CN117063933B - Kasugamycin organic acid salt, pesticide composition containing kasugamycin organic acid salt and application of kasugamycin organic acid salt - Google Patents
Kasugamycin organic acid salt, pesticide composition containing kasugamycin organic acid salt and application of kasugamycin organic acid salt Download PDFInfo
- Publication number
- CN117063933B CN117063933B CN202311336790.6A CN202311336790A CN117063933B CN 117063933 B CN117063933 B CN 117063933B CN 202311336790 A CN202311336790 A CN 202311336790A CN 117063933 B CN117063933 B CN 117063933B
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- CN
- China
- Prior art keywords
- kasugamycin
- organic acid
- acid salt
- active substance
- acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 75
- -1 Kasugamycin organic acid salt Chemical class 0.000 title claims abstract description 57
- 239000000575 pesticide Substances 0.000 title claims abstract description 19
- PVTHJAPFENJVNC-MHRBZPPQSA-N kasugamycin Chemical compound N[C@H]1C[C@H](NC(=N)C(O)=O)[C@@H](C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H]1O PVTHJAPFENJVNC-MHRBZPPQSA-N 0.000 claims abstract description 210
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000013543 active substance Substances 0.000 claims abstract description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 24
- 229960001494 octreotide acetate Drugs 0.000 claims abstract description 22
- DEQANNDTNATYII-OULOTJBUSA-N (4r,7s,10s,13r,16s,19r)-10-(4-aminobutyl)-19-[[(2r)-2-amino-3-phenylpropanoyl]amino]-16-benzyl-n-[(2r,3r)-1,3-dihydroxybutan-2-yl]-7-[(1r)-1-hydroxyethyl]-13-(1h-indol-3-ylmethyl)-6,9,12,15,18-pentaoxo-1,2-dithia-5,8,11,14,17-pentazacycloicosane-4-carboxa Chemical compound C([C@@H](N)C(=O)N[C@H]1CSSC[C@H](NC(=O)[C@H]([C@@H](C)O)NC(=O)[C@H](CCCCN)NC(=O)[C@@H](CC=2C3=CC=CC=C3NC=2)NC(=O)[C@H](CC=2C=CC=CC=2)NC1=O)C(=O)N[C@H](CO)[C@H](O)C)C1=CC=CC=C1 DEQANNDTNATYII-OULOTJBUSA-N 0.000 claims abstract description 21
- 108010016076 Octreotide Proteins 0.000 claims abstract description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 18
- NSJANQIGFSGFFN-UHFFFAOYSA-N octylazanium;acetate Chemical compound CC([O-])=O.CCCCCCCC[NH3+] NSJANQIGFSGFFN-UHFFFAOYSA-N 0.000 claims abstract description 18
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 17
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 16
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 12
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940123208 Biguanide Drugs 0.000 claims abstract description 8
- 239000003899 bactericide agent Substances 0.000 claims abstract description 8
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims abstract description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims abstract description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims abstract description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 7
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims abstract description 6
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- YIKWKLYQRFRGPM-UHFFFAOYSA-N 1-dodecylguanidine acetate Chemical compound CC(O)=O.CCCCCCCCCCCCN=C(N)N YIKWKLYQRFRGPM-UHFFFAOYSA-N 0.000 claims description 7
- 239000005766 Dodine Substances 0.000 claims description 5
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- 239000003090 pesticide formulation Substances 0.000 claims 3
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- 239000002244 precipitate Substances 0.000 abstract description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract description 4
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- ZDRBJJNXJOSCLR-YZKQBBCCSA-N 2-amino-2-[(2r,3s,5s,6r)-5-amino-2-methyl-6-[(2r,3s,5s,6s)-2,3,4,5,6-pentahydroxycyclohexyl]oxyoxan-3-yl]iminoacetic acid;hydron;chloride Chemical compound Cl.N[C@H]1C[C@H](N=C(N)C(O)=O)[C@@H](C)O[C@@H]1OC1[C@H](O)[C@@H](O)C(O)[C@H](O)[C@@H]1O ZDRBJJNXJOSCLR-YZKQBBCCSA-N 0.000 description 13
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
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- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 8
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- FKWDSATZSMJRLC-UHFFFAOYSA-N Iminoctadine acetate Chemical compound CC([O-])=O.CC([O-])=O.CC([O-])=O.NC([NH3+])=NCCCCCCCC[NH2+]CCCCCCCCN=C(N)[NH3+] FKWDSATZSMJRLC-UHFFFAOYSA-N 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/04—Nitrogen directly attached to aliphatic or cycloaliphatic carbon atoms
-
- 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
- A01N47/40—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides
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- A01N47/44—Guanidine; Derivatives thereof
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Abstract
The invention provides kasugamycin organic acid salt, a pesticide composition containing the kasugamycin organic acid salt and application of the kasugamycin organic acid salt. The composition contains an active substance a and an active substance b, wherein the active substance a is a kasugamycin organic acid salt, and the kasugamycin organic acid salt is selected from one or more of kasugamycin acetate, kasugamycin lactate, kasugamycin propionate, kasugamycin malate, kasugamycin butyrate, kasugamycin tartrate, kasugamycin malonate, kasugamycin succinate, kasugamycin maleate, kasugamycin salicylate, kasugamycin benzoate and kasugamycin citrate; the active substance b is an alkyl polyamine organic acid salt and/or alkyl guanidine organic acid salt bactericide, and the alkyl polyamine organic acid salt and/or alkyl guanidine organic acid salt bactericide is selected from one or more of multi-fruit, octreotide acetate and biguanide octylamine acetate. The composition has good solubility in water solvent, does not generate floccule or precipitate, effectively expands the types of kasugamycin mixture, and avoids the problem that single dosage is easy to generate resistance.
Description
Technical Field
The invention belongs to the technical field of agriculture, and particularly relates to kasugamycin organic acid salt, a pesticide composition containing the kasugamycin organic acid salt and application of the kasugamycin organic acid salt.
Background
The kasugamycin serving as a pesticide antibiotic is used for preventing and controlling agricultural diseases for over 40 years, has the characteristics of high efficiency, low toxicity and environmental friendliness, and is widely used for preventing and controlling various plant diseases. The kasugamycin free base is unstable in a slightly alkaline environment, and the kasugamycin after salt formation has more beneficial effects on stability, solubility and preparation processing than the kasugamycin free base. Based on the production characteristics of the prior art, kasugamycin hydrochloride is the most dominant kasugamycin salt type.
The compound use of pesticides is a main method for reducing disease resistance and maintaining continuous pesticide effect in agriculture. The compound of kasugamycin and various bactericides has been widely studied, at present, about 100 registration certificates of the kasugamycin mixed agent and about 27 compounds are involved, the main types are the compound of the kasugamycin and copper preparation substances such as quinoline copper or copper king, but the compound of the kasugamycin and the copper preparation is limited by lower solubility of the copper preparation, the suspending agent or wettable powder is mainly used as the mixed agent of the kasugamycin and the copper preparation, and the suspending agent and the wettable powder have strict preparation requirements, more auxiliary agent types, complex preparation process and higher production cost, and are also more complicated for farmers.
The soluble preparation has better solubility in water without adding complex auxiliary ingredients, so that the corresponding preparation process is simpler, the production cost of enterprises is greatly reduced, and the application of farmer terminals is facilitated. The applicant finds that the kasugamycin hydrochloride serving as the active ingredient of the soluble preparation cannot form a stable solution when being compounded with part of bactericides in the preparation development process, so that the development of the kasugamycin mixture is greatly limited.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a pesticide composition, wherein the kasugamycin organic acid salt in the composition can be compounded with other bactericides to form a composition with good solubility, and the composition has stable performance and does not generate precipitation after being dissolved in water.
In one aspect of the invention, there is provided a pesticide composition comprising an active substance a and an active substance b, wherein the active substance a is kasugamycin organic acid salt and the active substance b is selected from alkyl polyamine organic acid salts or alkyl guanidine organic acid salt bactericides.
Further, the active substance a may be specifically selected from one or more of kasugamycin acetate, kasugamycin lactate, kasugamycin propionate, kasugamycin malate, kasugamycin butyrate, kasugamycin tartrate, kasugamycin malonate, kasugamycin succinate, kasugamycin maleate, kasugamycin salicylate, kasugamycin benzoate, and kasugamycin citrate;
further, the active substance b can be specifically selected from one or more of dodine, octylamine acetate and biguanide octylamine acetate.
Further, the active substance a is selected from one or more of kasugamycin acetate, kasugamycin lactate, kasugamycin citrate, kasugamycin malate, kasugamycin tartrate and kasugamycin propionate; the active substance b is one or two of octylamine acetate and biguanide octylamine acetate.
According to the composition of the invention, the mass ratio of the active substance a to the active substance b is 0.1:10-10:0.1; further, the mass ratio of active material a to active material b is any one or a range of values between any two values of 0.1:9,0.1:8,0.1:7,0.1:6,0.1:5,0.1:4,0.1:3,0.1:2,0.1:1,1:2,1:3,1:4,1:5,1:6,1:7,1:8,1:9,2:1,3:1,4:1,5:1,6:1,7:1,8:1 or 9:1.
According to the composition of the invention, further, the mass ratio of the active substance a to the active substance b is 0.1:1-2.5:1, further, the mass ratio of the active substance a to the active substance b is 1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2,1:1,1.5:1,1.8:1,2:1,2.1:1,2.2:1,2.3:1 or 2.4:1, or any value or a range between any two values.
Further, the composition is a formulation containing a pesticidally acceptable adjuvant. Still further, the formulation of the present invention is any one selected from the group consisting of powders, granules, pellets, macrogranules, fine granules, microgranules, microcapsule, wettable powder, oil dispersion powder, water dispersible granules, emulsion granules, effervescent granules, dispersible tablets, effervescent tablets, sustained release agents, sustained release blocks, sustained release tubes, sustained release granules, soluble powder, soluble granules, soluble tablets, soluble solutions, aqueous solutions, soluble solutions, oil solutions, film spreading oil solutions, ultra-low volume microcapsule suspensions, emulsifiable concentrates, latex, dispersible solutions, pastes, concentrated gelatin, aqueous emulsions, oil emulsions, microemulsions, greases, suspending agents, microcapsule suspensions, oil suspensions, suspoemulsions, seed-treated dispersible powders, seed-treated soluble powders, seed-treated solutions, seed-treated emulsions, seed-treated suspensions, suspended seed-dressing agents, seed-treated microcapsule suspensions.
Preferably, the formulation of the present invention is selected from the group consisting of soluble formulations including, but not limited to, soluble powders, soluble granules, soluble tablets, soluble solutions, aqueous solutions, soluble solutions or soluble effervescent agents.
The total content of the active substance a and the active substance b is 0.01-65% based on the total mass of the preparation; further, the total content of the active material a and the active material b is 0.05%,0.1%,0.5%,1%,2%,3%,4%,5%,6%,7%,8%,9%,10%,11%,12%,13%,15%,20%,25%,30%,35%,40%,45%,50%,55% or 60%.
In another aspect of the invention there is provided the use of a composition as described above in the control of plant diseases.
In another aspect of the present invention, there is provided the use of a composition as described above for the preparation of a plant disease control formulation.
In another aspect of the invention, there is provided the use of an organic acid salt of kasugamycin in the preparation of a pesticidal mixture; the kasugamycin organic acid salt is selected from one or more of kasugamycin acetate, kasugamycin lactate, kasugamycin propionate, kasugamycin malate, kasugamycin butyrate, kasugamycin tartrate, kasugamycin malonate, kasugamycin succinate, kasugamycin maleate, kasugamycin salicylate, kasugamycin benzoate and kasugamycin citrate; preferably, the kasugamycin organic acid salt is selected from one or more of kasugamycin acetate, kasugamycin lactate, kasugamycin citrate, kasugamycin malate, kasugamycin tartrate and kasugamycin propionate.
In another aspect of the invention, there is provided the use of kasugamycin organic acid salt as a mixture active ingredient in plant disease control; the kasugamycin organic acid salt is selected from one or more of kasugamycin acetate, kasugamycin lactate, kasugamycin propionate, kasugamycin malate, kasugamycin butyrate, kasugamycin tartrate, kasugamycin malonate, kasugamycin succinate, kasugamycin maleate, kasugamycin salicylate, kasugamycin benzoate and kasugamycin citrate; preferably, the kasugamycin organic acid salt is selected from one or more of kasugamycin acetate, kasugamycin lactate, kasugamycin citrate, kasugamycin malate, kasugamycin tartrate and kasugamycin propionate.
In another aspect of the invention, the preparation steps of the kasugamycin salt compound include:
1) Acidifying, filtering and removing impurities from fermentation liquor;
2) Ceramic membrane filtration;
3) Adsorbing resin and resolving sodium hydroxide solution;
4) Adjusting the pH value by an acid agent;
5) Nanofiltration for desalting;
6) Evaporating, concentrating and crystallizing.
The invention has the positive progress effects that:
the composition compounded by the kasugamycin organic acid salt and the alkyl polyamine organic acid salt or the alkyl guanidine organic acid salt has good solubility, is not easy to generate floccules or precipitates, has obvious synergistic effect, and effectively expands the types of the kasugamycin mixture.
Drawings
Fig. 1 shows the dissolution of a mixture of different kasugamycin salt compounds, wherein a is a kasugamycin hydrochloride and octreotide acetate mixture, b is a kasugamycin oxalate and octreotide acetate mixture, c is a kasugamycin lactate and octreotide acetate mixture, and d is a kasugamycin acetate and octreotide acetate mixture.
Detailed Description
For the purposes of the present invention, the terms used in this application have the following meanings, unless otherwise indicated:
the term "formulation" refers to a stable product processed from a pesticide base stock (parent) and suitable adjuvants, or processed by methods such as biological fermentation, plant extraction, etc.
The term "adjuvant" refers to any substance, other than the active ingredient, which is added to a pesticidal product, does not itself have pesticidal activity and active ingredient function, but is capable of or contributes to the enhancement, improvement, or physical and chemical properties of the pesticidal product, of a single component or of multiple components.
The term "plant disease" refers to a phenomenon that a plant is significantly hindered from growing and developing due to infection by other organisms and adverse abiotic factors during the growth and development of the plant, and pathological changes and even death occur in physiological and tissue structures inside and outside the plant, resulting in reduced yield and deteriorated quality. "plant disease" in this application refers specifically to diseases of plants caused by infestation by other organisms including, but not limited to, fungi (e.g., pyricularia grisea which cause rice blast), or bacteria (e.g., pseudomonas syringae variant which cause bacterial angular leaf spot in melons), and the like.
The term "soluble formulation" refers to a clear liquid formulation in which the solvent is water, or a solid formulation in which the active ingredient forms a true solution in water when dissolved in water, including but not limited to soluble powders, soluble granules, soluble tablets, soluble solutions, aqueous solutions, soluble solutions or soluble effervescent agents.
The term "organic acid salt" refers to compounds prepared by reacting an organic acid with a free base compound, such as kasugamycin acetate prepared by reacting acetic acid with kasugamycin, and octreotide acetate prepared by reacting octreotide with acetic acid. The free base compound is bound to one or more organic acids, depending on the difference in the number of primary or secondary amino groups in the free base compound. Unless otherwise indicated, "organic acid salt" shall include mono-, di-or tri-organic acid salts, e.g., biguanide octylamine acetate may be inclusive of monoacetate, diacetate or triacetate.
The term "pesticidal mixture" refers to a pesticide that is a mixture of two or more pesticidal active ingredients.
The term "octylamine" refers to di-n-octyldiethylenetriamine, CAS 57413-95-3.
The term "dodine" refers to dodecyl guanidine acetate, CAS 2439-10-3.
The terms "about", "about" and "substantially" refer to a numerical variation in the content of the error range of a normal experiment or measurement, e.g., that "substantially" represents an error of no more than 15%, preferably no more than 10%.
The reagents and solvents used in the following examples are commercially available or may be prepared by conventional methods known to those skilled in the art. All commercial reagents and solvents were not further purified.
1. Preparation example
Example 1: preparation of kasugamycin hydrochloride
(1) Adjusting pH of 20L kasugamycin fermentation broth to about 3.0, filtering to remove impurities, and collecting filtrate;
(2) Filtering the filtrate by adopting an ultrafiltration ceramic membrane, adsorbing active ingredients of the obtained filtrate by adopting a strong acid cation exchange resin with a styrene-divinylbenzene copolymerization cross-linked structure, and removing impurities; the adsorption flow rate is 1BV;
(3) Resolving by using 0.2 mol/L sodium hydroxide solution as resolving agent to obtain resolving solution, wherein the eluting flow rate is 1BV;
(4) Adjusting pH of the solution to about 3.0 with hydrochloric acid, concentrating by nanofiltration, and circularly filtering to remove residual Na + A salt; repeated nanofiltration to obtain about 5L mother liquor;
(5) Evaporating and concentrating the mother solution to 0.8L at 70 ℃, cooling to 10 ℃ at the speed of 0.5 ℃/min for cooling and crystallizing, collecting crystallized products, and drying at normal temperature to obtain about 63 g kasugamycin hydrochloride.
Example 2: preparation of kasugamycin oxalate
(1) Adjusting pH of 20L kasugamycin fermentation broth to about 3.0, filtering to remove impurities, and collecting filtrate;
(2) Filtering the filtrate by adopting an ultrafiltration ceramic membrane, adsorbing active ingredients of the obtained filtrate by adopting a strong acid cation exchange resin with a styrene-divinylbenzene copolymerization cross-linked structure, and removing impurities; the adsorption flow rate is 1BV;
(3) Resolving by using 0.2 mol/L sodium hydroxide solution as resolving agent to obtain resolving solution, wherein the eluting flow rate is 1BV;
(4) Adjusting pH of the solution to about 3.5 with oxalic acid, concentrating by nanofiltration, and circularly filtering to remove residual Na + A salt; repeated nanofiltration to obtain about 5L mother liquor;
(5) Evaporating and concentrating the mother solution to 0.8L at 70 ℃, cooling to 10 ℃ at the speed of 0.5 ℃/min for cooling and crystallizing, collecting crystallized products, and drying at normal temperature to obtain about 65 g kasugamycin oxalate.
Example 3: preparation of kasugamycin lactate
(1) Adjusting pH of 20L kasugamycin fermentation broth to about 3.0, filtering to remove impurities, and collecting filtrate;
(2) Filtering the filtrate by adopting an ultrafiltration ceramic membrane, adsorbing active ingredients of the obtained filtrate by adopting a strong acid cation exchange resin with a styrene-divinylbenzene copolymerization cross-linked structure, and removing impurities; the adsorption flow rate is 1BV;
(3) Resolving by using 0.2 mol/L sodium hydroxide solution as resolving agent to obtain resolving solution, wherein the eluting flow rate is 1BV;
(4) Adjusting pH of the obtained analytical solution to about 4.1 with lactic acid as acid agent, concentrating by nanofiltration, and circularly filtering to remove residual Na + A salt; repeated nanofiltration to obtain about 5L mother liquor;
(5) Evaporating and concentrating the mother solution to 0.8L at 70 ℃, cooling to 10 ℃ at the speed of 0.5 ℃/min for cooling and crystallizing, collecting crystallized products, and drying at normal temperature to obtain about 66 g kasugamycin lactate.
Example 4: preparation of kasugamycin acetate
(1) Adjusting pH of 20L kasugamycin fermentation broth to about 3.0, filtering to remove impurities, and collecting filtrate;
(2) Filtering the filtrate by adopting an ultrafiltration ceramic membrane, adsorbing active ingredients of the obtained filtrate by adopting a strong acid cation exchange resin with a styrene-divinylbenzene copolymerization cross-linked structure, and removing impurities; the adsorption flow rate is 1BV;
(3) Resolving by using 0.2 mol/L sodium hydroxide solution as resolving agent to obtain resolving solution, wherein the eluting flow rate is 1BV;
（4）adjusting pH of the obtained analytical solution to about 4.0 with acetic acid, concentrating by nanofiltration, and circularly filtering to remove residual Na + A salt; repeated nanofiltration to obtain about 5L mother liquor;
(5) Evaporating and concentrating the mother solution to 0.8L at 70 ℃, cooling to 10 ℃ at the speed of 0.5 ℃/min for cooling and crystallizing, collecting crystallized products, and drying at normal temperature to obtain about 64 g kasugamycin acetate.
Example 5: preparation of octyl fungus amine acetate
The octreotide acetate is prepared by reacting octreotide with acetic acid. The method comprises the following steps: dissolving 0.6 mol of glacial acetic acid (purity > 99%) in 1L deionized water at room temperature to prepare an acetic acid solution, slowly dropwise adding 0.2 mol of octylamine (purity > 95%) into the acetic acid solution at room temperature under stirring, and continuously stirring for 30min after the dropwise adding is finished, and then evaporating in vacuum to obtain a dry crystal, namely octylamine acetate.
Example 6: preparation of kasugamycin citrate
(1) Adjusting pH of 20L kasugamycin fermentation broth to about 3.0, filtering to remove impurities, and collecting filtrate;
(2) Filtering the filtrate by adopting an ultrafiltration ceramic membrane, adsorbing active ingredients of the obtained filtrate by adopting a strong acid cation exchange resin with a styrene-divinylbenzene copolymerization cross-linked structure, and removing impurities; the adsorption flow rate is 1BV;
(3) Resolving by using 0.2 mol/L sodium hydroxide solution as resolving agent to obtain resolving solution, wherein the eluting flow rate is 1BV;
(4) Adjusting pH of the obtained analytical solution to about 3.8 with citric acid as acid agent, concentrating by nanofiltration, and circularly filtering to remove residual Na + A salt; repeated nanofiltration to obtain about 5L mother liquor;
(5) Evaporating and concentrating the mother solution to 0.8L at 70 ℃, cooling to 10 ℃ at the speed of 0.5 ℃/min for cooling and crystallizing, collecting crystallized products, and drying at normal temperature to obtain about 69g of kasugamycin citrate.
Example 7: preparation of kasugamycin malate
(1) Adjusting pH of 20L kasugamycin fermentation broth to about 3.0, filtering to remove impurities, and collecting filtrate;
(2) Filtering the filtrate by adopting an ultrafiltration ceramic membrane, adsorbing active ingredients of the obtained filtrate by adopting a strong acid cation exchange resin with a styrene-divinylbenzene copolymerization cross-linked structure, and removing impurities; the adsorption flow rate is 1BV;
(3) Resolving by using 0.2 mol/L sodium hydroxide solution as resolving agent to obtain resolving solution, wherein the eluting flow rate is 1BV;
(4) Adjusting pH of the obtained analytical solution to about 3.9 with malic acid, concentrating by nanofiltration, and circularly filtering to remove residual Na + A salt; repeated nanofiltration to obtain about 5L mother liquor;
(5) Evaporating and concentrating the mother solution to 0.8L at 70 ℃, cooling to 10 ℃ at the speed of 0.5 ℃/min for cooling and crystallizing, collecting crystallized products, and drying at normal temperature to obtain about 68 g kasugamycin malate.
Example 8: preparation of kasugamycin tartrate
(1) Adjusting pH of 20L kasugamycin fermentation broth to about 3.0, filtering to remove impurities, and collecting filtrate;
(2) Filtering the filtrate by adopting an ultrafiltration ceramic membrane, adsorbing active ingredients of the obtained filtrate by adopting a strong acid cation exchange resin with a styrene-divinylbenzene copolymerization cross-linked structure, and removing impurities; the adsorption flow rate is 1BV;
(3) Resolving by using 0.2 mol/L sodium hydroxide solution as resolving agent to obtain resolving solution, wherein the eluting flow rate is 1BV;
(4) Adjusting pH of the obtained analytical solution to about 3.7 with acid agent tartaric acid, concentrating by nanofiltration, and circularly filtering to remove residual Na + A salt; repeated nanofiltration to obtain about 5L mother liquor;
(5) Evaporating and concentrating the mother solution to 0.8L at 70 ℃, cooling to 10 ℃ at the speed of 0.5 ℃/min for cooling and crystallizing, collecting crystallized products, and drying at normal temperature to obtain about 70g kasugamycin tartrate.
Example 9: preparation of kasugamycin propionate
(1) Adjusting pH of 20L kasugamycin fermentation broth to about 3.0, filtering to remove impurities, and collecting filtrate;
(2) Filtering the filtrate by adopting an ultrafiltration ceramic membrane, adsorbing active ingredients of the obtained filtrate by adopting a strong acid cation exchange resin with a styrene-divinylbenzene copolymerization cross-linked structure, and removing impurities; the adsorption flow rate is 1BV;
(3) Resolving by using 0.2 mol/L sodium hydroxide solution as resolving agent to obtain resolving solution, wherein the eluting flow rate is 1BV;
(4) Adjusting pH of the obtained analytical solution to about 4.1 with acid agent propionic acid, concentrating by nanofiltration, and circularly filtering to remove residual Na + A salt; repeated nanofiltration to obtain about 5L mother liquor;
(5) Evaporating and concentrating the mother solution to 0.8L at 70 ℃, cooling to 10 ℃ at the speed of 0.5 ℃/min for cooling and crystallizing, collecting crystallized products, and drying at normal temperature to obtain about 65 g kasugamycin propionate.
According to the preparation of the kasugamycin organic acid salt, other kasugamycin organic acid salts can be prepared by adjusting the types of the acid agents correspondingly.
2. Effect experiment
1. Active substance bacteriostasis experiment
Raw materials of kasugamycin hydrochloride (prepared in example 1), kasugamycin oxalate (prepared in example 2), kasugamycin lactate (prepared in example 3) and kasugamycin acetate (prepared in example 4); the rice blast bacteria are separated from leaves of field disease-causing rice.
The test method refers to a potting method of ' national agricultural industry standard NY/Tll54.7-2006 of the people's republic of China '. Selecting three-leaf-period rice seedlings with consistent growth vigor, wherein 2 seedlings are planted in each pot, and 5 seedlings to be tested are selected in each treatment. Culturing Pyricularia oryzae on tomato oat agar medium, and washing spores with sterile water to obtain 1×10 5 The suspension of each spore/mL is evenly sprayed and inoculated on the rice seedlings to be tested, and a black plastic bag is sleeved for moisture preservation and culture for 24 hours after inoculation. After 24h inoculation, treatment with the agents was carried out, each agent set at 5The concentration gradient was about 5mL per pot using a Potter spray tower at a pressure of 50 Psi. After spraying, the rice seedlings are placed at about 26 ℃ and the relative humidity is high>Culturing under 90% condition, investigating disease index of whole plant leaf after 7d according to disease grading standard of rice blast, and calculating control effect.
Disease index = { [ Σ (number of leaf of each stage of disease of each treatment×number of corresponding stage) ]/total leaf number of investigation×9} ×100;
control effect (%) = [ (blank control disease index-agent treatment disease index)/blank control disease index ] ×100.
The control effect was converted into a few-value (y), the concentration of the drug solution (ug/ml) was converted into a pair of values (x), and the EC50 of the concentration in inhibition was calculated, and the results are shown in table 1.
TABLE 1 antibacterial effects of different kasugamycin salt-type Compounds
The bactericidal active substance of the kasugamycin salt compound is kasugamycin free alkali, so that the antibacterial effect of different kasugamycin salt compounds is basically equivalent, and the EC50 is about 24-29 mug/mL, and the antibacterial effect is excellent.
2. Solubility experiments of different mixes
2 g kasugamycin hydrochloride (prepared in example 1), 2 g kasugamycin oxalate (prepared in example 2), 2 g kasugamycin lactate (prepared in example 3) and 2 g kasugamycin acetate (prepared in example 4) are dissolved in 98 mL deionized water in a beaker respectively to prepare different kinds of kasugamycin salt-type aqueous solutions with mass fractions of 2%.
Slowly adding 1g octylamine acetate into different types of kasugamycin salt type aqueous solutions under stirring at room temperature, stopping stirring after the octylamine acetate is added, pouring the solution into a test tube for observation, respectively standing for 1min and 30min, irradiating the liquid in the test tube by using a fluorescent lamp, and determining the clarification condition and the precipitation condition by naked eyes, wherein the experimental results are shown in table 2 and figure 1.
TABLE 2 dissolution of different kasugamycin salt compounds and Xinjunan acetate formulations
As can be seen from Table 2 and FIG. 1, a large amount of flocculent insoluble substances appear after the solution of the kasugamycin hydrochloride and the octreotide acetate is left for 1min, and obvious precipitates are formed at the bottom of a test tube after the solution is left for 30min, which indicates that the kasugamycin hydrochloride is not suitable for being compounded with the octreotide acetate to prepare the pesticide mixture. Similarly, the solution compounded by kasugamycin oxalate and octylamine acetate also has partial flocculent insoluble matter after standing for 1min, and partial precipitate exists at the bottom after 30min, and is not suitable for being used as a pesticide mixture. The solution of kasugamycin lactate and kasugamycin acetate, which are compounded with the octreotide acetate, has brown color, but the formed solution has good clarity and no obvious precipitate, is suitable for spraying and storing, and can be used as a pesticide mixture. The experimental results show that not all types of kasugamycin organic acid salts are suitable for being prepared into pesticide mixtures, and the pesticide mixtures need to be verified through a compound solubility experiment.
The same solubility test method was used to compound kasugamycin citrate (prepared in example 6), kasugamycin malate (prepared in example 7), kasugamycin tartrate (prepared in example 8), kasugamycin propionate (prepared in example 9) and octreotide acetate, and their solubility was tested. The result shows that the solution after the kasugamycin citrate and the kasugamycin malate are compounded is also a good clear solution, the solution after the kasugamycin tartrate and the kasugamycin propionate are compounded is basically clear, a little mist insoluble matter exists in the solution, and the four kasugamycin organic acid salts can be prepared into pesticide mixture for use
In order to further verify the effect of the specific kasugamycin organic acid salt after compounding, we selected kasugamycin lactate for the co-toxicity experiment.
3. Co-toxicity test of kasugamycin lactate and octreotide acetate
Raw materials of kasugamycin lactate (prepared by the method of example 3) and octylamine acetate (prepared by the method of example 5); the rice blast bacteria are separated from leaves of field disease-causing rice.
The method comprises the steps of determining EC50 values of the kasugamycin lactate-octreotide acetate mixture under different mass ratios according to a related method in the section 1 active substance bacteriostasis experiment, and calculating toxicity index and co-toxicity coefficient (CTC) of the medicament according to the Sunyanpei method.
Single dose toxicity index = standard dose EC 50/test single dose EC50 x 100;
measured virulence index (ATI) = (standard agent EC 50/test agent EC 50) ×100;
the theoretical drug toxicity index (TTI) =a drug toxicity index x percentage of drug in the drug mixture+b drug toxicity index x percentage of drug in the drug mixture;
co-toxicity coefficient (CTC) = [ mix measured toxicity index (ATI)/mix Theoretical Toxicity Index (TTI) ]x100;
when CTC is less than or equal to 80, the composition shows antagonism, when CTC is less than or equal to 80 and CTC is less than or equal to 120, the composition shows additive effect, and when CTC is more than or equal to 120, the composition shows synergistic effect.
TABLE 3 Co-toxicity test data
Note that: "spring" is kasugamycin lactate, "octyl" is octylamine acetate
As shown in Table 3, the kasugamycin lactate and octreotide acetate mixture has additive control effect in the mass ratio range of 5:1-10:1, and the solution of the mixture dissolved in water in the ratio range can keep a clear state, thereby being beneficial to the application of the mixture at a terminal and further avoiding the problems of resistance and the like caused by single medicament; meanwhile, the mixture has unexpected synergistic effect within the mass ratio range of 0.1:1-2.5:1.
Example 10: preparation of kasugamycin lactate and octreotide acetate aqueous solution
The following components are provided:
kasugamycin lactate (prepared in example 3) 2 g;
1g of octylamine acetate (prepared in example 5);
tween 80.5 g;
AEO-9 0.2 g；
96.3g of deionized water;
firstly, dissolving the octreotide acetate in 50mL of deionized water to form an octreotide acetate solution; sequentially adding kasugamycin lactate, tween 80 and AEO-9 into the rest deionized water, stirring and dissolving to form a kasugamycin lactate solution, and slowly adding an octreotide acetate solution into the kasugamycin lactate solution under the stirring condition to prepare the 3% kasugamycin lactate-octreotide acetate aqueous solution.
The test of the reference 'GB/T34774-2017 kasugamycin aqueous solution' requires that the water insoluble substance, dilution stability, low-temperature stability and heat storage stability of the kasugamycin lactate-octreotide acetate aqueous solution are tested, and the results are shown in the table 4, and the indexes of related control projects all meet the requirements.
Table 4 test results of kasugamycin lactate and octreotide acetate aqueous solutions
Example 11: kasugamycin lactate-polyvidin soluble powder
30g of kasugamycin lactate (prepared in example 3), 10g of dodine (purchased from Washington chemical Co., ltd. In Tokyo county), 10g of Sokalan HP, 20g of sodium dodecyl sulfate, 930g of sodium sulfate were weighed. The raw materials are mixed and crushed by air flow to prepare 4 percent kasugamycin lactate and multi-fruit powder.
10g of the soluble powder was added to 50ml of deionized water, stirred for about 10 seconds and allowed to stand for 5 minutes, and then observed as a substantially clear solution without significant precipitation.
Example 12: kasugamycin acetate-polyvidin soluble powder
The preparation method of the 4% kasugamycin acetate-multi-fruit-setting soluble powder is basically the same as that of the embodiment 11, except that the kasugamycin acetate is replaced by the kasugamycin lactate.
10g of the soluble powder was added to 50ml of deionized water, stirred for about 10 seconds, and allowed to stand for 5 minutes, and then observed as a clear solution without significant precipitation.
Comparative example 1: kasugamycin hydrochloride and dodine soluble powder
The preparation method of the 4% kasugamycin hydrochloride-multi-fruit setting soluble powder is basically the same as that of example 11 except that the kasugamycin lactate is replaced with the kasugamycin hydrochloride.
10g of the kasugamycin hydrochloride-polyvidone soluble powder is added into 50ml of deionized water, and after stirring for about 10s and standing for 5min, suspended matters in the solution and obvious precipitates at the bottom of the solution can be obviously observed, so that the kasugamycin hydrochloride-polyvidone soluble powder is not suitable for being used as a pesticide mixture.
Example 13: kasugamycin lactate and biguanide octylamine acetate soluble powder
30g of kasugamycin lactate (prepared in example 3), 20g of iminoctadine acetate (purchased from Hubei ferry chemical Co., ltd.), 15g of Sokalan HP, 20g of sodium dodecyl sulfate, 915g of sodium sulfate were weighed out. The raw materials are mixed and crushed by air flow to prepare 5 percent kasugamycin lactate and iminoctadine acetate soluble powder.
10g of the soluble powder was added to 50ml of deionized water, stirred for about 10 seconds, and allowed to stand for 5 minutes, and then observed as a clear solution without significant precipitation.
Comparative example 2: kasugamycin hydrochloride and biguanide octylamine acetate soluble powder
The preparation method of the 5% kasugamycin hydrochloride-biguanide octylamine acetate soluble powder is basically the same as that of example 13, except that the kasugamycin lactate is replaced with the kasugamycin hydrochloride,
10g of the 5% kasugamycin hydrochloride-guazatine acetate soluble powder was added to 50ml of deionized water, and after stirring for about 10 seconds, standing for 5 minutes, a clear floccule was observed in the solution, and a partial precipitate was observed at the bottom.
Example 14: kasugamycin citrate and benziothiazolinone water dispersible granule
40g of kasugamycin citrate (prepared in example 6), 10g of benziothiazolinone (purchased from Shanxi Dahuate technology and technology industries, inc.), 20g of sodium dodecyl benzene sulfonate, 55g of starch, 5g of polyethylene glycol and 870g of anhydrous sodium sulfate are weighed, fully mixed according to the weight of the formula, crushed by a superfine crusher, added with a certain amount of water, extruded and manufactured, dried and screened to obtain the 5% kasugamycin citrate-benziothiazolinone water dispersible granule.
10g of the water dispersible granules are added into 50ml of deionized water, stirred for about 10 seconds, and then kept stand for 5 minutes, and the solution is basically clear and has no obvious precipitation.
Example 15: kasugamycin lactate and benziothiazolinone water dispersible granule
The preparation method of the 5% kasugamycin lactate and benziothiazolinone water dispersible granule is basically the same as that of example 14, except that the kasugamycin citrate is replaced by the kasugamycin lactate.
10g of the water dispersible granules are added into 50ml of deionized water, stirred for about 10 seconds, and then kept stand for 5 minutes, and the solution is clear and has no obvious precipitation.
Example 16: kasugamycin propionate-propamocarb solution
20g of kasugamycin propionate (prepared in example 9), 50g of propamocarb (purchased from Jiangsu lan Feng biochemical engineering Co., ltd.), 10g of TX-10, 20g of AEO-9, 30g of urea and 870g of deionized water are weighed, the components are sequentially added into the deionized water, and the mixture is stirred uniformly, so that a clear and precipitate-free 7% kasugamycin propionate-propamocarb solution is obtained.
Example 17: kasugamycin acetate and propamocarb solution
The preparation method of the 7% kasugamycin acetate-propamocarb solution is basically the same as that of the embodiment 16, except that the kasugamycin propionate is replaced by the kasugamycin acetate, and the solution is clear and free of sediment.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Claims (12)
1. A pesticidal composition, characterized in that the composition contains an active substance a and an active substance b, wherein,
the active substance a is a kasugamycin organic acid salt, wherein the kasugamycin organic acid salt is selected from one or more of kasugamycin acetate, kasugamycin lactate, kasugamycin propionate, kasugamycin malate, kasugamycin butyrate, kasugamycin tartrate, kasugamycin malonate, kasugamycin succinate, kasugamycin maleate and kasugamycin citrate;
the active substance b is an alkyl polyamine organic acid salt and/or alkyl guanidine organic acid salt bactericide, and the alkyl polyamine organic acid salt and/or alkyl guanidine organic acid salt bactericide is one or more selected from the group consisting of dodine, octylamine acetate and biguanide octylamine acetate;
the mass ratio of the active substance a to the active substance b is 0.1:10-10:0.1.
2. The composition of claim 1, wherein the active substance a is selected from one or more of kasugamycin acetate, kasugamycin lactate, kasugamycin citrate, kasugamycin malate, kasugamycin tartrate, and kasugamycin propionate.
3. The composition of claim 2, wherein the active substance b is one or both of octreotide acetate and biguanide octylamine acetate.
4. A composition according to any one of claims 1 to 3, wherein the mass ratio of active substance a to active substance b is from 0.1:1 to 2.5:1.
5. A composition according to any one of claims 1 to 3, wherein the composition is a pesticide formulation comprising a pesticidally acceptable adjuvant.
6. The composition of claim 5, wherein the pesticide formulation is in the form of a soluble formulation.
7. The composition according to claim 5, wherein the total content of the active substance a and the active substance b is 0.01 to 65% based on the total mass of the pesticide formulation.
8. The composition according to claim 6, wherein the total content of the active substance a and the active substance b is 0.01 to 65% based on the total mass of the pesticidal formulation.
9. Use of the composition according to any one of claims 1 to 8 for controlling plant diseases.
10. Use of the composition according to any one of claims 1 to 8 for the preparation of a plant disease control formulation.
11. The application of the kasugamycin organic acid salt in preparing pesticide mixture is characterized in that the kasugamycin organic acid salt is selected from one or more of kasugamycin acetate, kasugamycin lactate, kasugamycin propionate, kasugamycin malate, kasugamycin butyrate, kasugamycin tartrate, kasugamycin malonate, kasugamycin succinate, kasugamycin maleate and kasugamycin citrate.
12. The application of the kasugamycin organic acid salt as an active ingredient of a pesticide mixture in plant disease control is characterized in that the kasugamycin organic acid salt is selected from one or more of kasugamycin acetate, kasugamycin lactate, kasugamycin propionate, kasugamycin malate, kasugamycin butyrate, kasugamycin tartrate, kasugamycin malonate, kasugamycin succinate, kasugamycin maleate and kasugamycin citrate.
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| CN112042653A (en) * | 2020-09-22 | 2020-12-08 | 江门市植保有限公司 | Bactericidal composition containing kasugamycin and hymexazol and preparation method thereof |
| CN112205409A (en) * | 2020-11-27 | 2021-01-12 | 陕西麦可罗生物科技有限公司 | Kasugamycin and Xinjunan compound water aqua and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3358001A (en) * | 1963-12-28 | 1967-12-12 | Umezawa Hamao | Antibiotic kasugamycin |
| CN101069505A (en) * | 2007-06-21 | 2007-11-14 | 王建军 | Sterilizing composition containing kasugamycin and isoprothiolane |
| CN106818752A (en) * | 2016-12-26 | 2017-06-13 | 王震 | A kind of preparation method of high content kasugarnycin aqua |
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