drug is loaded, the aqueous solution of the prochloraz is positively charged, so that the Zeta potential value is increased to be 0.2mV; after the hydroformylation zinc oxide quantum dot is grafted, the hydroformylation zinc oxide quantum dot contains a large amount of aldehyde groups, so that the Zeta potential value of the nano particles is increased; after the hymexazol is adsorbed, the overall potential is obviously reduced due to the hydroxyl group in the hymexazol.
TABLE 1 Zeta potential parameter Table of Cu-MSNs, pro@Cu-MSNs-ZnO/Hym
Performance test 3
The X-ray diffraction patterns of the Cu-MSNs, pro@Cu-MSNs-ZnO and Pro@Cu-MSNs-ZnO/Hym prepared in example 1 are shown in FIG. 2. As can be seen from fig. 2, the Cu-MSNs exhibit a distinct diffraction peak at the (101) crystal plane, which is a characteristic peak of the Cu-MSNs, indicating that it has a highly ordered mesoporous structure; after prochloraz is loaded, the peak is obviously reduced, which indicates that prochloraz technical is loaded successfully; after the aldehyde zinc oxide quantum dots are connected, the nanoparticle has a characteristic peak of zinc oxide, which indicates that the zinc oxide is successfully grafted; after a layer of hymexazol original drug is adsorbed on the surface of the nano system, a plurality of hetero peaks appear, which can be characteristic peaks of the hymexazol and indicate that the hymexazol is successfully adsorbed.
Performance test 4
FT-IR spectroscopy for the Cu-MSNs, pro@Cu-MSNs-ZnO/Hym prepared in example 1 is shown in FIG. 3. As can be seen from FIG. 3, about 3443cm -1 The peak at which is attributable to O-H stretching of the hydroxyl groups on the Cu-MSNs surface and the physically adsorbed water molecules, 1074cm -1 Asymmetric telescopic vibration absorption peak of-Si-O-C-, 798cm -1 The symmetrical telescopic vibration absorption peak of-Si-O-Si-shows that the target product Cu-MSNs is successfully prepared; prochloraz and hymexazol are 1698cm in length -1 ，1552cm -1 ，2938cm -1 The equal parts have characteristic absorption peaks, and Pro@Cu-MSNs-ZnO/Hym has characteristic absorption peaks of prochloraz and hymexazol after prochloraz and hymexazol are loaded, which indicates that the medicines prochloraz and hymexazol are successfully loaded.
Performance test 5
The drug loading rate of Pro@Cu-MSNs-ZnO/Hym prepared in example 1 was measured, and the method comprises the following steps:
(1) 20mgPro@Cu-MSNs-ZnO/Hym is mixed with 30mL of methanol, crushed for 6 hours by a cell crusher, and centrifuged at 1500rpm for 10 minutes to obtain a supernatant;
(2) Detecting prochloraz and hymexazol by High Performance Liquid Chromatography (HPLC), wherein the detection conditions of prochloraz are as follows: the mobile phase is acetonitrile: 0.1% formic acid aqueous solution=70:30, sample injection volume v=10 μl, wavelength 220nm, column temperature 30 ℃, retention time 12min; detection conditions of hymexazol: the mobile phase is methanol: 0.1% aqueous formic acid=40:60, sample volume v=5 μl, wavelength 238nm, column temperature 25 ℃, retention time 10min.
The calculated drug loading of prochloraz in Pro@Cu-MSNs-ZnO/Hym is 9.3%, and the drug loading of hymexazol is 14.71%.
Performance test 6
The cumulative release rate of Pro@Cu-MSNs prepared in example 1 was measured, comprising the steps of:
3 groups of 5mg Pro@Cu-MSNs were weighed and evenly suspended in 2mL deionized water containing 0.5% Tween-80 and having pH values of 4.0, 7.0 and 9.0, the suspensions were transferred to dialysis bags, the dialysis bags were sealed in 48mL release bottles containing 0.1% Tween-80 as release medium, release under acidic, neutral and alkaline conditions was simulated, and the beakers were placed in a shaking table at 100 rpm.
The cumulative release rate of Pro@Cu-MSNs-ZnO/Hym in example 1 was determined in agreement with Pro@Cu-MSNs, the only difference being that Pro@Cu-MSNs was replaced with Pro@Cu-MSNs-ZnO/Hym.
The cumulative release curves of Pro@Cu-MSNs and Pro@Cu-MSNs-ZnO/Hym under different pH conditions in example 1 are shown in FIG. 4, and as can be seen from FIG. 4, the drug is released in a large amount within 12 hours before the aldehyde zinc oxide quantum dot is grafted, and the release amount under the acidic condition is greater than that of neutral and alkaline, because of Cu-MSNs-NH 2 Unstable framework and is easy to be H-substituted under acidic condition + Disruption, resulting in burst release of the drug; after the aldehyde zinc oxide quantum dot is grafted, prochloraz burst release is obviously reduced due to the hole blocking effect of zinc oxide, and the analysis of the release behavior of the hymexazol shows that the hymexazol adsorbed on the surface of the material is almost completely released within 24 hours, so that the prochloraz burst release is realized.
Performance test 7
The scanning electron microscope images of Pro@Cu-MSNs-ZnO/Hym prepared in example 1 at different times at pH 4.0 are shown in FIG. 5. As can be seen from fig. 5, the pro@cu-MSNs-ZnO/Hym nano system slightly degraded in structure and significantly blurred in edge at 24 hours; at 48 hours, the nano system is obviously deformed, and the nano system is partially crashed, so that fragments can be obviously seen to fall off from the nano system; finally, 72 hours, the shedding fragments of the nanosystems can be seen, indicating the breakdown and prochloraz release of the whole nanosystems.
Performance test 8
The prochloraz technical, hymexazol technical, and the mixture of prochloraz technical and hymexazol technical, and the Pro@Cu-MSNs-ZnO/Hym prepared in example 1 have a sterilization effect on Rhizoctonia solani for 14 days as shown in FIG. 6.
The prochloraz technical, the hymexazol technical, the mixture of prochloraz technical and hymexazol technical, and the Pro@Cu-MSNs-ZnO/Hym prepared in example 1 are shown in table 2.
As can be seen from table 2 and fig. 6, EC50 of prochloraz and hymexazol against rhizoctonia are 0.1602mg/L and 93.82mg/L, respectively, EC50 of a mixture of prochloraz and hymexazol (prochloraz: hymexazol = 1:1.5) is 0.1924mg/L, and EC50 of pro@cu-MSNs-ZnO/Hym (effective concentration ratio of 1:1.5) is 0.1642mg/L after nano-carrier encapsulation; as can be seen from table 2, the synergy coefficient (SR) of the mixture of prochloraz and hymexazol is 2.07, and the SR of pro@cu-MSNs-ZnO/Hym is 2.43, indicating that the synergy of the nano system pro@cu-MSNs-ZnO/Hym against rhizoctonia is more obvious. The possible reason is that the system has smaller particle size, better dispersibility than prochloraz original drug in a culture medium, more contact opportunities with hypha and easier penetration into the hypha to play a role in sterilization. And the drug release amount in the burst release stage is larger, the inhibition effect on the rhizoctonia solani is good, and the drug is released continuously in the later stage, so that the drug can be maintained at a certain concentration level, and therefore, the good inhibition effect is shown.
TABLE 2 Prochloraz (Pro), hymexazol (Hym), mixture of Prochloraz and hymexazol (Pro+ Hym), the Pro@Cu-MSNs-ZnO/Hym (NPs) prepared in example 1 against Rhizoctonia solani
Example 2
The preparation method of the intelligent degradable silicon-based nano-pesticide fertilizer is the same as that in the embodiment 1, and the difference is that prochloraz and Cu-MSNs-NH in the n-hexane solution of prochloraz in the step (3) 2 The mass ratio of (2): 1, a step of; the amount of the hydroformylation ZnOQDs in the step (7) is 150mg; the amount of hymexazol in step (8) was 250mg.
Example 3
The preparation method of the intelligent degradable silicon-based nano-pesticide fertilizer is the same as that in the embodiment 1, and the difference is that prochloraz and Cu-MSNs-NH in the n-hexane solution of prochloraz in the step (3) 2 The mass ratio of (2) is 4:1, a step of; the amount of the hydroformylation ZnOQDs in the step (7) is 200mg; the amount of hymexazol in step (8) is 350mg.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The preparation method of the intelligent degradable silicon-based nano-pesticide fertilizer is characterized by comprising the following steps of:
(1) Preparation of Cu-MSNs: mixing cetyl trimethyl ammonium bromide, ammonia water solution and ethanol solution of tetraethoxysilane, adding ethanol solution of copper nitrate and ethanol solution of tetraethoxysilane after mixing, and performing hydrothermal reaction to obtain Cu-MSNs;
(2) Preparation of aminated Cu-MSNs: mixing Cu-MSNs, methanol and 3-aminopropyl triethoxysilane to obtain Cu-MSNs-NH 2 Namely, the aminated Cu-MSNs;
(3) Preparation of Pro@Cu-MSNs: n-hexane solution of prochloraz, cu-MSNs-NH 2 Mixing and drying to obtain Pro@Cu-MSNs;
(4) Preparation of ZnO QDs: heating absolute ethyl alcohol, then adding zinc acetate and magnesium acetate, and mixing to obtain a mixed solution of zinc acetate and magnesium acetate;
adding a mixed solution of zinc acetate and magnesium acetate into an absolute ethyl alcohol solution of sodium hydroxide to react to obtain zinc oxide quantum dots, namely ZnO QDs;
(5) Preparation of aminated ZnO QDs: mixing ZnO QDs with N, N-dimethylformamide for dispersion, heating to a reaction temperature, and adding 3-aminopropyl triethoxysilane for reaction to obtain aminated ZnO QDs;
(6) Preparation of aldehyde ZnO QDs: mixing 4-formylbenzoic acid, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide, N-dimethylformamide and aminated ZnO QDs to obtain aldehyde ZnO QDs;
(7) Preparation of Pro@Cu-MSNs-ZnO: mixing aldehyde ZnO QDs, tris buffer solution and Pro@Cu-MSNs to obtain Pro@Cu-MSNs-ZnO;
(8) Preparation of Pro@Cu-MSNs-ZnO/Hym: dispersing hymexazol in deionized water, and then adding Pro@Cu-MSNs-ZnO nano particles to obtain Pro@Cu-MSNs-ZnO/Hym, namely the intelligent degradable silicon-based nano medical fertilizer;
the mass volume ratio of tetraethoxysilane in the ethanol solution of the hexadecyl trimethyl ammonium bromide, the ammonia water solution and the tetraethoxysilane added for the first time in the step (1) is 400-700 mg: 100-500 mL: 0.1-0.4 mL, wherein the volume ratio of tetraethoxysilane to ethanol in the ethanol solution of the tetraethoxysilane added for the first time is 0.1-0.4: 3 to 6;
the mass volume ratio of the hexadecyl trimethyl ammonium bromide in the step (1), the copper nitrate in the ethanol solution of the copper nitrate, the ethanol in the ethanol solution of the copper nitrate and the tetraethoxysilane in the ethanol solution of the tetraethoxysilane added for the second time is 400-700 mg: 35-42 mg: 3-7 mL: 0.5-2.5 mL, wherein the volume ratio of tetraethoxysilane to ethanol in the ethanol solution of the tetraethoxysilane added for the second time is 0.5-2.5: 4 to 8;
the mass volume ratio of the Cu-MSNs to the methanol to the 3-aminopropyl triethoxysilane in the step (2) is 300-700 mg: 30-80 mL: 0.1-0.4 mL;
the prochloraz and Cu-MSNs-NH in the n-hexane solution of prochloraz in the step (3) 2 The mass ratio of the prochloraz to the n-hexane is 2-4:0.5-2, and the concentration of the prochloraz to the n-hexane solution is 1-20 mg/mL;
the mass volume ratio of the absolute ethyl alcohol to the zinc acetate to the magnesium acetate in the step (4) is 2-4 mL: 40-60 mg: 4-6 mg, wherein the mass ratio of the sodium hydroxide in the anhydrous ethanol solution of the zinc acetate and the sodium hydroxide is 3-6: 0.5-2, wherein the mass volume ratio of the sodium hydroxide to the absolute ethyl alcohol in the absolute ethyl alcohol solution of the sodium hydroxide is 100-120 mg:1 to 1.2mL;
the mass volume ratio of ZnO QDs, N-dimethylformamide and 3-aminopropyl triethoxysilane in the step (5) is 90-115 mg: 10-20 mL: 40-60 mu L;
the mass volume ratio of the 4-formylbenzoic acid, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the N-hydroxysuccinimide, the N, N-dimethylformamide and the aminated ZnO QDs in the step (6) is 50-70 mg: 65-80 mg: 60-70 mg: 3-7 mL: 120-160 mg;
the mass volume ratio of the hydroformylation ZnO QDs, the Tris buffer solution and the Pro@Cu-MSNs in the step (7) is 0.5-2 mg: 0.05-0.25 mL: 0.5-2 mg;
in the step (8), the mass ratio of the hymexazol to the water to the Pro@Cu-MSNs-ZnO is 10-30:1: 5 to 20.
2. The method for preparing the intelligent degradable silicon-based nano-pesticide fertilizer according to claim 1, wherein the hydrothermal reaction conditions in the step (1) are as follows: the temperature is 30-60 ℃ and the time is 12-24 h;
the mixing conditions in step (2): mixing for 15-24 h at 20-30 ℃;
the mixing conditions in step (3): mixing for 15-24 h at 25-35 ℃;
the drying temperature in the step (3) is 40-60 ℃, and the drying time is 8-12 h;
the heating temperature in the step (4) is 70-90 ℃;
the reaction conditions in step (4): reacting for 6-12 h under the dark condition;
the reaction temperature in the step (5) is 100-130 ℃, and the reaction time is 15-25 min.
3. The method for preparing the intelligent degradable silicon-based nano-pesticide fertilizer according to claim 1 or 2, wherein the mixing conditions in the step (6) are as follows: mixing for 15-24 h at 20-30 ℃;
the mixing conditions in step (7): mixing for 10-15 h at 20-30 ℃ under the condition of avoiding light;
the mixing conditions in step (8): mixing for 20-25 h at 20-30 ℃ under the condition of avoiding light.
4. The intelligent degradable silicon-based nano-pesticide fertilizer prepared by the preparation method of the intelligent degradable silicon-based nano-pesticide fertilizer according to any one of claims 1 to 3.
5. The use of the intelligent degradable silicon-based nano-pesticide fertilizer in plant growth.
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