TW201024278A - Uses of thaxtomin and thaxtomin compositions as herbicides - Google Patents
Uses of thaxtomin and thaxtomin compositions as herbicides Download PDFInfo
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- TW201024278A TW201024278A TW98144895A TW98144895A TW201024278A TW 201024278 A TW201024278 A TW 201024278A TW 98144895 A TW98144895 A TW 98144895A TW 98144895 A TW98144895 A TW 98144895A TW 201024278 A TW201024278 A TW 201024278A
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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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
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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
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
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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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
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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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
- A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
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- Dentistry (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Catching Or Destruction (AREA)
Abstract
Description
201024278 六、發明說明: 【發明所屬之技術領域】 本發明係涉及一種可控制闊葉樹、莎草和雜草發芽生長的 成份和方法’該成份含薩克多敏(thaxt〇min、一種植物毒素), 即一種環肽鏈黴菌(斯Sp)活性成份。 【先前技術】 天然產品由微生物、植物和其他生物所製成。微生物天然 產品提供豐富多樣的化學成份來源,而藥用天然產品的使用已 有悠久的歷史。但微生物製成的次生代謝產物也可成功應用農 業中,用於控制雜草和蟲害。 薩克多敏(thaxtomin、一種植物毒素)(4-硝基吲哚-3-基-含 2,5-一氧〇底嗪)為植物病原種鍵徽菌(伽沒加Sp )(疮鍵霉菌 (β. scabies),敗疮寐t連霉議(β. acidiscabies))所數成的二版植物 毒素產品,此產品會引發馬龄薯⑼/⑽脈/w&myww)(King, Lawrenceetal. 1992)的病蟲害。在生病的組織中,也會產生毒 素’可在優質化的燕麥麵培養基體外培養(L〇ria,Bukhalid et al. 1995; Beausdjour,Goyer et al. 1999)。King 等人(King, Lawrence et al. 2001)指出所有在科植物病原種鍵 黴菌’可生成一個或多個具有除草活性的薩克多敏 (thaxtomin、一種植物毒素)成份。Hiltunen 等人(Hiltunen,Laakso et al. 2006)則自疮鏈霉菌(S.似^㈣和义iwWcfecW從培養 液,進行4個薩克多敏(thaxtomin、一種植物毒素)成份的純化 比較(包括薩克多敏A (thaxtomin A、一種植物毒素)、薩克多 敏鄰(thaxtomin、一種植物毒素)異構體、薩克多敏b (thaxtomin B、一種植物毒素)(thaxtominB、一種植物毒素)和薩克多敏d (thaxtomin D、一種植物毒素)),而顯示所有4種成份,在馬铃 薯體外繁殖的培養液中,引發類似抑制發芽生長、根系生長 (10-200 ppb)和壞死(200-1000 ppb)的症狀。此外,在薩克多 敏(thaxtomin、一種植物毒素)用於混合成份中,顯示有加性效 201024278 應,但無協同作用(Hiltunen,Laakso et al. 2006)。依據 〇1^(〇1^^奶〇11^1.2003)的研究,薩克多敏入伸加〇111比 A、一種植物毒素)(圖i)和薩克多敏d (thaxtominD、一種植 物毒素)在非系統性除草劑的使用前和使用後,具有顯著活 性’而濃度小於1 uM的薩克多敏A (thaxtomin A、一種植物 毒素)’促成細胞的腔服和壞死,且抑制單子葉和雙子葉幼苗 的 J長(Healy,Wach et al, 2000)。薩克多敏(thaxt〇min、一種植 〇 Ο 物毒素)已由Dow Agro Sciences公司將其評估視為一種具有活 性的除草劑,但缺乏系統性的作用(King,Lawrence et al. 2001)。需diketopipemzine L,L-結構的吲嗦環中,所出現的硝 基顯示提供最低所需的藥害。吲哚環中的硝基位置,非常具有 局部性,而丙氨酸的苯基在藥害結構中,發揮必要作_ Lawrence et al. 1989; King, Lawrence et al. 1992; King; Lawrence et al. 2003)。除草劑的作用即中斷細胞壁的合成(Fry andLoria2002) ’以抑制纖維素的生物合成為主要目標(Kinget al.,2001; Duval et al.,2005; Johnson et al· 2007)。最近的201024278 VI. Description of the Invention: [Technical Field] The present invention relates to a composition and method for controlling the germination and growth of broad-leaved trees, sedges and weeds, which contains saxtamine (thaxt〇min, a plant toxin) , is a cyclic peptide Streptomyces (Sp) active ingredient. [Prior Art] Natural products are made of microorganisms, plants, and other organisms. Microbial natural products provide a rich source of chemical ingredients, and the use of medicinal natural products has a long history. However, secondary metabolites made from microorganisms can also be successfully used in agriculture to control weeds and pests. Saxedamine (thaxtomin, a phytotoxin) (4-nitroindol-3-yl-containing 2,5-monooxazinidine) is a plant pathogen of the genus Bacillus (Gago plus Sp) The second edition of the plant toxin product, which is a mixture of mold (β. scabies) and β. acidiscabies, which causes horses (9)/(10) veins/w&myww) (King, Lawrenceetal) 1992) Pests and diseases. Toxins are also produced in diseased tissues, which can be cultured in vitro on high quality oatmeal medium (L〇ria, Bukhalid et al. 1995; Beausdjour, Goyer et al. 1999). King et al. (King, Lawrence et al. 2001) pointed out that all of the plant pathogens, key mold, produce one or more herbicide-active thaxtomin (a plant toxin) component. Hiltunen et al. (Hiltunen, Laakso et al. 2006) compared the purification of four sax-tomin (thaxtomin, a phytotoxin) component from the culture broth by Streptomyces faecalis (S.) and IwWcfecW (including Saxedamine A (a phytotoxin), a saxedamine (thaxtomin, a phytotoxin) isomer, a sactomin b (thaxtomin B, a phytotoxin) (thaxtomin B, a plant toxin) And Sacradamine D (thaxtomin D, a phytotoxin)), and showed that all four components, in the in vitro propagation of potato, induced similar inhibition of germination growth, root growth (10-200 ppb) and necrosis Symptoms (200-1000 ppb). In addition, in the mixed ingredients of thaxtomin (a phytotoxin), it showed additive effect 201024278, but no synergy (Hiltunen, Laakso et al. 2006) According to the study of 〇1^(〇1^^奶〇11^1.2003), SacDomin is added to the 〇111 to A, a phytotoxin) (Fig. i) and Sac Damine D (thaxtominD, a plant). Toxin) has significant activity before and after use of non-systemic herbicides 'Of less than 1 uM and the concentration of Sakeduomin A (thaxtomin A, a plant toxin)' clothing and contribute to cell necrosis chamber, and inhibits monocotyledonous and dicotyledonous seedling length J (Healy, Wach et al, 2000). Sachdogin (thaxt〇min, a plant toxin) has been evaluated by Dow Agro Sciences as an active herbicide but lacks a systemic effect (King, Lawrence et al. 2001). In the ankle ring of the Diketopipemzine L, L-structure, the nitro group appears to provide the minimum required phytotoxicity. The nitro position in the anthracene ring is very local, and the phenyl group of alanine plays a necessary role in the phytotoxic structure _ Lawrence et al. 1989; King, Lawrence et al. 1992; King; Lawrence et al 2003). The role of herbicides is to disrupt cell wall synthesis (Fry and Loria 2002) to target inhibition of cellulose biosynthesis (King et al., 2001; Duval et al., 2005; Johnson et al. 2007). recent
Kang(Kang,Sem嶋et al. 2008)研究,則說明使用薩克多敏 (faxtonun、一種植物毒素),而將薩克多敏(thaxt〇min、一種植 物毒素)成份視為除藻劑,用於控制在水中環境的藤類 【發明内容】 ’、 本發明個錢乡卿^(祕、—種獅毒旬,作為除 草劑使用前後’在-般榖物、牧草、魏草和人工草 J的,草舰份。所謂的「生長系統」為任何驗般穀物、牧 草、猶尾草和人工草皮生長的生態系統。例如,「穀物生長 用的,長培養環可能是包含榖物或種子的田 =境。同樣地,「人工草皮生長系統」可為人工草皮生長系 、摘培養環境或田野、草地或高爾夫球場,這些包含人皮 料和雜草的生長,其中包括但不限鱗、筒麻、向日莫举諸 201024278 、曰田ίί:芬、西洋蒲公英、龍葵、圓葉錦葵、 巧狗尾卓、干錢、早熟禾、草地早熟禾、黑麦草、j、 '稗草’和尤其是徽菜—黎、豬草-反枝宽、 H菜-野介、_公英—西m、和麟_龍葵含^ 她min、-雌物毒素)的活性成份。另一個目 g 草fΪΪ除不會傷害穀物、牧草、描尾草和人: 旱皮生長,並環境無害的除草方法。 種碑述 疋或人卫草皮和穀物的生長系統。尤其是本發0月的& 系有至少一種薩克多敏(—η、-種植物 的本發明的成份可再含有載體和/或稀釋劑 實施例中’此成份為溶液。而在另一個具Ξ 含有一_物#素诚份可溶解在 基基=釋=醇’或脂細如丙網、甲基乙Kang (Kang, Sem嶋 et al. 2008) studies that use saxedon (a phytotoxin) and saxedamine (a phytotoxin) as an algaecide. Vine used to control the environment in the water [Summary of the invention] ', the invention of a Qianxiangqing ^ (secret, - a variety of lion poison, used as a herbicide before and after 'in the common animal, pasture, Weicao and artificial grass J., the grass ship. The so-called "growth system" is an ecosystem for the growth of grains, pastures, yarrows and artificial turf. For example, "for growing grains, long culture rings may contain scorpions or seeds. Similarly, the "artificial turf growth system" can be an artificial turf growth system, a picking culture environment or a field, grassland or golf course, which includes the growth of human leather and weeds, including but not limited to scales. Tube numbness, pilgrimage to 201024278, Putian ίί: Fen, Western dandelion, Solanum nigrum, Lobelia mallow, Qiaotailtail, dry money, bluegrass, bluegrass, ryegrass, j, '稗草' and Especially the Anhui cuisine - Li, ragweed - anti-branches , H dishes - mediated wild, British public _ - West m, Solanum nigrum and Lin _ ^ containing her min, - female biotoxins) active ingredient. Another goal is that it does not harm grains, pastures, sedges, and humans: dry-skin growth and environmentally sound weeding methods. Inscriptions 生长 or human turf and grain growth systems. In particular, in the present invention, at least one of the components of the present invention, which may be further contained in the carrier and/or diluent embodiment, is a solution. One with 一 containing a _ thing #素诚份 can be dissolved in the base = release = alcohol 'or fat such as the network, methyl
^Z::Z ΙΙΙΤΛ%ΙΙι^ ϊ 草除=以 射成份ΛΐϊΓ克多S物f素)和—種化學和/或生物除草 在穀物(如小麥、黑小麥(、:;麥-、=素= 201024278 中:可再蝴鮮生長系統 帽 成份,為 ;I;«t ^ί':5 〇 ❹ =ΙΓ3長4些髫包括但不限於玉米、小麥、t 1111^ 生長系統中或j'ί穀物 Ϊ根:雀麦属、黑麦草属、翦股穎属、结 :ii^;tt。、一種植物毒素)或鹽分,有效調節抑制 和/或貓尾草的生長。尤其是本發明提供的方法,除 敏(thaxt〇min、一種植物毒素)外,可提供至少第二種的除^ 201024278 )mm 種=毒素)和第二種的除草劑成份,可用於穀物、人工草 皮、牧卓和/或描尾草的生長系統中。 【實施方式】 在提供有相關數值的情況下,除另有說明,干擾單位值钟 ^到低限值的1/10為準,干擾界限間為下限和上限值間; 範圍内的任何標讀或干擾值。這些較小細的下限和上限 值,可個別列入較小的範圍中,而特別排除某些標示值範圍 外。標:示範圍包含-個《兩個限值範圍,其範圍可排除任何屬 相關範圍的一個或兩個干擾區間的限值。 除另有說明,本文使用的技術和科學用語,其意義相同於 本發明領域的一般用語。雖然有其他跟本發明類似或同等的方 法和材料’也可用於本發明的應用和測試中,本文内容引用最 應注意的是,在本文内容和提出的專利聲明中,所使用的 「一個」或「一種」的字義,除非另有說明,否則可表示單數 或複數的意思。 本發明使用的薩克多敏(thaxtomin、一種植物毒素),可採 自下列的放線菌培養液疮鏈霉菌(S.腳6㈣-ATCC 49173, 酸疮麻鏈霉菌(S· aczVfccaMes) - ATCC 49003 和 BL37-EQ-〇l〇 -或自市場購買。 本發明使用的薩克多敏(thaxtomin、一種植物毒素)包含但 不限於如含有cyclo-(L-4-nitrotryptophyl-L-苯丙氨酰)物質的環 狀二肽物質。在具體實施例中,適當的二酮哌嗪基團可N-甲 基化’而包含含笨丙氨酰α和環碳羥基的同族元素。在本具 體實施例的化學成份含有: ' 201024278^Z::Z ΙΙΙΤΛ%ΙΙι^ ϊ 除 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = 201024278 Medium: The composition of the fresh growth system cap can be; I; «t ^ί': 5 〇❹ = ΙΓ 3 length 4 髫 including but not limited to corn, wheat, t 1111^ growth system or j'ί Cereal roots: brome, ryegrass, bentgrass, knots: ii ^; tt., a phytotoxin) or salt, effective regulation of inhibition and / or growth of Timothy. Especially provided by the present invention The method, in addition to the sensitive (thaxt〇min, a phytotoxin), can provide at least a second type of herbicide (201024278) mm and a second herbicide component, which can be used for cereals, artificial turf, grazing and / or the growth system of the grass. [Embodiment] In the case where the relevant value is provided, unless otherwise stated, the interference unit value clock is 1/10 of the low limit value, and the interference limit is between the lower limit and the upper limit value; Read or interfere with the value. These smaller fine lower and upper limits can be individually listed in smaller ranges, with the exception of certain excluded values. Mark: The scope includes - two limits, the range of which excludes any one or two interference intervals that are within the relevant range. Unless otherwise indicated, the technical and scientific terms used herein have the same meaning as the ordinary terms used in the field of the invention. Although other methods and materials similar or equivalent to the present invention can also be used in the application and testing of the present invention, the most important thing to note in this document is the "one" used in the content of this document and the proposed patent statement. Or the meaning of "a", unless otherwise stated, may mean singular or plural. The saxedamine (thaxtomin, a phytotoxin) used in the present invention can be obtained from the following actinomycete culture Streptomyces sp. (S. foot 6 (four) - ATCC 49173, S. acz Vfcca Mes - ATCC 49003 And BL37-EQ-〇l〇- or purchased from the market. The saxedamine (thaxtomin, a phytotoxin) used in the present invention includes, but is not limited to, containing cyclo-(L-4-nitrotryptophyl-L-phenylalanyl) a cyclic dipeptide material of a substance. In a particular embodiment, a suitable diketopiperazine group can be N-methylated' and comprises a homologous element comprising a strepalanyl a and a cyclic carbyl group. The chemical composition of the example contains: ' 201024278
r2 R5 0 r4 其中的R!為甲基或H,&為羥基或h,R3是曱基或 Η ’ R4是羥基或Η,Rs羥基或HH,Rg是羥基或η等這些物 質的混合物。 依據本發明,適當的薩克多敏(thaxtomin、一種植物毒素) 〇 成份其未加以限制的實施例,得包括但不限於使用薩克多敏 A (thaxtomin A、一種植物毒素)、薩克多敏 a (thaxtomin A、 一種植物毒素)鄰異構物、薩克多敏B、薩克多敏c、經基薩 克多敏C、薩克多敏a (thaxtomin A、一種植物毒素)p_異構 物、經基薩克多敏A (thaxtomin A、一種植物毒素)和des_N_ 曱基薩克多敏C和任何的此類物質的衍生物(參考圖1)。 本發明的成份可噴灑在植物或土壤上,具體說明如案例 中,這些成伤可為粉塵狀、粗粉狀、小顆粒狀、顆粒狀、濕粉 狀、乳油、液體製劑、懸浮劑、水狀或油降解顆粒懸浮狀物質。 本發明的成份含載體和/或和/或稀釋劑,本文所謂的載體 為惰性、有機或無機材質,此物質混合有活性成份或配方,有 助於植物和標的物的處理、儲存、運送和/或處理。在使用除 草劑前後的稀釋劑或載體成份,包括但不限於水劑、粉劑、酒 精、礦物油和甘油成份等。R2 R5 0 r4 wherein R! is methyl or H, & is hydroxy or h, R3 is fluorenyl or ’ ' R4 is hydroxy or hydrazine, Rs hydroxy or HH, and Rg is a mixture of hydroxy or η and the like. In accordance with the present invention, suitable unrestricted examples of thactomin (a phytotoxin) oxime component include, but are not limited to, the use of saxedin A (a phytotoxin), sacdo Min (a), thaxtomin A Isomers, viasacsin A (thaxtomin A, a phytotoxin) and des_N_decyl sacredamine C and any derivatives of such substances (cf. Figure 1). The ingredients of the present invention can be sprayed on plants or soils. Specifically, in the case of such cases, the wounds can be dusty, coarse powder, small granules, granules, wet powder, emulsifiable concentrate, liquid preparation, suspending agent, water. Shape or oil degrades the particulate suspended matter. The ingredients of the present invention comprise a carrier and/or a diluent, and the carrier herein is an inert, organic or inorganic material which is mixed with an active ingredient or formulation to aid in the handling, storage, transport and disposal of plants and the subject matter. / or deal with. The diluent or carrier component before and after the use of the herbicide includes, but is not limited to, a liquid, a powder, an alcohol, a mineral oil, and a glycerin component.
本發明的成份含有至少兩種除草劑成份,其中一種為上述 的薩克多敏(thaxtomin、一種植物毒素)。如同具體實施例所提 到的薩克多敏(thaxtomin、一種植物毒素),其劑量範圍自〇〇1 到約5.0 mg/mL。另一種除草劑則為生物除草劑和/或化學除草 劑成份。生物除草劑則選自丁香、肉桂、轉樣、掛橘油、橘皮 油、腾毒素、克乃可莘頓(comexistin,一種植物毒素)、AAL 201024278 毒素^AAL-toxin ’ 一種植物毒素)、纖精酮、假筠亭碱、稻壳酮 B、咼梁醌、艾斯可雷毒素(ascaulat〇xin、一種植物毒素)和艾 斯可雷毒素(ascaulatoxin、一種植物毒素)配糖體的成份。在具 體實施例中,此成份可含有薩克多敏、一種植物毒 素)、香茅油、表面活性劑和/或植物油配方。而在另一具體實 施例中,成份含有薩克多敏(thaxtomin、一種植物毒素)、假錦 亭碱^ ^離子表面活性劑和/或植物油。生物除草劑如香茅油 或假筠亭碱的成份含量約為mg/mL到5〇 mg/mL,而最 佳的成份含量則約0.5 mg/mL到10 mg/mL。化學除草劑可選 自含除蟲劑和鹽份、麥草和鹽份、托普拉梅佐恩(t〇p ramezone » 一種殺蟲劑)、特博特瑞文(temb〇trione,一種除草劑)、左旋莫 多草(S-Metolachlor)、草脫淨(Atrazine)、曱基績草酮 (mesotrione)、氟氣確隆、2,4-滴丁醋(2,4-dichlorophenoxyacetic acid)、煙响續隆(nicosulfUron)、嗔續隆 (thifensulfUron-methyl)、續草靈(asulam)、β秦草嗣(metribuzin)、 禾草靈(diclofop-methyl)、伏寄普(fluazif〇p)、精嗯σ坐禾草靈 (fenoxaprop-p-ethyi)、續草靈(asulam)、復祿芬(oxyfluorfen)、 砜嘧磺隆(rimsulfUron)、2 曱 4 氯丙酸(mecoprop)、and 二氯喹 琳酸(quinclorac)、禾草丹(thiobencarb)、可滅縱(clomazone)、 赛伏草(cyhalofop)、敵稗(propanil)、免速隆 (bensulfUron-methyl)、平速爛(penoxsulam)、綠草定(triclopyr)、 味草烟(丨11137技1^口711)、氯'»比哺績隆(11&1〇3111^11:011-1116111>4)、施得 圃(pendimethalin)、雙草越(bispyribac-sodium)、《坐草嗣 (carfentrazone ethyl)、本達隆 / 三氟羧草醚(s〇dium bentazon/sodium acifluorfen) and 績酰腺(orthosulfamuron) 〇 化學除草劑如施得圃(pendimethalin)或可滅蹤 (clomazone)為除草劑使用前的成份配方,成份劑量約自〇.5 mg/mL到15 mg/mL,化學除草劑成份如赛伏草(cyhalofop)、 左旋莫多草(S-Metolachlor)、雙草醚(bispyribac-sodium)、平速 爛(penoxsulam)在使用後的成份含量,約自1 mg/mL到40 201024278 mg/mL,在特別情況下’則約15 mg/ml到35 mg/mL。成份進 一步含混合有佐劑,此蔬菜油成份為油酸乙酯、聚乙氧基化烷 基酯和壬基紛。此成份進一步含表面活性劑,用於乳化、分散、 潤濕、傳播、整合和分化的調配、穩定活性成份和改善流動性 和抑制鏽化。乳化劑跟分散劑的選擇,如非離子、陰離子、兩 性和陽離子分散劑和乳化劑,使用成份量則依據成份特性,以 及成份劑量有助於本發明除草劑的散佈特性而定。 使用後的配方,其成份使用含有蒙脫石枯土、凹凸棒石枯 土及類似的膨脹性枯土和增稠劑,如黃原膠、阿拉伯樹膠和其 他多醣增稠劑及分散穩定劑,如非離子表面活性劑(如聚氧乙 Ο 烯(20)單月桂酸酯或聚山梨醇酯60 POE (20)山梨醇單硬脂 酸、乙一醇單硬脂酸酯)。粘土濃度的差異約為所有成份量的 0-2.5%之間,多醣增稠劑的範圍約為總成份量的〇_〇.5%w/w, 而表面活性劑的成份量約為總成份量的〇_5% w/w。 實施例 本發明的成份和方法,如下列無限制值的說明内容中。其 實施例提供不同的具體實施例内容,但不限於材質、條件、重 量比、處理過程參數和本文類似内容的相關發明内容。 實施例1 〇 在溫室處理的研究檢測中,使用6英吋的玉米植物(Zea may var. Sunglow)喷灑有增量濃度的薩克多敏a (thaxt〇min A、一種植物毒素),混合於4%乙醇、〇 〇2〇/〇多山醇酯6〇p〇E (20)山梨醇單硬脂酸溶液中。此噴霧溶液含〇 125、〇 25、〇 5 和l.Omg薩克多敏A(thaxtominA、一種植物毒素)/mL,而 喷灌在整個植物表面上。各處理步驟重複3次,溶液濃度控制 即含有4%4%乙醇、0.02〇/〇多山醇酯6〇p〇E(2〇)山梨醇單硬 脂酸作為表面活性敝用。在處理前後,植_在人造光的溫 室中生長(12-h光/暗循環),溫度為25〇c。 植物則進行為期1週間隔的評估,於處理後7日開始 行。於處理後的3週内,完成最後的評估,評估時,觀察使 11 201024278 是使用最高薩克多敏A(thaxtominA、一種植物毒素)濃度處理 的植物檢測上,無任何毒性存在。 實施例2 在玉米(Zea wi% var. Early Sunglow)和小麥 advww var· PR1404)的毒害性測試中,為確認闊葉雜草和藜草 的活性,則種植在相同的盆栽中,使用3個玉 米種子或5個小麥種子,且同時進行這些測試植物的喷灑處 理。在生長光調節下’有低於3英吋的生長量(各12_h光/暗循 ϊ衣)’ /jbl度為28 C ’且喷濃有酸疮癌鏈霉菌(义㈣製 成的薩克多敏A (thaxtomin A、一種植物毒素)溶液,其中每 ml的溶液含〇.5和i.〇mg的薩克多敏A(thaxt〇minA、一種植❹ 物毒素)(4 °/0乙醇和0.2%非離子表面活性劑),有4 %乙醇+ 0.2%非離子的表面活性劑但不含薩克多敏A(thaxt〇minA、一 種,物毒素)的成份,則控制組所使用的檢測劑。各處理步驟 執行3次,在生長光於18°c所處理的植物,分別在處理後的 第7、14和21日’就玉米和小麥和藜草的毒害性進行相關的 觀察。 在各觀察期間中,使用薩克多敏A (thaxtomin A、一種植 物毒素)處理的穀物,則未發現到毒害性的症狀。使用最高劑 量的薩克多敏A (thaxtomin A、一種植物毒素)(1.〇 mg/mL)處 理後的藜草’形成跟玉米和小麥_控管航下的生長結果。◎ 實施例3 為能夠在高粱植物中,測試薩克多敏A(thaxt〇minA、一 種植物毒素)的毒害性’貞I〗將5 ;^冑_植物咖响種 植在各為4”x 4”的培養土盆栽中。在使用含〇 5和【〇 薩 土多敏A (thaxtomin A、一種植物毒素)/mL的溶液喷灑處理 刖,植物在最佳的溫室條件生長。在嘴灑處時, 處理步驟重複3次,而控制處理步驟,= 物 ,仃载體處理(4%乙醇、0.02%多山醇醋6〇ρ〇Ε⑽山梨 單硬脂酸)。毒害性的檢測評估,則在處理後的7日間隔期間 12 201024278 仃最後的評估檢測為處理3週後期間,在以任何濃度處 理後,未發現有毒害性。 〜 實施例4 酸疮痂鏈霉菌(又诚㈣(ATCC_49〇〇3)則在燕麥麩The composition of the present invention contains at least two herbicide components, one of which is thaxtomin (a phytotoxin) as described above. As shown in the specific examples, thactomin (a phytotoxin) is dosed from 〇〇1 to about 5.0 mg/mL. Another herbicide is a bioherbicidal and/or chemical herbicide ingredient. The biological herbicide is selected from the group consisting of clove, cinnamon, transcript, orange oil, orange peel oil, toxin, comexistin (a phytotoxin), AAL 201024278 toxin ^AAL-toxin 'a phytotoxin), Ingredients of fibrinone, scutellarin, rice huskone B, scorpion scorpion, ascole toxin (ascaulat〇xin, a phytotoxin) and eskeletinxin (a phytotoxin) glycoside . In a specific embodiment, the ingredient may contain a saturin, a phytotoxin, a citronella oil, a surfactant, and/or a vegetable oil formulation. In yet another embodiment, the composition comprises saxtomin (a phytotoxin), a ruthenium salt, and/or a vegetable oil. The content of the biological herbicide such as citronella oil or sulphate base is about mg/mL to 5 〇 mg/mL, and the optimum ingredient content is about 0.5 mg/mL to 10 mg/mL. Chemical herbicides may be selected from the group consisting of insecticides and salts, wheat straw and salt, topramezone (an insecticide), and tembrit trione (a herbicide). ), S-Metolachlor, Atrazine, mesotrione, fluorine gas, 2,4-dichlorophenoxyacetic acid, tobacco Nicosulfuron, thifensulfuron-methyl, asulam, metaribuzin, diclofop-methyl, fluazif〇p, fine σ 坐 禾 禾 oxa oxa ( fenoxaprop-p-ethyi), sylvain (asulam), oxyfluorfen, rimsulfuron (rimsulfuron), 2 曱 4 chloropropionic acid (mecoprop), and dichloroquine Acid (quinclorac), thiobencarb, clomazone, cyhalofop, propanil, bensulfuron-methyl, penoxsulam, green grass (triclopyr), taste grass smoke (丨11137技1^口 711), chlorine '» than 哺 隆 (11&1〇3111^11:011-1116111>4), pendimethalin, shuangcao ( Bispyrib Ac-sodium), carfentrazone ethyl, s〇dium bentazon/sodium acifluorfen and orthosulfamuron 〇 chemical herbicides such as pendimethalin or Clomazone is a formulation of the herbicide before use. The dosage range is from about 5 mg/mL to 15 mg/mL. Chemical herbicide ingredients such as cyhalofop and S-Metolachlor ), bispyribac-sodium, penoxsulam, after use, the content of ingredients from about 1 mg / mL to 40 201024278 mg / mL, in special cases 'about 15 mg / ml to 35 Mg/mL. The ingredients further comprise an adjuvant which is an ethyl oleate, a polyethoxylated alkyl ester and a sulfhydryl group. This ingredient further contains a surfactant for the formulation of emulsification, dispersion, wetting, spreading, integration and differentiation, stabilizing the active ingredient and improving fluidity and inhibiting rusting. The choice of emulsifier and dispersant, such as nonionic, anionic, amphoteric and cationic dispersants and emulsifiers, the amount of ingredients used will depend on the characteristics of the ingredients, and the dosage of the ingredients will contribute to the dispersion characteristics of the herbicides of the present invention. After use, the ingredients used include montmorillonite, attapulgite and similar expansive soils and thickeners such as xanthan gum, gum arabic and other polysaccharide thickeners and dispersion stabilizers. For example, a nonionic surfactant (e.g., polyoxyethylene (20) monolaurate or polysorbate 60 POE (20) sorbitan monostearate, ethyl alcohol monostearate). The difference in clay concentration is between 0 and 2.5% of the total amount of the component, the range of the polysaccharide thickener is about 〇_〇.5% w/w of the total component amount, and the composition of the surfactant is about the total component. The amount of 〇 _ 5% w / w. EXAMPLES The ingredients and methods of the present invention are as set forth in the following non-limiting examples. The embodiments provide different specific embodiments, but are not limited to the materials, conditions, weight ratios, process parameters, and related inventions herein. Example 1 In a greenhouse treatment study, a 6-inch corn plant (Zea may var. Sunglow) was sprayed with an increasing concentration of saxedamine A (thaxt〇min A, a plant toxin), mixed In 4% ethanol, 〇〇 2 〇 / 〇 polysorbate 6 〇 p 〇 E (20) sorbitol monostearic acid solution. This spray solution contained 〇 125, 〇 25, 〇 5 and 1.0 mg of saxtomin A (a phytotoxin) / mL, and sprinkled over the entire surface of the plant. Each treatment step was repeated 3 times, and the solution concentration control contained 4% 4% ethanol, 0.02 〇/〇 polysorbate 6〇p〇E (2〇) sorbitol monostearic acid as a surface active hydrazine. Before and after treatment, the plants were grown in a greenhouse of artificial light (12-h light/dark cycle) at a temperature of 25 〇c. Plants were evaluated at intervals of 1 week and started on the 7th day after treatment. The final assessment was completed within 3 weeks of treatment. At the time of the evaluation, observations were made on the plants tested using the highest concentration of thaxtomin A (a phytotoxin) without any toxicity. Example 2 In the toxicity test of corn (Zea wi% var. Early Sunglow) and wheat advww var· PR1404), in order to confirm the activity of broadleaf weeds and valerian, it was planted in the same pot, using 3 Corn seeds or 5 wheat seeds were sprayed simultaneously with these test plants. Under the growth light regulation, 'there is less than 3 inches of growth (each 12_h light/dark ϊ ))' /jbl degree is 28 C ' and the sark is made of Streptomyces sphaeroides (S. A solution of sympathetic A (thaxtomin A, a phytotoxin) containing 〇.5 and i.〇mg of saxdamine A (thaxt〇minA, a planting scorpion toxin) (4 ° / 0 ethanol) And 0.2% nonionic surfactant), with 4% ethanol + 0.2% nonionic surfactant but no Sachsin A (thaxt〇minA, one, toxin), the control group used The detection agent was carried out three times, and the plants treated with light growth at 18 ° C were observed on the 7th, 14th and 21st day after treatment, respectively, regarding the toxicity of corn and wheat and valerian. No toxic symptoms were found in grains treated with saxedin A (a phytotoxin) during each observation period. The highest dose of thaxtomin A (a phytotoxin) was used. (1. 〇mg/mL) treated yarrow 'formed with corn and wheat _ control tube growth results. ◎ Example 3 is able to be high In the alfalfa plants, the toxic '贞I〗 of Saccharin A (thaxt〇minA, a phytotoxin) was tested and planted in a 4" x 4" culture potted pot. The plants are grown in the optimal greenhouse conditions by spraying the solution containing 〇5 and [thaxtomin A (a phytotoxin)/mL. When the mouth is sprinkled, the treatment steps are repeated 3 times. And control treatment steps, = substance, 仃 carrier treatment (4% ethanol, 0.02% poly-alcohol vinegar 6 〇 〇Ε 〇Ε (10) Yamanashi monostearic acid). The detection of toxicity is measured at 7-day intervals after treatment. Period 12 201024278 仃The final evaluation was found to be toxic after treatment at any concentration for 3 weeks after treatment. ~ Example 4 Streptomyces solanacearum (Chengcheng (4) (ATCC_49〇〇3) in oat bran
Ο 長5日(25t>c/ 2⑻啊),使用薩克多敏a (^ctomm A、一種植物毒素)處理的整個細胞培養物,使用薩 A (thaXtomin A、一種植物毒素)XAD樹脂提取。乾燥 提取物’則懸浮在4%的乙醇和0.00 mg/mL濃度為 子表面活性劑中,此溶液有兩種不同的薩克多敏A axtomin A、一種植物毒素)(〇 5和j 濃度成份進 行下列闊葉雜草品種的檢測: 徽菜-# 冏麻-^ 向日葵-向沒紊 豚草-凝草 藜草、三黃-及#克 旋在-田旋花 野生芬菜-导齐 请公集-西洋蒲公英 龍葵、黑色-瘧奏 錦凑~圓葉錦葵a 也用於下列的雜草品種: 狗尾草-金芑拷名草 雀麥~旱雀麦 藍草-子遵禾 月德基藍草-草地子燕术 黑麥草/多年生-(,黑產草) 高羊茅高丰表安盛2號,LS1100) 稗萆-稗草 所有植物以4”χ4”的塑膠盆栽進行檢測3次,未處理的控 13 201024278 制組植物’則喷灑有載體溶液成份(4%乙醇和〇 〇2% glyc〇sperse) ’而呈現正向反應的控制組植物,則以1 fl 〇z/acre 的速率進行重複檢測。處理後的植物放置在溫室中,於12h光 /暗循環條件下培養。闊葉品種的每週測試評估資料,如表j 所示。 表1 ·就不同雜草品種’進行蓮克多敏A(tha;xtomin A、 一種植物毒素)的乾碟病嫌4Γ斯s. iic/他caW吻提取物控制處 理:評估等級:0 -未進行控制、1 _ 10%控制處理、2 _ 25% 控制處理、3-5〇%控制處理、4_75%控制處理、5 — 100 %5 5 days (25t>c/ 2(8)), whole cell cultures treated with sacDomin a (^ctomm A, a phytotoxin) were extracted using Sa A (thaXtomin A, a phytotoxin) XAD resin. The dried extract is suspended in 4% ethanol and 0.00 mg/mL in a sub-surfactant. This solution has two different saxedin A axtomin A, a phytotoxin) (〇5 and j concentration components) The following broadleaf weed species were tested: 徽菜-# 冏麻-^ Sunflower-to-no turkey grass--grass-grass, three yellow-and #克旋在-田旋花野芬菜- The public collection - Western dandelion Solanum nigrum L., black - malaria nectar ~ Lobelia mallow a is also used in the following weed species: foxtail - 芑 芑 名 草 ~ ~ ~ ~ ~ ~ ~ ~ ~ 遵 遵 遵 遵 遵 遵 遵 遵 遵 遵Grass - Grassland Swift Ryegrass / Perennial - (, Black Grass) Tall Fescue Gaofeng Table Ansheng 2, LS1100) All plants of 稗萆-稗草 were tested 3 times 4 4" in plastic pots, untreated Control group 13 201024278 The group of plants 'is sprayed with carrier solution components (4% ethanol and 〇〇 2% glyc〇sperse)' and the positive control group of plants, at a rate of 1 fl 〇z / acre Repeat the test. The treated plants were placed in a greenhouse and cultured under a 12 h light/dark cycle. Weekly test evaluation data for broadleaf varieties, as shown in Table j. Table 1 · For different weed species 'Lianke Domin A (tha; xtomin A, a phytotoxin) dry dish disease 4 s. iic / his caW kiss extract control treatment: evaluation level: 0 - not Control, 1 _ 10% control processing, 2 _ 25% control processing, 3-5 〇% control processing, 4_75% control processing, 5 - 100%
蒲公英 0.0 莊屬植物 0.0 微菜 0.0 豚草 0.0 冏麻 0.0 旋花 0.0 芥菜 0.0 向日葵 0.0 錦葵 0.0 藜草 0.0 0.0 0.0 2.0 0.0 0.0 2.7 0.0 0.0 2.0 0.0 0.0 1.0 0.0 0.0 1.7 0.0 0.0 1.0 0.0 0.0 3.3 0.0 0.0 1.0 0,0 0.0 1.0 0.0 0.0 3.5 2.3 4.0 2.0 2.2 2.3 2.7 2.0 2.0 2.0 0.5 0.0 1.0 1.0 1.0 2.0 1.0 0.0 1.2 4.0 4.5 3.5 2.0 0.5 1.0 1.0 1.0 1.2 4.0 4.0 4.2 2.0 3.7 2.0 2.3 2.0 2.0 0.5 0.0 1.0 0.3 1.0 0.0 2.8 3.5 1.7 0.5 1.0 1.0 3.0 3.7Dandelion 0.0 Zhuangyuan 0.0 Microlore 0.0 Ragweed 0.0 Castor 0.0 Convolvulus 0.0 Mustard 0.0 Sunflower 0.0 Mallow 0.0 Herba 0.0 0.0 0.0 0.0 0.0 0.0 2.7 0.0 0.0 2.0 0.0 0.0 1.0 0.0 0.0 1.7 0.0 0.0 1.0 0.0 0.0 3.3 0.0 0.0 1.0 0,0 0.0 1.0 0.0 0.0 3.5 2.3 4.0 2.0 2.2 2.3 2.7 2.0 2.0 2.0 0.5 0.0 1.0 1.0 1.0 2.0 1.0 0.0 1.2 4.0 4.5 3.5 2.0 0.5 1.0 1.0 1.0 1.2 4.0 4.0 4.2 2.0 3.7 2.0 2.3 2.0 2.0 0.5 0.0 1.0 0.3 1.0 0.0 2.8 3.5 1.7 0.5 1.0 1.0 3.0 3.7
混有濃度為0.5 mg/mL或更高的薩克多敏A (thaxtomin A 種植物毒素)的酸疮疮鍵霉菌(《S. 培養液,在 最常見的雜草品種,在一般闊葉雜草品種(蒲公英、芥末和藜 草)的人工草皮和穀物生長系統中,出現有很好的效果 201024278 (>50%)。一些雜草的控制,如龍葵和徽菜則不完全,但薩克 多敏A (thaxtomin A、一種植物毒素)即使以最低的濃度(〇 5 mg/mL),則會造成這些雜草的不良發育。 在此相同的研究中,使用〇·5或1.0 mg/mL薩克多敏A (thaxtominA、一種植物毒素)濃度處理者,則看到有反效果出 現。在所有已檢測的雜草品種中,即使以較高的薩克多敏A (thaxtominA^ —種植物毒素)濃度處理,仍未看到毒害性的效 果。圖4顯示在使用薩克多敏A(thaxt〇minA、一種植物毒素) 處理1週後,不同雜草的處理效果(Downy Brome,Tall Fe_ 和 Kentucky bluegrass)。 〇 實施例5 薩克多敏A (thaxtomin A、一種植物毒素)和兩種市售除草 劑(雙草醚(Bipyribac-sodium)調配為瑞吉孟(Regimem,除草 劑)’而檸檬草油調配為綠對(GreenMatchEX,除草劑))對小傘 莎草和水草,則使用小盆栽(1平方英吸)進行檢測。所有的單 一產品處理和水箱混合劑,則以每英畝喷灑57加侖。百分比 %的控制評估試劑,則在處理14日後完成,其結果如下表2。 各欄位的平均值則相同的字母,列於表2,彼此無統計差異性 p<0.05 〇 、 ❹依據此結果,25%重量百分比的檸檬草油未能改善薩克多 敏A (thaxtomin A、一種植物毒素)(〇·25 mg/mL)對莎草的效 果,但明顯增加對某些水草(田野檢測)和千金子草(溫室檢測) 的果 表2 : ®克多敏A (thaxtomin A、一種植物毒素)單一藥渐 亡混合,雙苎ft^bispyribac-sodiimO和檸樣草油對兩種稻米草 處理 期、小化纱早和水軍的效果 莎草控制(%) 水草控制(%) 95aS. cerevisiae (S. broth, the most common weed species, in general broadleaf mixed with Saxedamine A (thaxtomin A phytotoxin) at a concentration of 0.5 mg/mL or higher In the artificial turf and grain growth systems of grass varieties (dandelion, mustard and valerian), there is a good effect 201024278 (>50%). Some weed control, such as Solanum nigrum and Huizhou, is not complete, but Sachsin A (a phytotoxin), even at the lowest concentration (〇5 mg/mL), causes poor development of these weeds. In this same study, 〇·5 or 1.0 mg was used. /mL Saxedamine A (thaxtominA, a phytotoxin) concentration treatment, it is seen that there is a counter-effect. Among all the tested weed species, even with a higher Sachsamine A (thaxtominA^ - The concentration of phytotoxin) did not show the toxic effect. Figure 4 shows the treatment effect of different weeds after 1 week of treatment with saxedin A (thaxt〇minA, a phytotoxin) (Downy Brome, Tall Fe_ and Kentucky bluegrass). Example 5 Saxedo A (thaxtomin A, one Plant toxin) and two commercially available herbicides (Bipyribac-sodium blended with Regimem) and lemongrass oil blended with green (GreenMatchEX, herbicide) Sedge and water plants are tested using small pots (1 square ounce). All single product treatments and tank mixes are sprayed at 57 gallons per acre. Percentage of control evaluation reagents are completed after 14 days of treatment. The results are shown in Table 2. The average values of the fields are the same, listed in Table 2, and there is no statistical difference between each other p < 0.05 〇, ❹ According to this result, 25% by weight of lemongrass oil failed to improve Sa The effect of ketomin A (thaxtomin A, a phytotoxin) (〇·25 mg/mL) on sedge, but significantly increased for some aquatic plants (field test) and thousand gold grass (greenhouse test) fruit table 2: ® 克多敏 A (thaxtomin A, a phytotoxin) single drug gradually mixed, double 苎 ft^bispyribac-sodiimO and lemon-like grass oil on the two rice straw treatment period, small chemical yarn early and the water army effect sedge control (%) Aquatic control (%) 95a
薩克多敏(thaxtomin、一 種植物毒素)0.25 mg/mL 15 201024278 薩克多敏(thaxtomin A、 一種植物毒素)0.5 mg/mL 100a 5d 雙草醚 (bispyribac-sodium) (12 g/英畝) 87.5a 32.5a 雙草醚 (bispyribac-sodium) % (6g/英故) 47.5c 15c 雙草鍵 (bispyribac-sodium) V2 + fk 先多故(thaxtomin Λ、 一種植物毒素)0.5 mg/mL 67.5b 25ab 雙草鍵 (bispyribac-sodium) XA + 薩克多敏(thaxtomin A、 一種植物毒素)0.25 mg/mL 55bc 7.5c 檸檬草油5% 15d 10c 檸檬草油2.5% 12.5d 10c 檸檬草油1.25% 20d 依據檢測結果’ 1.25%的擰檬草油未能改善薩克多敏A (thaxtomin A、一種植物毒素)(〇25 mg/mL)對莎草的效果,但 明顯改善對某些水草(田野檢_叶金子草的效果。薩克多敏 A(thaxt〇min A、一種植物毒素)(〇 5吨就)可改善als抑制劑 Wpyribac sodium的效果,對莎草和一般草類而有標示值的一 半效果速率。 實施例6Saxedamine (thaxtomin, a plant toxin) 0.25 mg/mL 15 201024278 Saxedamine (thaxtomin A, a plant toxin) 0.5 mg/mL 100a 5d Bispyribac-sodium (12 g/acre) 87.5 a 32.5a bispyribac-sodium % (6g/inch) 47.5c 15c double-grass (bispyribac-sodium) V2 + fk first (thaxtomin Λ, a plant toxin) 0.5 mg/mL 67.5b 25ab Bispyribac-sodium XA + Sacradamine (thaxtomin A, a phytotoxin) 0.25 mg/mL 55bc 7.5c Lemongrass oil 5% 15d 10c Lemongrass oil 2.5% 12.5d 10c Lemongrass oil 1.25% 20d According to the test results, 1.25% of the lemongrass oil failed to improve the effect of saxedamine A (a phytotoxin) (〇25 mg/mL) on sedge, but improved significantly on some aquatic plants (field inspection The effect of _ leaf gold grass. Sachdogin A (thaxt〇min A, a plant toxin) (〇 5 tons) can improve the effect of the als inhibitor Wpyribac sodium, which has a labeled value for sedge and general grasses. Half effect rate. Example 6
取自酸疮痂鏈霉菌(& 培養液的薩克多敏A (thaxtomin A、一種植物毒素)則進行稻米的田野檢測,使用4 9 平方英叹的金屬環盆栽進行培養檢查。使用薩克多敏A (thaxtomin A、一種植物毒素)或將薩克多敏A (thaxt〇min A、 201024278 一種植物毒素)混合有檸檬草油(調配為綠對(GreenMatch EX ’除草劑))或赛伏草(cyhalofop)(調配為ClincherCA),在 完成調配後,則使用手提式的喷灑器每英畝喷灑57加侖。稻 米(品種名稱M209)則生長直到成熟為止’然後手動採收進行 雜草的計量。採收結果(kg/ha),以及各盆栽青果榕、小花莎草 和千金子草的相關檢測值,如表3所示。 表3 ·· Effect of麄克多敏A(thaxtomin A、一種植物毒素) 單一藥劑和混合有檸樣草油和赛伏草(Cyhalofop)對稻米收 赛制的效果A field test of rice was carried out from Streptomyces amyloliquefaciens (&s culture medium), and a culture inspection was carried out using a metal ring pot of 49 square inches of sigh. Sensitive A (thaxtomin A, a phytotoxin) or Sacramento A (thaxt〇min A, 201024278 a plant toxin) mixed with lemongrass oil (mixed to green pair (GreenMatch EX 'herbicide)) or cypress (cyhalofop) (mixed to ClincherCA), after completion of the blending, use a hand-held sprayer to spray 57 gallons per acre. Rice (variety name M209) grows until maturity' then manual harvesting for weed measurement The harvesting results (kg/ha), as well as the relevant detection values of each potted green stalk, sedge and sage, are shown in Table 3. Table 3 · · Effect of ax克多敏 A (thaxtomin A, a kind Phytotoxin) Effect of single agent and mixed with lemon-like grass oil and Cyhalofop on rice harvesting system
UTC ❹ 2·薩克多敏A(thaxtominA、一種植物毒素)(i8〇g/英畝) 3. 摔樣草〇il 1.25% +薩克多敏A (thaxtomin A、一種植 物毒素)(90克/英畝) 4. 賽伏草(cyhalofop)(—半標示值:52克/英畝)+薩克多 敏A (thaxtomin A、一種植物毒素)(90克/英故)+蔬菜油2.5 %UTC ❹ 2 · Sachdogin A (thaxtomin A, a phytotoxin) (i8〇g/acre) 3. Wrestling grass 〇 il 1.25% + Sac Tacmine A (thaxtomin A, a plant toxin) (90 g / Acres) 4. Cyhalofop (-half-labeled value: 52 g/acre) + Saxdormin A (thaxtomin A, a plant toxin) (90 g/inch) + vegetable oil 2.5%
各攔位的平均值以相同字母標示,無統計差異性p<〇 〇5。 結果顯示薩克多敏使用量為180克/英故可明顯降低莎草 數量,但不影響千金子的生長或收穫量。使用一半比值(薩克 多敏A(thaxtominA、一種植物毒素)90克/英畝)而混合有檸檬 草油,對莎草較使用赛伏草(cyhai〇fop)有更佳的效果(使用一 半標示值52克/英畝)。薩克多敏(9〇克/英畝)混有一半比值的 赛伏草(cyhalofop)時,對千金子有良好的控制效果-此混合 劑可明顯改善收穫量。 實施例7 赛伏草(cyhalofop) (2-[4-(4-氰基-2-氟苯氧基)苯氧]丙酸 丁酯)也可混合有含油酸乙酯,聚乙烯二炫基酯、乙氧基化壬 17 201024278 基酚(2.5% v/v)的佐劑’且增加薩克多敏a他邮咖匕八、 一種植物毒素)的濃度(自ATCC株49003純化),其濃度為〇1 0.2和0.4 m克/ml。在稀釋前’ 2-[4-(4-氣基-2-氣苯氧基^苯氧] 丙酸丁酯的濃度為 29.6% (2.38 lb/gal)和 21.7% (2 lb/gal)。這些 混合劑對車前草、青果榕、小花莎草和千金子的生長影響,^ 在溫室中進行檢測。同樣地,M104種的稻米植物對藥^的影 響,也進行相關的生長檢測,而所有的植物則在處理7、15^ 21日後’進行相關的評估檢測。使用赛伏草(cyhal〇f〇p)調配 為Clincher CA在處理後第21日的檢測結果,如下表4。 〇 青果榕 %控制 A Clincher C A (6·5 oz/acre)+ 麄克多敏A (thaxtomin Λ 一種植物毒 素)(m 克/mL)The average value of each block is indicated by the same letter, and there is no statistical difference p < 〇 〇 5. The results showed that the use of sacdomin was 180 g/ying, which significantly reduced the number of sedge, but did not affect the growth or harvest of the ginseng. Use half the ratio (thaxtomin A (a phytotoxin) 90 g/acre) mixed with lemongrass oil, which has a better effect on sedge than cyhai〇fop (using half of the mark) Value 52 g / acre). Sakdogin (9 gram/acre) has a good control of a thousand gold when mixed with half the ratio of cyhalofop - this mixture can significantly improve the yield. Example 7 Cyhalofop (butyl 2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propionate) may also be mixed with ethyl oleate, polyethylene dimer Ester, ethoxylated hydrazine 17 201024278 phenol (2.5% v / v) adjuvant 'and increase the concentration of sac Dominica a espresso, a phytotoxin) (purified from ATCC strain 49003), The concentrations were 〇1 0.2 and 0.4 m g/ml. The concentration of '2-[4-(4-carbo-2-cyclophenoxyphenoxy)propionate before dilution was 29.6% (2.38 lb/gal) and 21.7% (2 lb/gal). The effects of these mixtures on the growth of plantain, sorghum, sedge and sage, are tested in the greenhouse. Similarly, the effects of M104 rice plants on the drug are also related to growth detection, and all The plants were subjected to relevant evaluation tests after 7, 15^21 days of treatment. The results of the 21st day of treatment with Clincher CA were formulated using cyhal〇f〇p, as shown in Table 4 below. Control A Clincher CA (6·5 oz/acre) + 多克多敏 A (thaxtomin Λ a plant toxin) (m g / mL)
队傳释娜叩吕,umcfter (JA (29.6 % 赛伏草(Cyhal〇f0p) / 重量為計)使用一半的標示比值(6.5 〇z/acre),對雜草有良好的 控制效果,但對闊葉種或莎草則效果不佳4尾合有aincher ca 〇 表4.薩克多敏A(thaxtomin A、一種植物♦责)單一藥劑 和混合有赛伏草(cyhalofop),對稻米收獲董和雜草控制的效 (賽伏草(cyhalofop))和薩克多敏a (thaxtomin A、一種植物毒 的藥劑’在本檢測實驗中,對稻米雜草有良好的控制效果。 若混合有Clincher,薩克多敏A(thaxt〇minA、一種植物 對雜草有良好的改善效果。薩克多敏A(th她minA、一種植) 齡* — CA騎餘何賴敍下,造成稻米 的樂害。 實施例8 平速爛(penoxsulam) (2-(2,2-二氟代乙氧基)_N_(5,8_二甲氧 201024278 基[1,2,4]三偶氮[1,5(;]氣吡啶啉-2-71)-6-三氟甲基)苯績)則混 合有含油酸乙酯、聚乙烯二烷基酯和乙氧基化壬基酚(2.5 〇/0 ν/ν) ’且增加薩克多敏A(thaxtominA、一種植物毒素)的濃度 (純化自ATCC株49003),其濃度為0.1,〇·2和〇.4m克/ml。 2-[4-(4-氰基-氟苯氧基)苯氧]丙酸、滴丁酯或2_(2,2_二氟代乙 氧基)_义(5,8-二甲氧基[1,2,4]三偶氮[1,5C]氣吡啶啉_2_yl)_6_甲 基11比咬)苯橫的稀釋前濃度則分別為29.6% (2.38 lb/gal)和 2U% (2 lb/gal)。這些混合劑對車前草、青果榕、小花莎草和 千^子的生長影響效果,則在溫室中進行測定。同樣地,M1〇4 〇 Ο 稻米品種也進行生長和藥害檢測,而所有的植物在處理後第 7、14和21日,進行檢測。 實施例9 酸疮痂鏈霉菌(& fldda&吻則在燕麥麵發酵液中培養5 日(25°C,200 rpm) ’整個細胞的發酵液則使用樹脂提取, 而乾燥的粗提取物,再懸浮於4%的乙醇和0 2%非離子表面 活性劑,其濃度為10 m克/mL。稀釋提取物每ml含〇 2和 0.4mg的薩克多敏A(thaxtominA、一種植物毒素),進行3種 草類的檢測(青果榕(水莧菜屬)、小花莎草(莎草屬)和千金子 (千金子屬))。其他的處理包括使用假筠亭碱的劑量為2 5和5 〇 m克/mL,每個ml混合0.2mg薩克多敏A(thaxt〇minA、二 種植物毒素)和2.5mg的armentine。各處理步驟進行3次。處 理後的植物則放置在溫室中,進行12h光/暗循環的條件培養。 在處理後的第25日,其檢測結果如表5。 ' 口 表5 ·使用tt克多敏A(thaxtomin A、一種植物畚紊洲2 和0.4 m克/mL)或假筠亭喊(2.5 or 5.0 m克如乙)單一藥劑·, 或混合劑(0.2 + 2.5 m克/11^)對控制闊葉種、莎草和雜宜 草劑的溢室培養影響效果。 雅早職 處理 青果^制 莎萆控制 千金子控制 (/〇) (%)(%)The team passed on Nalu, umcfter (JA (29.6 % Cyhal〇f0p) / weight) using half the marked ratio (6.5 〇z/acre), which has good control effect on weeds, but Broad-leaved species or sedges are not effective. 4 tails are combined with aincher ca. Table 4. Sakedomin A (thaxtomin A, a plant ♦ blame) single agent and mixed with cyhalofop, for rice harvesting Dong And the effects of weed control (cyhalofop) and saxedin a (thaxtomin A, a plant poisoning agent) have good control effect on rice weeds in this test. If mixed with Clincher , Saxedo A (thaxt〇minA, a plant has a good effect on weeds. Sac Domin A (th her minA, a planting) Age* - CA riding Yu Lai, the rice music Example 8 Penoxsulam (2-(2,2-difluoroethoxy)_N_(5,8-dimethoxycarbonyl 201024278-based [1,2,4]trisazo [1, 5 (;) gas pyridin-2-71)-6-trifluoromethyl) benzene) mixed with ethyl oleate, polyethylene dialkyl ester and ethoxylated nonyl phenol (2.5 〇 / 0 ν/ν) 'And increase Sackdormin A (thaxt The concentration of ominA, a phytotoxin) (purified from ATCC strain 49003) at a concentration of 0.1, 〇·2 and 〇.4 m g/ml. 2-[4-(4-Cyano-fluorophenoxy)phenoxy ]propionic acid, butyl butyrate or 2_(2,2-difluoroethoxy)-(5,8-dimethoxy[1,2,4]trisazo[1,5C]pyridinoline The concentration of _2_yl)_6_methyl 11 to benzophenone was 29.6% (2.38 lb/gal) and 2U% (2 lb/gal) before dilution. These mixtures were for plantain, sorghum, sedge The effects of growth and the effects of the seeds were measured in the greenhouse. Similarly, the M1〇4 稻 rice varieties were also tested for growth and phytotoxicity, and all plants were treated on days 7, 14 and 21 after treatment. Example 9 Streptomyces faecalis (& fldda & kiss was cultured in oatmeal fermentation broth for 5 days (25 ° C, 200 rpm) 'The whole cell fermentation broth was extracted with resin, and the dried crude extract was extracted. Resuspended in 4% ethanol and 0% nonionic surfactant at a concentration of 10 m/mL. Diluted extract contains 〇2 and 0.4 mg of saxedamine A (thaxtomin A, a plant toxin per ml) ), testing of three kinds of grasses (green fruit) (Amaranthus), small flower sedge (Cygnus) and Thousands of Gold (Thousands of Gold). Other treatments include the use of sputum base at doses of 25 and 5 〇m g/mL, mixed per ml 0.2 mg of sacredin A (thaxt〇minA, two plant toxins) and 2.5 mg of armentine. Each processing step was performed 3 times. The treated plants were placed in a greenhouse and conditioned for 12 h light/dark cycles. On the 25th day after the treatment, the test results are shown in Table 5. ' 口表 5 · Use tt ketomin A (thaxtomin A, a plant 畚 洲 2 and 0.4 m gram / mL) or false 筠 喊 (2.5 or 5.0 m gram such as B) single agent, or mixture ( The effect of 0.2 + 2.5 m g / 11 ^) on the control of overflow culture of broadleaf species, sedge and hybrid grass. Ya morning job processing green fruit ^ system Shakes control Qian Qian control (/ 〇) (%) (%)
UTC 0aUTC 0a
Oa 0a 19 201024278 薩克多敏A (thaxtominA、一種植 物毒素)0.2 mg/mL 5.0b 48.3b 8.3ab 薩克多敏A (thaxtominA、一種植 物毒素)0.4 mg/mL 11.7c* 91.7d 10.0b 薩克多敏0.2 + 假筠亭域2.5 mg/mL 11.7c* 61.7c 73.3c 假碎亭喊2.5 mg/mL 0a 8.3a 8〇.〇c 假詞亭域5.0 m克 /mL 2.5ab 6.7a 92.3d * stunted 彼此無統計差異 在欄位中的平均值,以相同的字母表$ 性 p< 0.05。 ’ 薩克多敏A (thaxtomin A、一種植物毒 〇·4 m克/mL提供莎草良好的控制效果, 制效果不佳。混合有假竭亭减,對雜控Oa 0a 19 201024278 Sacradamine A (thaxtomin A, a plant toxin) 0.2 mg/mL 5.0b 48.3b 8.3ab Saxedamine A (thaxtomin A, a plant toxin) 0.4 mg/mL 11.7c* 91.7d 10.0b Sa Keduomin 0.2 + False Pavilion 2.5 mg/mL 11.7c* 61.7c 73.3c False pavilion shouting 2.5 mg/mL 0a 8.3a 8〇.〇c False word pavilion 5.0 m/mL 2.5ab 6.7a 92.3 d * stunted There is no statistical difference between each other in the field, with the same alphabet $ sex p < 0.05. ‘Saxdormin A (a plant poison 〇·4 m g/mL provides a good control effect of sedge, the effect is not good. Mixed with fake vestibule reduction, for miscellaneous control
=歸料_效果,她於只朗相敏 間葉種(青果峨使用所有其J ,然本發明已提出許多的具體實施例,但♦法詳細說明, =即使使用不同的等價物、變化和修改物,仍屬本發明範圍 藉由本說明内容,已提出不同的參考内内容即引 用各參考資料中的完整内容作為說明。㈣*本文 201024278 . 參考資料:= returning _ effect, she is only in the symmetry of the mesophyll species (green fruit 峨 use all of its J, but the invention has been proposed a number of specific examples, but ♦ detailed description, = even using different equivalents, changes and modifications The scope of the present invention is still covered by the description of the present invention, and the contents of the different references have been proposed, that is, the complete contents in each reference material are cited as explanations. (4) * This article 201024278. References:
Beausejour, J., C. Goyer, et al. (1999). "Production of thaxtomin A by Streptomyces scabies strains in plant extract containing media.n Can J Microbiol 45: 764-768.Beausejour, J., C. Goyer, et al. (1999). "Production of thaxtomin A by Streptomyces scabies strains in plant extract containing media.n Can J Microbiol 45: 764-768.
Duke, S. 0., S. R. Baerson, et al. (2003). "United States Department of Agriculture-Agricultural Research Service research on natural products for pest management." Pest Manas Sci 59: 708-717.Duke, S. 0., S. R. Baerson, et al. (2003). "United States Department of Agriculture-Agricultural Research Service research on natural products for pest management." Pest Manas Sci 59: 708-717.
Duke, S. 0., F. E. Dayan, et al. (2000). "Natural products as sources of herbicides: current status and future trends." Weed O Research 40: 99-111.Duke, S. 0., F. E. Dayan, et al. (2000). "Natural products as sources of herbicides: current status and future trends." Weed O Research 40: 99-111.
Fry, B. A. and R. Loria (2002). 'THAXTOMIN A: Evidence for a plant cell wall target." Physiological and Molecular PlantFry, B. A. and R. Loria (2002). 'THAXTOMIN A: Evidence for a plant cell wall target." Physiological and Molecular Plant
Pathology 60: 1-8.Pathology 60: 1-8.
Gerwick, B. C., P. R. Graupner, et al. (2005). Methylidene mevalonates and their use as herbicides. U. p. 7393812: 16.Gerwick, B. C., P. R. Graupner, et al. (2005). Methylidene mevalonates and their use as herbicides. U. p. 7393812: 16.
Healy, F. G., M. J. Wach, et al. (2000). "The txtAB genes of the plant pathogen Streptomyces acidiscabies encode a peptidesynthetase required for phytotoxin THAXTOMIN A ❹ prodcution and pathogenicity." Molecular Microbiology 38: 794-804.Healy, F. G., M. J. Wach, et al. (2000). "The txtAB genes of the plant pathogen Streptomyces acidiscabies encode a peptidesynthetase required for phytotoxin THAXTOMIN A ❹ prodcution and pathogenicity." Molecular Microbiology 38: 794-804.
Hiltunen, L. Η., I. Laakso, et al. (2006). "Influence of Thaxtomins in different combinations and concentrations on growth of micropropagated potato shoot cultures." J Agric Food Chem 54: 3372-3379.Hiltunen, L. Η., I. Laakso, et al. (2006). "Influence of Thaxtomins in different combinations and concentrations on growth of micropropagated potato shoot cultures." J Agric Food Chem 54: 3372-3379.
Hoagland, R. E. (2001). "Microbial allelochemicals and pathogens as bioherbicidal agents." Weed Technology 15: 835-857.Hoagland, R. E. (2001). "Microbial allelochemicals and pathogens as bioherbicidal agents." Weed Technology 15: 835-857.
Kang, Y., S. Semones, et al. (2008). Methods of controlling algae with THAXTOMIN and THAXTOMIN compositions. USA, Novozymes Biologicals, Inc. 21 201024278Kang, Y., S. Semones, et al. (2008). Methods of controlling algae with THAXTOMIN and THAXTOMIN compositions. USA, Novozymes Biologicals, Inc. 21 201024278
King, R. R., C. H. Lawrence, et al. (1992). "Chemistry of phytotoxins associated with Streptomyces scabies^ the causal organism of potato common scab." J. Aerie. Food Chem 40: 834-837.King, R. R., C. H. Lawrence, et al. (1992). "Chemistry of phytotoxins associated with Streptomyces scabies^ the causal organism of potato common scab." J. Aerie. Food Chem 40: 834-837.
King, R. R., C. H. Lawrence, et al. (1989). "Isolation and characterization of phytotoxin associated with Streptomyces scabies.” Journal of the Chemical Society. Chemical Communications 13: 849-850.King, R. R., C. H. Lawrence, et al. (1989). "Isolation and characterization of phytotoxin associated with Streptomyces scabies.” Journal of the Chemical Society. Chemical Communications 13: 849-850.
King, R. R., C. H. Lawrence, et al. (2003). "More chemistry of the thaxtomin phytotoxins." Phytochemistry 64: 1091-1096.King, R. R., C. H. Lawrence, et al. (2003). "More chemistry of the thaxtomin phytotoxins." Phytochemistry 64: 1091-1096.
King, R. R., C. H. Lawrence, et al. (2001). "Herbicidal properties o of the THAXTOMIN group of phytotoxins." J Agric Food Chem 49: 2298-2301.King, R. R., C. H. Lawrence, et al. (2001). "Herbicidal properties o of the THAXTOMIN group of phytotoxins." J Agric Food Chem 49: 2298-2301.
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22 201024278 【圖式簡單說明】 圖1為薩克多敏A(thaxtominA、一種植物毒素)的結構。 【主要元件符號說明】22 201024278 [Simple description of the diagram] Figure 1 shows the structure of saxedin A (a plant toxin). [Main component symbol description]
23twenty three
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| JP3350863B2 (en) * | 1991-04-26 | 2002-11-25 | ダウ・ケミカル日本株式会社 | Granule composition for paddy field weeding |
| JP3299812B2 (en) * | 1993-04-16 | 2002-07-08 | ダウ・アグロサイエンス・エル・エル・シー | Herbicide composition |
| JP3660380B2 (en) * | 1994-12-19 | 2005-06-15 | 住化武田農薬株式会社 | Agrochemical granules |
| KR970073338A (en) * | 1996-05-23 | 1997-12-10 | 에들러 마크 에스. | Herbicidal compositions showing synergistic action and weed control method using the same |
| JP4191406B2 (en) * | 2000-12-28 | 2008-12-03 | 三共アグロ株式会社 | Herbicide for paddy field |
| GB0116956D0 (en) * | 2001-07-11 | 2001-09-05 | Syngenta Ltd | Weed control process |
| KR20050114652A (en) * | 2003-03-13 | 2005-12-06 | 바스프 악티엔게젤샤프트 | Synergistically acting herbicidal mixtures |
| US7560416B2 (en) * | 2005-09-21 | 2009-07-14 | Riceco, Llc | Synergistic composition and method of use |
| US8110530B2 (en) * | 2006-12-21 | 2012-02-07 | Kumiai Chemical Industry Co., Ltd. | Herbicidal composition |
| MY147629A (en) * | 2007-01-22 | 2012-12-31 | Archer Daniels Midland Co | Water dispersible compositions and methods of using the water dispersible compositions |
| JP2008189578A (en) * | 2007-02-02 | 2008-08-21 | Kumiai Chem Ind Co Ltd | Herbicidal composition |
| JP2008239635A (en) * | 2007-02-26 | 2008-10-09 | Sumitomo Chemical Co Ltd | Antistatic resin composition and thermoplastic resin multilayer sheet |
| US7989393B2 (en) * | 2007-04-09 | 2011-08-02 | Novosymes Biologicals, Inc. | Methods of controlling algae with thaxtomin and thaxtomin compositions |
| AU2008263903A1 (en) * | 2007-06-12 | 2008-12-18 | Basf Se | Herbicidally effective composition |
| BRPI0812877A2 (en) * | 2007-06-12 | 2014-12-09 | Basf Se | "PIPERAZINE COMPOUNDS, USE OF A PIPERAZINE COMPOUND, COMPOSITION, AND UNWANTED VEGETATION METHOD". |
| DE102007028019A1 (en) * | 2007-06-19 | 2008-12-24 | Bayer Cropscience Ag | Synergistic crop tolerated combinations containing herbicides from the group of benzoylcyclohexanediones for use in rice crops |
| TW201024278A (en) * | 2008-12-31 | 2010-07-01 | Marrone Bio Innovations Inc | Uses of thaxtomin and thaxtomin compositions as herbicides |
-
2009
- 2009-12-25 TW TW98144895A patent/TW201024278A/en unknown
- 2009-12-30 KR KR1020117017287A patent/KR101682052B1/en active Active
- 2009-12-30 AU AU2009334514A patent/AU2009334514B2/en active Active
- 2009-12-30 JP JP2011544610A patent/JP2012514046A/en not_active Withdrawn
- 2009-12-30 CA CA2750141A patent/CA2750141C/en active Active
- 2009-12-30 MX MX2011007042A patent/MX2011007042A/en active IP Right Grant
- 2009-12-30 BR BRPI0924103A patent/BRPI0924103A2/en not_active Application Discontinuation
- 2009-12-30 NZ NZ59391609A patent/NZ593916A/en unknown
- 2009-12-30 KR KR1020177016550A patent/KR101767509B1/en active Active
- 2009-12-30 WO PCT/US2009/069856 patent/WO2010078452A2/en not_active Ceased
- 2009-12-30 KR KR1020167032388A patent/KR20160137659A/en not_active Ceased
- 2009-12-30 EP EP09837174A patent/EP2373170A4/en not_active Withdrawn
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2015
- 2015-04-08 JP JP2015079358A patent/JP2015178499A/en not_active Withdrawn
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2017
- 2017-04-06 JP JP2017076229A patent/JP6557698B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| EP2373170A2 (en) | 2011-10-12 |
| JP2015178499A (en) | 2015-10-08 |
| KR101767509B1 (en) | 2017-08-23 |
| AU2009334514B2 (en) | 2014-11-06 |
| CA2750141C (en) | 2017-11-28 |
| MX2011007042A (en) | 2011-07-20 |
| KR20160137659A (en) | 2016-11-30 |
| AU2009334514A1 (en) | 2011-07-28 |
| WO2010078452A2 (en) | 2010-07-08 |
| KR20110108367A (en) | 2011-10-05 |
| KR20170073718A (en) | 2017-06-28 |
| CA2750141A1 (en) | 2010-07-08 |
| NZ593916A (en) | 2013-05-31 |
| KR101682052B1 (en) | 2016-12-02 |
| EP2373170A4 (en) | 2012-06-27 |
| JP2012514046A (en) | 2012-06-21 |
| JP6557698B2 (en) | 2019-08-07 |
| JP2017171662A (en) | 2017-09-28 |
| BRPI0924103A2 (en) | 2018-03-20 |
| WO2010078452A3 (en) | 2010-10-21 |
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