LU505016B1 - An amphiphilic xylan polymer, preparation method therefor and application thereof in pesticide - Google Patents
An amphiphilic xylan polymer, preparation method therefor and application thereof in pesticide Download PDFInfo
- Publication number
- LU505016B1 LU505016B1 LU505016A LU505016A LU505016B1 LU 505016 B1 LU505016 B1 LU 505016B1 LU 505016 A LU505016 A LU 505016A LU 505016 A LU505016 A LU 505016A LU 505016 B1 LU505016 B1 LU 505016B1
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- LU
- Luxembourg
- Prior art keywords
- xylan
- avermectin
- amphiphilic
- emulsion
- water
- Prior art date
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- 150000004823 xylans Chemical class 0.000 title claims abstract description 85
- 229920001221 xylan Polymers 0.000 title claims abstract description 83
- 229920000642 polymer Polymers 0.000 title claims abstract description 55
- 239000000575 pesticide Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000005660 Abamectin Substances 0.000 claims abstract description 98
- RRZXIRBKKLTSOM-XPNPUAGNSA-N avermectin B1a Chemical compound C1=C[C@H](C)[C@@H]([C@@H](C)CC)O[C@]11O[C@H](C\C=C(C)\[C@@H](O[C@@H]2O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](O)[C@@H](OC)C3)[C@@H](OC)C2)[C@@H](C)\C=C\C=C/2[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\2)O)C[C@H]4C1 RRZXIRBKKLTSOM-XPNPUAGNSA-N 0.000 claims abstract description 98
- 239000000839 emulsion Substances 0.000 claims abstract description 89
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000005639 Lauric acid Substances 0.000 claims abstract description 40
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims abstract description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 25
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 17
- 241000607479 Yersinia pestis Species 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003090 pesticide formulation Substances 0.000 claims description 4
- 241000985245 Spodoptera litura Species 0.000 claims description 3
- 230000002265 prevention Effects 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 241000244206 Nematoda Species 0.000 claims description 2
- 241000500437 Plutella xylostella Species 0.000 claims description 2
- 241000570011 Pomacea canaliculata Species 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 43
- 238000011161 development Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 30
- 239000000693 micelle Substances 0.000 description 18
- 240000007124 Brassica oleracea Species 0.000 description 15
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 15
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 15
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 15
- 230000002209 hydrophobic effect Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920002488 Hemicellulose Polymers 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000002296 dynamic light scattering Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 239000003937 drug carrier Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002088 nanocapsule Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000000447 pesticide residue Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000003075 superhydrophobic effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- MPDGHEJMBKOTSU-YKLVYJNSSA-N 18beta-glycyrrhetic acid Chemical compound C([C@H]1C2=CC(=O)[C@H]34)[C@@](C)(C(O)=O)CC[C@]1(C)CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@H](O)C1(C)C MPDGHEJMBKOTSU-YKLVYJNSSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000500441 Plutellidae Species 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009666 routine test Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
- A01N25/02—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 liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- 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
- A01N25/10—Macromolecular compounds
-
- 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- 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
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Insects & Arthropods (AREA)
- General Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention discloses an amphiphilic xylan polymer, a preparation and an application thereof in pesticide preparations. The preparation method for the amphiphilic xylan polymer comprises the following steps: dissolving a xylan and lauric acid in dimethyl sulfoxide, adding a coupling agent N,N'-dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, reacting in a protective gas atmosphere, centrifuging to remove a reaction byproduct N-N'-dicyclohexylurea, washing with absolute ethyl alcohol, and extracting and purifying with a mixed solution of acetone and isopropanol, and drying in vacuum to obtain a xylan grafted lauric acid polymer, namely the amphiphilic xylan polymer. The amphiphilic xylan polymer prepared by the method is used as a pesticide carrier for preparing an emulsion in water containing avermectin, so that the storage stability and the wettability can be improved, and an effective way is provided for the development of green pesticide preparations.
Description
Specification LU505016
An amphiphilic xylan polymer, preparation method therefor and application thereof in pesticide
The present invention relates to the field of pesticide preparations, in particular relates to an amphiphilic xylan polymer, preparation method therefor and application thereof in pesticide.
Pesticides are the most effective means to prevent and control pests. However, for a long time, limited by pesticide formulations, environment, methods of use and other application conditions, the effective utilization rate of pesticides is low, resulting in excessive use of pesticides, excessive pesticide residues and environmental pollution. In recent years, the use of nanomaterials and advanced technology to prepare efficient and safe green pesticide formulations can improve the dispersion and stability of pesticides, promote the adhesion and deposition of pesticides to target crops, and reduce the amount of pesticides and residual pollution, so as to achieve the reduction and efficiency of pesticides. Avermectin is a new biological pesticide with broad-spectrum insecticidal, acaricidal and nematicidal activity. However, the avermectin has poor photostability and solubility, and is easy to decompose under ultraviolet light, which leads to the increase of actual dosage in the application process, thus causing harm to plants and the environment. The solubility and stability of the avermectin can be improved by using nano-micelles as the carrier of avermectin.
Nanomicelles with core-shell structure formed by self-assembly of amphiphilic block polymers are a new type of nanomaterials with excellent physicochemical properties such as quantum effect, small size effect, surface and interface effect, which can be used to load insoluble pesticide molecules and improve the stability and dispersibility of insoluble pesticides. This is because the hydrophobic region of the micelle core can load hydrophobic pesticide molecules to increase their solubility and stability, while the hydrophilic shell outside the micelle separates the internal encapsulated molecules from the external environment to prevent the interaction of encapsulated molecules and the influence of the external environment, thus improving the stability 1 of pesticide molecules. LU505016
Xylan is the most abundant natural macromolecular polymer in nature except for cellulose, which has the advantages of wide source, low cost, good biodegradability and biocompatibility, and the degraded products will not cause secondary pollution to the environment, so it is an ideal green pesticide carrier. However, commercial xylans usually exhibit different water solubility due to their different extraction sources and methods, which cannot well embed drugs or form complexes with them. At present, the modification methods of xylan mainly focus on grafting active groups onto xylan (such as Chinese patent application CN108079001A), or preparing hydrogels (such as Chinese patent application CN111961230A) to achieve the delivery of drugs or biomacromolecules. Or the xylan is modified to enhance the medicinal activity of the xylan (such as Chinese patent application CN110698594A and CN111961144A).
An amphiphilic compound is composed of a hydrophilic end and a hydrophobic end, and the amphiphilic compound can self-assemble into a micelle in water, the cavity of the hydrophobic end can interact with various hydrophobic drugs and is stabilized in an aqueous solution, and the hydrophilic end can protect the drugs from being influenced by an external environment. There is no report on the synthesis of amphiphilic compounds by modifying xylan and its application in pesticides. Therefore, it is urgently necessary to develop a xylan carrier with easily available lipophilic end, simple preparation process and low preparation cost, which can be applied to pesticides.
The first objective of the present invention is to overcome the disadvantages and deficiencies of the prior art, and provide a preparation method for an amphiphilic xylan polymer.
The second objective of the present invention is to provide the amphiphilic xylan polymer prepared by the method described.
The third objective of the present invention is to provide an application of the amphiphilic xylan polymer in preparing a pesticide carrier or a pesticide formulation.
The fourth objective of the present invention is to provide an emulsion in water containing 4.4% avermectin (Avermectin EW).
The fifth objective of the present invention is to provide a preparation method for the emulsion in water containing 4.4% avermectin.
The sixth objective of the present invention is to provide an application of the emulsion in water containing 4.4% avermectin for preventing and controlling pests.
Objectives of the present invention are realized by the following technical solutions: 2
A preparation method for an amphiphilic xylan polymer comprises the following steps: ; ,Ç dissolving a xylan and lauric acid in dimethyl sulfoxide (DMSO), then adding a coupling ° agent N,N'-dicyclohexylcarbodiimide (DCC) and a catalyst 4-dimethylaminopyridine (DMPA), reacting in a protective gas atmosphere, then centrifugating to remove a reaction byproduct N,N"- dicyclohexylurea, washing with an an absolute ethyl alcohol, and extracting and purifying with a mixed solution of acetone and isopropanol, and drying in vacuum to obtain a xylan grafted lauric acid polymer, namely an amphiphilic xylan polymer.
The mass ratio of the xylan to the lauric acid is 1 to 2:2, preferably 1 to 1.5:2, and more preferably 1.32:2.
The mass ratio of the coupling agent N,N'-dicyclohexylcarbodiimide (DCC) to the catalyst 4-dimethylaminopyridine (DMPA) is 6 to 7:1, preferably 6 to 6.5:1, more preferably 6.24:1.
The mass ratio of the sum of the coupling agent and the catalyst to the xylan is 1:1.5 to 2, preferably 1:1.81.
The usage of the dimethyl sulfoxide is calculated according to the ratio of 35 to 40 mL of the dimethyl sulfoxide per gram of the xylan.
The protective gas is nitrogen.
The time for reacting is 60 to 120 minutes.
The volume ratio of the acetone to the isopropanol in the mixed solution of acetone and isopropanol is preferably 1:1.
An amphiphilic xylan polymer prepared by any of the above-described methods.
The amphiphilic xylan polymer is applied to the preparation of a pesticide carrier or a pesticide preparation.
The pesticide is preferably avermectin and preferably avermectin Bla technical.
An emulsion in water containing 4.4% avermectin comprises the following components in percentage by mass: 4.4% of avermectin, 1% to 2% of the above-described amphiphilic xylan polymer, 24% to 25% of cyclohexanone, 3% to 5% of emulsifier T-028, 2% to 6% of emulsifier 7-029 and a balance of water.
An emulsion in water containing 4.4% avermectin preferably comprises the following components in percentage by mass: 4.4% of avermectin, 2% of the above-described amphiphilic xylan polymer, 25% of cyclohexanone, 5% of emulsifier T-028, 6% of emulsifier Z-029 and a balance of water. 3
The water is preferably deionized water. LU505016
A preparation method for the emulsion in water containing 4.4% avermectin comprises the following steps: (1) dissolving avermectin in cyclohexanone, adding emulsifier T-028, and stirring evenly to be used as an oil phase; (2) adding the above-described amphiphilic xylan polymer (X-LA) into water, and dissolving the amphiphilic xylan polymer (X-LA) under the assistance of ultrasound to obtain a X-LA solution; and (3) adding the X-LA solution into the oil phase, oscillating and uniformly mixing at the constant temperature of 50 °C, then adding emulsifier Z-029, adding water to make up to 100 % while stirring, and continuously oscillating and mixing at the constant temperature of 50 °C to obtain the emulsion in water containing 4.4% avermectin.
The concentration of the X-LA solution described in the step (3) is preferably 72 mg/mL.
The time of oscillating and mixing at the constant temperature in the step (3) is more than 30 minutes.
The emulsion in water containing 4.4% avermectin is applied in prevention and control of pest.
The pests comprise at least one of mites, nematodes, prodenia litura, diamondback moths, golden apple snails and the like.
Relative to the prior art, the present invention has the following advantages and effects:
In the present invention, the lauric acid is firstly adopt to carry out amphiphilic graft modification on the xylan to prepare the xylan grafted lauric acid polymer (X-LA), and then it is used as a pesticide carrier to prepare the emulsion in water containg 4.4% avermectin. The emulsion in water has good storage stability (low temperature stability and heat storage stability) and wettability, providing an effective way for the development of the green pesticide preparation of the amphiphilic xylan polymer.
Fig. 1 shows a synthesis process diagram of a xylan grafted lauric acid polymer of the present invention.
Fig. 2 shows a FTIR spectrum of a xylan and a xylan grafted lauric acid polymer of the present invention. 4
Fig. 3 shows a "H-NMR spectrum of a xylan and a xylan grafted lauric acid polymer of the
LU505016 present invention.
Fig. 4 shows a transmission electron micrograph of a xylan grafted lauric acid polymer (X-
LA), an emulsion in water containing 4.4% avermectin, and a commercial emulsion in water(Commercial EW); wherein, A is the X-LA; B is the emulsion in water containing 4.4% avermectin; and C is the commercial emulsion in water.
Fig. 5 shows a graph of a change in particle size of an emulsion in water containing 4.4% avermectin and a commercial emulsion in water under different storage conditions.
Fig. 6 shows a particle size distribution of an emulsion in water containing 4.4% avermectin and a commercial emulsion in water under different storage conditions, where A is the emulsion in water containing 4.4% avermectin and B is the commercial emulsion in water.
Fig. 7 shows a graph of a change in surface tension of an emulsion in water containing 4.4% avermectin and a commercial emulsion in water under different storage conditions.
Fig. 8 shows a statistical diagram of liquid retention rate of an emulsion in water containing 4.4% avermectin and a commercial emulsion in water on cabbage leaves.
The present invention will be described in further detail below with reference to examples, but embodiments of the present invention are not limited thereto. Unless otherwise specified, the reagents, methods, and devices used in the present invention are conventional in the art. Test methods for which specific test conditions are not specified in the following examples are generally based on routine test conditions or on test conditions recommended by the manufacturer.
Unless otherwise specified, the reagents and starting materials used in the present invention are commercially available.
Example 1 1. Materials and Methods 1.1 Materials and apparatus 1.1.1 Material
Materials include the following: avermectin Bla technical (97% purity, CAS number: 65195- 55-3); xylan (molecular weight (150.13000) n, 99% purity, CAS accession number: 9014-63-5); lauric acid (LA), dimethyl sulfoxide (DMSO), N,N'-dicyclohexylcarbodiimide (DCC) and 4- dimethylaminopyridine (DMPA) with being analytically pure (Aladin Reagent Co., Ltd.); acetone, isopropanol, cyclohexanone and absolute ethanol with being analytically pure (Guangzhou
Chemical Reagent Factory); emulsifier Z-029 and emulsifier T-028 (purchased from Guangzhou
Yueyouyan Photoelectric Materials Co., Ltd.); and commercial emulsion in water containing 4.47%, 505016 avermectin (purchased from Jiangmen Plant Protection Co., Ltd.). 1.1.2 Apparatus
Apparatus include the following: RW20 stirrer (IKA, Germany); centrifuge, DZF-6055 vacuumdrying oven (Shanghai Yiheng Scientific Instrument Co., Ltd.); TEN-SOR27 fourier infrared spectrometer (Bruker, Germany), AVIII-400MHz nuclear magnetic resonance spectrometer (Bruker, Germany); KQ-600GKDV ultrasonic cleaning machine (Kunshan
Ultrasonic Instrument Co., Ltd.); JET-2100 transmission electron microscope (Japan Electronics
Co., Ltd.); Nano-ZS & MPT-2 dynamic light scattering instrument (Malvern Instruments, UK);
ZJ-7000 optical contact angle measuring instrument (Shenzhen Zhijia Instrument Equipment Co.,
Ltd.); and SHZ-B constant temperature water bath oscillator (Jintan Chengxi Chunlan Instrument
Factory). 1.2 Method 1.2.1 Preparation and characterization of an amphiphilic xylan polymer
The synthesis process of the xylan grafted lauric acid polymer is shown in Figure 1. The xylan grafted lauric acid polymer (X-LA) is an amphiphilic substance grafted with the lauric acid molecules on the xylan skeleton through esterification reaction, and the preparation steps are as follows: weighing 6.6 g of the xylan and adding into 150 mL of the dimethyl sulfoxide to obtain a lauric acid/DMSO solution; weighing 10.016 g of the lauric acid and adding into 50 mL of the dimethyl sulfoxide to obtain a xylan/DMSO solution; weighing 10.3 g of a coupling agent DCC and adding into 50 mL of the dimethyl sulfoxide to obtain a DCC/DMSO solution; then adding the lauric acid/DMSO solution to the xylan/DMSO solution and stirring for 10 min, adding slowly 1.65 g of the catalyst DMAP, and then adding dropwise the DCC/DMSO solution (with a mass ratio of the xylan to the lauric acid being about 1.32:2, a mass ratio of the coupling agent DCC to the catalyst DMPA being about 6.24:1, and the total addition amount of the coupling agent and the catalyst being 1.81 parts (mass ratio) of the coupling agent and the catalyst according to 1 part of xylan in the reaction system), inducting nitrogen for protection, reacting for 60 to 120 minutes at room temperature, then centrifuging to remove a by-product N-N'-dicyclohexylurea, washing with the absolute ethyl alcohol, extracting and purifying with acetone/isopropanol (v:v = 1:1), drying in vacuum to obtain a product. The product is characterized by TEN-SOR27 fourier transform 6 infrared spectrometer and AVIII-400 MHz nuclear magnetic resonance spectrometer, and the, 505016 degree of substitution is calculated. 1.2.2 Preparation of the emulsion in water containing 4.4% avermectin
The emulsion in water containing 4.4% avermectin is prepared by a phase inversion method.
The following steps are performed: dissolving the avermectin in a proper amount of cyclohexanone, adding a small amount of the emulsify T-028, and stirring evenly to be used as an oil phase; adding the xylan grafted lauric acid polymer (X-LA) into ultrapure water and dissolving under the assistance of ultrasound to obtain a X-LA solution with a concentration of 72 mg/mL, adding a small amount of the X-LA solution into the oil phase and oscillating at 50 °C for 30 min, then adding a small amount of the emulsifier Z-029 to make up 100 g of deionized water, stirring continuously while adding water to complete a phase inversion process, oscillating at the constant temperature of 50 °C for 30 min to obtain the emulsion in water containing 4.4% avermectin (W/V).
The mass fractions of the avermectin, the cyclohexanone, the X-LA, the emulsifier T-028 and the emulsifier Z-029 in the emulsion in water are 4.4%, 25%, 2%, 5% and 6% respectively. 1.2.3 Determination of storage stability of the emulsion in water containing avermectin
According to national standards GB/T 19136 2021 and GB/T 19137 2003, the samples of the emulsion in water containing 4.4% avermectin are stored at (54 + 2) °C for 14 days and (0 + 2) °C for 7 days, respectively. The thermal storage stability and low temperature stability of the emulsion in water containing 4.4% avermectin and the commercial emulsion in water are tested, and the emulsion in water standing still for 14 days at room temperature is used as control. The changes in the content of active ingredient of avermectin in EW is determined according to the method of
GB 2763-2021, and the degradation rate of the avermectin under various storage conditions is calculated with an emulsion in water containing 5% avermectin ( LUOJIN ®) sold in the market as the control:
Degradation rate = (content before treatment-content after treatment) / content before treatment* 100 1.3 Performance Characterization of Avermectin EW 1.3.1 Morphological observation
The emulsion in water containing 4.4% avermectin and the commercial EW are diluted to a certain concentration (1:500, v/v), and a small amount of the diluted solution is dropped on a 200- mesh copper mesh. After natural air drying for 2 minutes, the solution is negatively stained with a 7 newly prepared 2% (w/v) phosphotungstic acid for 2 minutes. After drying at room temperature, 505016 the morphology is observed by JET-2100 transmission electron microscope (TEM). 1.3.2 Particle size and its distribution
The emulsion in water containing 4.4% avermectin and the commercial EW are diluted 1000 times respectively, and a small amount of the diluted solution is filtered through a 0.45 m filter membrane, and the particle size and its distribution of the emulsion are measured by the Nano-ZS & MPT-2 dynamic light scattering instrument at a scattering angle of 90 °. Measurements are repeated for three times, and the average value is taken. 1.3.4 Zeta potential determination
The zeta potentials of the emulsion in water containing 4.4% avermectin and the commercial
EW are measured respectively by Nano-ZS & MPT-2 dynamic light scattering instrument.
Measurements are repeated for three times, and the average value is taken. 1.3.5 Determination of surface tension
After diluting the emulsion in water containing 4.4% avermectin and the commercial EW for 1000 times respectively, the surface tension is measured by ZJ-7000 optical contact angle meter with pendant drop method, and the average value is obtained after 10 times of repetition with ultrapure water as the control. 1.3.6 Determination of liquid retention on cabbage leaves
To measure the liquid retention rate of the solution on the cabbage leaves, fresh cabbage leaves with a diameter of 6.6 cm and a uniform size (cabbage at the six-leaf stage) are cut with a puncher, soaked in the emulsion in water containing 4.4% avermectin (with 1:1000 dilution) and the commercial EW (with 1:1000 dilution) for 1 minute, then lifted vertically, and weighed when the blade stops dripping the solution. Ultrapure water is used as the control. Measurements are repeated for three times, and the average value is taken.
The formula for liquid retention is as follows:
Liquid retention = (my — m9)/A (1)
In the formula, mg and m, are respectively the weight of the leaf before and after soaking, and A is the surface area of the leaf. 1.4 Determination of entrapment rate and entrapment capacity of the avermectin loaded by the X-LA as drug carrier
The method of GB 2763-2021 is used to determine the entrapment rate and entrapment 8 capacity of an avermectin loaded capsules (the emulsion in water containing 4.4% avermectin), 5950 16 using X-LA as the carrier, which is calculated according to the following formula:
Entrapment rate (%) = the mass of avermectin embedded in nanocapsules/the total mass of avermectin invested * 100
Drug loading capacity (%) = the mass of avermectin embedded in nanocapsules/the total mass of nanocapsules invested *100 2. Results and analysis 2.1 Structural characterization results of amphiphilic hemicellulose derivatives
Fig. 2 is the FTIR spectrum of the xylan and the xylan grafted lauric acid polymer (X-LA).
The FT-IR spectra of the xylan grafted with the lauric acid showed obvious changes, and the absorption peaks at 1744 cm! and 1256 cm”! are the characteristic absorption peaks of ester carbonyl (C = O) and ether bond (C-O) on the side chain of the lauric acid, respectively, which indicates that the side chain of the lauric acid is successfully grafted onto the main chain of the xylan.
Fig. 3 is a "H-NMR spectrum of the xylan and the xylan grafted lauric acid polymer (X-
LA). In the spectrum of the xylan, there are very weak signal peaks around 1.22 ppm and 0.84 ppm, because the xylan is a polysaccharide composed of many kinds of sugar groups, with a very small amount of CH2 and CH; on the side chains. After grafting of the xylan with the lauric acid, two strong signal peaks appeare at 1.23 ppm and 0.84 ppm respectively, in which 0.84 ppm is the chemical shift of methyl (CH3) on the side-chain of the lauric acid molecule. The strong signal peaks at 1.23, 1.49 and 2.26 ppm correspond to the chemical shifts of methylene (CH2) on the side chain of the lauric acid, indicating that the hydrophobic side chain of the lauric acid is successfully grafted onto the xylan chain.
The degree of substitution (DS) of the lauric acid in the xylan graft polymer can be calculated according to formula (2):
DS = —1a/3 (2) (IHı+IH4)/2
In the formula, Ia, In1, and IH represent the chemical shift integral areas of H on the methyl group (CH3) of the hydrophobic side chain and H1 and H4 on the hemicellulose structural unit, respectively. In this study, the substitution degree of the xylan grafted lauric acid polymer is about 0.318. 9
2.2 Performance characterization of EW LU505016 2.2.1 Morphological observation
The transmission electron micrographs of the X-LA, the emulsion in water containing 4.4% avermectin and the commercial EW are shown in Figure 4. The amphiphilic xylan polymer (X-
LA) self-assembles to form spherical nano-micelles with a particle size of less than 100 nm (Figure 4A). The particles of the emulsion in water containing 4.4% avermectin prepared with the X-LA maintained the size of the X-LA micelles, and the particle morphology is clearly visible in the shape of a smooth sphere (Fig. 4B). However, the particles of the commercial EW are irregular in shape, and the distribution of the particles is disorderly, and the particle size is greater than 100 nm (Fig. 4C). 2.2.2 Storage stability
The performance characterization of the emulsion in water containing 4.4% avermectin prepared by the present invention under different storage conditions is shown in Table 1, the degradation rate of the avermectin under different storage conditions is shown in Table 2, the particle size change is shown in Figure 5, and the particle size distribution is shown in Figure 6. It can be seen from Figure 5 that the indicators of the emulsion in water containing 4.4% avermectin prepared by the X-LA after cold storage are similar to those stored at room temperature, the average particle size after thermal storage is only 122.9 nm, the PDI index is about 0.2, and there is only one particle size distribution peak under different storage conditions (Figure 6A), and the total active ingredient content remains unchanged (Table 1). The results showed that the emulsion in water containing 4.4% avermectin prepared by the X-LA has good dispersibility. The emulsion particles are uniformly distributed, and the storage stability is good, especially the thermal storage stability. However, after cold storage and thermal storage, the commercial EW shows obvious chromatographic phenomena, in which the average particle size after thermal storage increases from 156.2 nm to 588.9 nm (Fig. 5), the PDI index is 0.61, and three particle size distribution peaks appeared after thermal storage (Fig. 6B), and the emulsion particles are obviously aggregated, indicating that the storage stability of the commercial EW is poor, especially the thermal storage stability.
In addition, by comparing with the particle sizes of the emulsion in water particles in Table 1 and Fig. 4, it can be seen that the particle size in the TEM image is smaller than the average particle size obtained by the dynamic light scattering method, which may be an error of the detection method. The hydrodynamic diameter of the solvated micelles is detected by dynamic light, 505016 scattering, while the TEM images are observed under high vacuum conditions, and the micelles show a certain degree of dehydration shrinkage during this process.
The same conclusion can be obtained by analyzing the surface zeta potential of the emulsion in water (Table 1). Under the same conditions, the zeta potential of the emulsion in water containing 4.4% avermectin is higher than that of the commercial EW. The higher surface charge value makes the particles repel each other and is not easy to aggregate due to electrostatic interaction, thereby improving the stability of the emulsion in water.
Table 1 Performance characterization of the emulsion in water containing 4.4% avermectin under different storage conditions
Average particle Zeta
Storage conditions Samples PDI size/nm potential/mV
The emulsion in water 225.5 0.204 -1.091
Room temperature containing 4.4% avermectin (Standing still for 14 The emulsion in water days) containing 5% avermectin 156.2 0.084 -0.741 (LUOJIN ®)
The emulsion in water 229.8 0.21 -1.292
Cold storage containing 4.4% avermectin (Stored at 0 + 2 °C for The emulsion in water 7 days) containing 5% avermectin 168.0 0.11 -0.884 (LUOJIN ®)
The emulsion in water 122.9 0.26 -7.677
Thermal reservoir containing 4.4% avermectin (Stored at 54 + 2 °C The emulsion in water for 14 days) containing 5% avermectin 588.9 0.61 -1.233 (LUOJIN ®) 11
Table 2 Degradation rate of the avermectin under different storage conditions
Appearance
Active ingredient | Degradati
Storage conditions Samples and shape content/% on rate/% change
The emulsion in water
Unchanged 4.3
Room temperature containing 4.4% avermectin (Standing still for 14 The emulsion in water days) containing 5% avermectin Unchanged 5.0 (LUOJIN ®)
The emulsion in water
Unchanged 4.3
Cold storage containing 4.4% avermectin (Stored at 0°C +2 °C The emulsion in water for 7 days) containing 5% avermectin Unchanged 5.0 (LUOJIN ®)
The emulsion in water
Unchanged 4.3 2.27 containing 4.4% avermectin
Thermal reservoir Occurring (Stored at 54°C + The emulsion in water detail 2 °C for 14 days) containing 5% avermectin stratification 4.0 20 (LUOJIN ®) and precipitation 2.2.3 Wettability results
The wettability of pesticide solution is the key factor affecting the effective utilization of pesticide, and better wettability can promote the wetting, spreading and deposition of pesticide 12 solution on target crops. LU505016
Fig. 7 shows the surface tension results of the EW. The surface tension of the emulsion in water containing 4.4% avermectin prepared with the X-LA under different storage conditions is about 52 mN/m, which is lower than that of ultrapure water. However, the surface tension of the commercial EW increases after both cold storage and thermal storage. Therefore, the emulsion in water containing 4.4% avermectin has lower surface tension and higher stability under different storage conditions compared with the commercial EW.
Fig. 8 shows the liquid retention rate of the emulsion in water on cabbage leaves. It can be seen from Fig. 8 that the liquid retention rate of the emulsion in water containing 4.4% avermectin on cabbage leaves is greater than that of ultrapure water, while that of the commercial emulsion in water is less than that of ultrapure water. This is because the emulsion in water containing 4.4% avermectin prepared by the X-LA has a low surface tension (Fig. 7) and is easy to wet and spread on cabbage leaves. In addition, the X-LA is an amphiphilic hemicellulose polymer, which is similar to the hydrophobically modified cellulose polymer and is a non-ionic surfactant. The addition of non-ionic surfactant can reduce the interfacial tension of cabbage leaves (superhydrophobic interface), thus inhibiting solution splashing and making pesticides adhere to and deposit on cabbage leaves. 2.3 Entrapment rate and entrapment capacity of the avermectin loaded by the X-LA as drug carrier
The entrapment rate and entrapment capacity of the avermectin loaded by the X-LA as drug carrier (the emulsion in water containing 4.4% avermectin) reached 65.72% and 4.40%, respectively (Table 3).
Table 3 Entrapment rate and entrapment capacity of the avermectin loaded by the X-LA me 65.72 4.40 loaded by the X-LA
As a natural polymer material, xylan has the advantages of wide source, low cost, good biocompatibility, biodegradability and the like. The nano pesticide preparation taking the xylan as a carrier can reduce the pesticide dosage and realize the target release of pesticide active substances, thereby improving the utilization rate of pesticides and reducing pesticide residues. The xylan is 13 biodegradable. The degraded product has no secondary pollution and is friendly to the environment, 505016
Nanomicelles with core-shell structure formed by self-assembly of amphiphilic block polymers are excellent carriers for poorly soluble pesticides, and their small size and large specific surface area can improve the dispersion and stability of poorly soluble pesticide molecules. In addition, some amphiphilic natural polymers can be used as non-ionic surfactants, which can inhibit the splashing of pesticide solution on cabbage (super-hydrophobic interface) leaves, increase the adhesion and deposition of pesticides on target crops, improve the wettability of pesticides, and thus improve the utilization rate of pesticides.
In the present invention, the lauric acid is used for carrying out hydrophobic graft modification on the xylan to prepare the amphiphilic xylan polymer (X-LA), and the X-LA is used for developing the emulsion in water containing 4.4% avermectin. The particle size, zeta potential, surface tension and liquid retention rate on cabbage leaves of the emulsion in water containing 4.4% avermectin under different storage conditions are represented. It is proved that the emulsion in water containing 4.4% avermectin prepared by the X-LA had good storage stability (thermal storage stability and low temperature stability) and wettability. The above results can provide a reference for the preparation of EW with good storage stability and wettability.
Nanomicelles are ordered aggregates with "core-shell” structure formed by self-assembly of amphiphilic block polymers, and their hydrophobic cores can be loaded with insoluble pesticides.
The use of nanomaterials and preparation technology to the development of new nanomedicines can effectively improve the utilization rate of pesticides, and reduce pesticide residues and environmental pollution. This is because of the small size and large specific surface area of nanoparticles, which can improve the dispersion, wettability and stability of insoluble pesticides, and increase the adhesion and deposition of pesticides on the target surface.
In the present invention, compared with the commercial emulsion in water, the emulsion in water containing 4.4% avermectin nano-micelles prepared by using the hemicellulose-lauric acid polymer has better storage stability, particularly thermal storage stability. Under different storage conditions, there is only one particle size distribution peak, and the total active ingredient content remained unchanged. The average particle size of the nano-micelles of the emulsion in water is respectively 225.5 nm and 229.8 nm after room temperature storage and cold storage, while the average particle size of the nano-micelles of the emulsion in water is only 122.9 nm after thermal storage, and the surface zeta potential is -7.677 mV. This is because the entrapment of the 14 avermectin by micelles increases the stability of the avermectin in water. Then the unique small, 505016 size and large specific surface effect of nano-micelles make the smaller particles have better dispersion and stability in water, and the negative charges on the surface of the particles also promote their stability.
Compared with the commercial emulsion in water, the emulsion in water containing 4.4% avermectin nano-micelles has better wetting performance. The surface tension is maintained at about 52 mN/m under different storage conditions, which shows good hydrophilicity and stability.
In addition, the liquid retention rate of the emulsion in water containing the nano-micelles on the cabbage leaves is higher than that of water and the control group, which is due to the fact that the amphiphilic polymer itself has a surface active effect and can inhibit the splashing of the micelle solution on the cabbage leaves (super-hydrophobic interface), so that the pesticide solution is adhered and deposited on the cabbages.
Therefore, the nano-micelles formed by the self-assembly of amphiphilic hemicellulose polymers can be used as an excellent carrier of the avermectin, and the application effect of the nano-micelles in avermectin nano-preparations can be improved. It is expected that this kind of preparation will play an important role in the prevention and control of diseases and insect pests such as spodoptera litura and plutella xylostella.
The above embodiments are the preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principle of the present invention should be equivalent and included in the scope of protection of the present invention.
Claims (10)
1. À preparation method for an amphiphilic xylan polymer, characterized in that, it comprises the following steps: adding a xylan and lauric acid in dimethyl sulfoxide, then adding a coupling agent N,N'- dicyclohexylcarbodiimide and a catalyst 4-dimethylaminopyridine, reacting in a protective gas atmosphere, centrifugating to remove a reaction byproduct N-N'-dicyclohexylurea, washing with absolute ethyl alcohol, extracting and purifying with a mixed solution of acetone and isopropanol, and drying in vacuum to obtain a xylan grafted lauric acid polymer, namely the amphiphilic xylan polymer.
2. The preparation method for the amphiphilic xylan polymer according to claim 1, characterized in that: the mass ratio of the xylan to the lauric acid is 1 to 2:2; the mass ratio of the coupling agent N,N'-dicyclohexylcarbodiimide to the catalyst 4- dimethylaminopyridine is 6 to 7:1; and the mass ratio of the sum of the coupling agent and the catalyst to the xylan is 1:1.5 to 2.
3. The preparation method for the amphiphilic xylan polymer according to claim 1, characterized in that: the time for reacting is 60-120 minutes; and the volume ratio of the acetone to the isopropanol in the mixed solution of the acetone and the isopropanol is 1:1.
4. An amphiphilic xylan polymer prepared by the method according to any one of claims 1-
3.
5. An application of the amphiphilic xylan polymer according to claim 4 in the preparation of a pesticide carrier or a pesticide formulation.
6. An emulsion in water containing 4.4% avermectin, characterized in that: it comprises the following components in percentage by mass: 4.4% avermectin, 1% to 2% of the amphiphilic xylan polymer according to claim 4, 24% to 25% cyclohexanone, 3% to 5% of emulsifier T-028, 2% to 6% of emulsifier Z-029, and a balance of water.
7. The emulsion in water containing 4.4% avermectin according to claim 6, characterized in that: it comprises the following components in percentage by mass: 4.4% of avermectin, 2% of the 1 amphiphilic xylan polymer according to claim 4, 25% of cyclohexanone, 5% of emulsifier T-028,, 505016 6% of emulsifier Z-029, and a balance of water.
8. A preparation method for the emulsion in water containing 4.4% avermectin according to claim 6 or 7, characterized in that: it comprises the following steps: (1) dissolving avermectin in cyclohexanone, adding emulsifier T-028, and stirring evenly to be used as an oil phase; (2) adding the amphiphilic xylan polymer into water, and dissolving the amphiphilic xylan polymer under the assistance of ultrasound to obtain an X-LA solution; and (3) adding the X-LA solution into the oil phase, oscillating and uniformly mixing at a constant temperature of 50 °C, then adding emulsifier Z-029, adding water to make up to 100% while stirring, and continuously oscillating and mixing at the constant temperature of 50 °C to obtain the emulsion in water containing 4.4% avermectin.
9. An application of the emulsion in water containing 4.4% avermectin of claim 6 or 7 in prevention and control of pest.
10. The application according to claim 9, characterized in that: the pest is at least one of acarid, nematode, prodenia litura, diamondback moth and golden apple snail. 2
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