CN101222848A - 环戊唑菌和氧唑菌在降低或防止禾谷类被真菌毒素污染中的联合应用 - Google Patents
环戊唑菌和氧唑菌在降低或防止禾谷类被真菌毒素污染中的联合应用 Download PDFInfo
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- CN101222848A CN101222848A CNA2006800258943A CN200680025894A CN101222848A CN 101222848 A CN101222848 A CN 101222848A CN A2006800258943 A CNA2006800258943 A CN A2006800258943A CN 200680025894 A CN200680025894 A CN 200680025894A CN 101222848 A CN101222848 A CN 101222848A
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- bacterium
- trichothecin
- fungi
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- penta azoles
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Classifications
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- 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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Storage Of Harvested Produce (AREA)
Abstract
本发明涉及环戊唑菌与氧唑菌在降低或防止禾谷类被产生单端孢菌素的真菌形成的真菌毒素污染中的联合应用。
Description
本发明涉及环戊唑菌(metconazole)和氧唑菌(epoxyconazole)在降低或防止禾谷类被产生单端孢菌素的真菌形成的真菌毒素污染中的联合应用。
所有禾谷类品种如小麦、大麦、黑麦、黑小麦、燕麦、稻和玉米的收获材料以及许多其他植物品种的收获材料可能被单端孢菌素毒素和来源于产生单端孢菌素的真菌的其他真菌毒素污染。最高度受侵染的是黑小麦、燕麦、普通小麦和尤其是硬粒小麦。这些毒素的来源是侵染这些植物的某些真菌，例如木霉属(Trichoderma)、葡萄穗霉属(Stachybotrys)和尤其是镰孢霉属(Fusarium)真菌。在全世界范围内，这类镰孢霉菌病(fusarioses)是重要的禾谷类病害，它们除了在美国和加拿大的传统产麦区外还影响澳大利亚和欧洲。镰孢霉属真菌主要寄生在土壤中，与其他微生物一起降解植物材料。它同样可以存在于活和死材料上。更经常作为禾谷类病害的出现由许多因素促进：
-在土壤上/中被镰孢霉属真菌侵染的有机物(作为接种物)，其中污染尤其被玉米茬和残留的玉米秆促进(例如参见A.Meier，B.Birzele，E.Oerke，U.Steiner，J.Krmer和H.Dehne，“小麦麦穗的镰孢霉属真菌侵染的不同接种物源的重要性”，Mycotoxin Research 1，2001，71-75)
-在春天和初夏充分湿润-温暖的气候，这使得真菌形成孢子囊
-传播孢子的降水和日照的更迭期
-植物(尤其是禾谷类)在孢子空气传播期间的开花(参见例如A.Obst，V.H.Paul，“Krankheiten und Schdlinge des Getreides”[禾谷类病害和禾谷类害虫]，Verlag Th.Mann，Gelsenkirchen-Buer，1993)。
禾谷类被镰孢霉属真菌侵染导致特征性的穗侵染，其中各穗白化且在某些情况下可以观察到微红色孢子包膜。在大多数情况下，穗在侵染位置以上干枯并且仅那里形成瘪粒。还有可能的是通常带浆的谷粒在侵染位置以下成熟；然而，这些谷粒通常被真菌毒素污染。因此，镰孢霉属真菌可能不仅降低产量，但是它们尤其还用真菌毒素污染收获的禾谷类。谷粒的污染可能发生在穗上以及不太常见的是发生在收获的材料的储存过程中。
在被污染植物或植物部分，例如禾谷类或由其制备的产品被摄取后，甚至微小剂量的其中所含真菌毒素也可能在人类和动物中导致严重的急性或慢性疾病。单端孢菌素毒素和其他来源于产生单端孢菌素的真菌的真菌毒素对健康的急性不利影响本身可能表现为大量症状，例如受损的免疫系统、IgA肾病(Berger病)、恶心、肾损伤、家养动物中的进食拒绝和呕吐以及家禽饲养中的产蛋减少。此外，在人类和动物中，这些真菌毒素具有雌激素和/或致突变活性(例如参见“Mykotoxine und ihr Einfluss auf dieImmunreaktionen”[真菌毒素及其对免疫响应的影响]，H.Khler，Bundesinstitut für gesundheitlichen Verbraucherschutz undVeterinrmedizin，Fachbereich 4，Jena，这例如可以在http://www.bgvv.de/sixcms_upload/media/98/koehler.pdf下找到)。在团簇小麦(bolus wheat)的情况下，怀疑在该类毒素的污染和啤酒的起泡之间存在关联(P.Gjersten，“啤酒中的喷涌：其本质、起因和预防”，Brewers Digest 42，1967，80-84)。
为了避免由于摄入上述真菌毒素而对健康产生的不利影响，国家机构和最高国家机构已经规定了可容许的真菌毒素最大量。因此，theCommittee on Food of the EU推荐成人的TDI(可容许日摄取量)为0.001mg DON(脱氧瓜萎镰菌醇；单端孢菌素毒素)/kg体重。根据德国对真菌毒素最大量的规定，直接消费的谷粒和加工的禾谷类产品中的谷粒至多可以含有0.5mg DON/kg所用禾谷类。在烘烤产品和馅饼中，DON含量必须不超过0.35mg/kg，而婴幼儿食品中的上限为0.1mg/kg(例如参见“Mykotoxine und ihr Einfluss auf die Immunreaktionen”，H.Khler，Bundesinstitut für gesundheitlichen Verbraucherschutz undVeterinrmedizin，Fachbereich 4，Jena，这例如可以在http://www.bgvv.de/sixcms upload/media/98/koehler.pdf下找到；此外，1999年6月2日的对食品中真菌毒素最大量的规定(Mykotoxin-Hchstmengenverordnung，MHmV)，Bundesgesetzblatt，1999年卷，第1部分，第29期，第1248页)。
为了降低上述真菌毒素在植物和植物部分以及由其得到的食品和动物饲料中的含量，当前使用的措施主要为如下措施：
-栽培不易受镰孢霉属真菌侵染的栽培品种；
-合适的轮作；尤其是避免将玉米作为前一茬作物；
-深耕(turning pillage)，尤其在前一茬作物为玉米时；
-防止镰孢霉属真菌发展的储存条件。
然而，这些纯预防性措施并不令人满意且效力并不可靠，尤其当盛行的气候条件有利于真菌侵染时。
EP-A-0769906以一般方式描述了环戊唑菌与其他三唑杀真菌剂组合用于在植物和植物产品中防治有害真菌。该组合物尤其用于在木材和木料产品以及纺织品中防治有害真菌。
需要更有效地降低或防止单端孢菌素毒素和来源于形成单端孢菌素的真菌的其他毒素对用于人类和动物消费的植物和植物产品，尤其是禾谷类的污染。
因此，本发明的目的是提供用于降低或防止禾谷类被产生单端孢菌素的真菌形成的毒素污染的化合物。
惊人的是，已经发现联合使用环戊唑菌和氧唑菌降低或防止了禾谷类被该类毒素的污染。
因此，该目的通过将环戊唑菌与氧唑菌组合用于降低或防止禾谷类被产生单端孢菌素的真菌形成的毒素污染而实现。
一方面，环戊唑菌和氧唑菌的联合使用可能包括使用包含这两种活性化合物的组合物。
因此，本发明还提供了包含环戊唑菌和氧唑菌的组合物在降低或防止禾谷类被产生单端孢菌素的真菌形成的毒素污染中的用途。
另一方面，联合使用环戊唑菌和氧唑菌还可以包括分开使用两种活性化合物，但相互在短时间内使用。有关环戊唑菌和氧唑菌的联合使用的更详细说明可以在下列描述中找到。
产生单端孢菌素的真菌形成的毒素是单端孢菌素和来自相同真菌且不同于单端孢菌素的毒素。
产生单端孢菌素的真菌优选为木霉属、葡萄穗霉属和尤其是镰孢霉属的那些。
在真菌毒素产生方面重要的是各种镰孢霉属真菌，例如作为最重要品种的大刀镰孢(F.culmorum)和禾本科镰孢(F.graminearum)(Mauler-Machnik A.& Suty A，2000：Aktueller Stand der internationalenForschung zur Bekmpfung von hrenfusariosen in Weizen[在小麦中对麦穗镰孢霉属病防治的当前国际研究状态]，22，Mycotoxin Workshop，Bonn，2000年6月5-7日)，此外还有脱顶镰孢(F.acuminatum)、燕麦镰孢(F.avenaceum)、F.crockwellense、木贼镰孢(F.equiseti)、串珠镰孢(F.moniliforme)、古巴尖镰孢(F.oxysporum)、早熟禾镰孢(F.poae)、F.proliferans、藨草镰孢(F.scirpi)、拟分枝孢镰孢(F.sporotrichioides)、微胶镰孢(F.subglutinans)和三隔镰孢(F.tricinctum)(H.Schnerr，“Quantitativer Nachweis von Deoxynivalenol undTrichothecene-bildenden Fusarium spp.mit Biosensor und PCR inGetreide”[在禾谷类中使用生物传感器和PCR定量检测脱氧瓜萎镰菌醇和形成单端孢菌素的镰孢霉属真菌]，Ph D thesis，2002，TechnischeUniversitt München；W.F.O.Marasas，P.E.Nelson和T.A.Toussoun，镰孢霉属真菌：识别和真菌毒理学，The Pennsylvania State UniversityPress，1984，University Park and London；L.Niessen和R.F.Vogel，在纯培养物和禾谷类样品中潜在的产生单端孢菌素的镰孢霉属真菌的组特异性PCR检测，System.Appl.Microbiol.，1998，21：618-631；A.Bottalico，禾谷类的镰孢霉属真菌病害：在欧洲的物种综合和相关真菌毒素特性，J.Plant Pathol.1998，80：85-103)。
在木霉属真菌的情况下，其代表尤其为在该方面具有重要性的绿色木霉(Trichoderma viride)。葡萄穗霉属真菌尤其为黑葡萄穗霉(Stachybotryschartarum)。
产生单端孢菌素的真菌尤其以镰孢霉属真菌为代表。
真菌毒素优选为单端孢菌素或玉米赤霉毒素。
玉米赤霉毒素是由镰孢霉属真菌的各个种形成的具有雌激素作用的真菌毒素。形成玉米赤霉毒素的真菌的优选底物是玉米和燕麦。然而，其他禾谷类品种也可能被重度侵染。因为玉米赤霉毒素在非常晚的真菌发育阶段形成，所以尤其在高度侵染的禾谷类中发现。玉米赤霉毒素没有急性毒性；然而，假定它具有致癌活性作用。在放牧动物时，它引起生殖障碍、早产和死胎(例如参见H.Schnerr，“Quantitativer Nachweis vonDeoxynivalenol und Trichothecene-bildenden Fusarium spp.mit Biosensorund PCR in Getreide”，PhD thesis，2002，Technische UniversittMünchen；“Mykotoxine und ihr Einfluss auf die Immunreaktionen”，H.Khler，Bundesinstitut für gesundheitlichen Verbraucherschutz undVeterinrmedizin，Fachbereich 4，Jena，这例如可以在http://www.bgvv.de/sixcms_upload/media/98koehler.pdf下找到)。
名称单端孢菌素指尤其由镰孢菌(fusaria)以及其他真菌在植物或植物产品上，尤其是禾谷类和禾谷类产品上形成的一组约100种真菌毒素。单端孢菌素具有宽谱生物作用。单端孢菌素通常抑制哺乳动物细胞中的蛋白质生物合成，有时甚至在低至1ng的浓度下。单端孢菌素中毒引起呕吐，腹泻，进食拒绝，胃肠道发炎，神经细胞、心肌、淋巴系统、睾丸、胸腺的损伤以及组织坏死的发展。动物和人类的中毒例如在术语“霉玉米中毒”(USA)、“豆壳中毒”(Japan)或“食物中毒性白细胞缺乏症”(CIS)下已知。根据它们的化学结构，将单端孢菌素分成A-D组。
尤其重要的是下列单端孢菌素毒素：T-2毒素，HT-2毒素，新茄病镰刀菌烯醇(neosolaniol)，单乙酰氧基镰草镰菌醇(monoacetoxyscirpenol)，草镰孢烯醇(diacetoxyscirpenol(DAS))，15-乙酰氧基镰孢烯二醇(15-acetoxyscirpendiol)，脱氧瓜萎镰菌醇(DON＝呕吐毒素)，瓜萎镰菌醇，3-乙酰氧基瓜萎镰菌醇，15-乙酰氧基瓜萎镰菌醇，镰刀烯酮(fusarenone)，T-2四醇和疣孢菌醇(verrucarol)。
真菌毒素尤其为脱氧瓜萎镰菌醇(DON).
禾谷类例如为小麦、稻、玉米、大麦、燕麦、黑小麦和黑麦。在本发明中，术语“禾谷类”表示植物本身及其收获产品，如谷粒或在玉米的情况下还表示玉米芯。
特别优选禾谷类选自小麦，如硬粒小麦或普通小麦。
环戊唑菌和氧唑菌组合尤其用于降低或防止小麦被脱氧瓜萎镰菌醇(DON)污染。
环戊唑菌和氧唑菌是已知的三唑类康唑(conazole)杀真菌剂且具有下列结构式(I＝环戊唑菌；II＝氧唑菌)：
这些化合物可以游离碱和盐用于组合物中。盐通过与酸反应而由游离形式得到。合适的酸例如包括无机酸，如氢氟酸、盐酸、氢溴酸、硫酸、硝酸和磷酸，以及有机酸，如乙酸、羟基乙酸、丙酸、甲磺酸、苯磺酸等。
这两种活性化合物(I)和(II)以及尤其是它们的盐还可以根据本发明以其溶剂化物，例如水合物或醇合物形式使用。
此外，化合物(I)和(II)可以纯立体异构体和以立体异构体混合物形式使用。这里的术语立体异构现象涉及Z/E异构体，在环戊唑菌的情况下是由于取代基在环戊烷环上1，5-位中的相对位置产生的，而在氧唑菌的情况下是由于取代基在环氧乙烷环上2，3-位中的相对位置产生的。
此外，可以使用(I)和/或(II)的相应Z和E异构体的单个对映体和对映体混合物。
环戊唑菌和氧唑菌以该组合对降低或防止禾谷类被所述真菌毒素污染存在协同增效效果的比例使用。环戊唑菌与氧唑菌的比例优选为20∶1-1∶20，特别优选10∶1-1∶10，更优选5∶1-1∶5，尤其是2∶1-1∶3，例如1∶1-1∶2。
根据本发明用于降低或防止上述真菌毒素的污染的环戊唑菌和氧唑菌的组合通常通过用这些活性化合物的组合处理禾谷类或其植物部分或禾谷类产品而使用。禾谷类或禾谷类产品的处理优选通过使禾谷类或其植物部分或禾谷类产品与两种活性化合物或包含这两种活性化合物的组合物接触而进行。为此，将组合物或单个活性化合物施用于禾谷类或其植物部分或禾谷类产品上。两种活性化合物环戊唑菌和氧唑菌因此可以混合物施用或分开施用。在分开使用的情况下，各活性物质可以同时施用或者作为处理顺序的一部分依次错开，其中在依次施用的情况下施用优选在几秒至几天，例如几秒至14天或几秒至7天的间隔内。此时各活性化合物以及包含它们的组合物通常以常用于作物保护领域的配制剂使用。更多详情在下面给出。
禾谷类或其植物部分或禾谷类产品的处理可以是保护性和治疗性的，即在被有害真菌侵染之前或之后。优选在尽可能接近侵染事件的时间进行，即在尽可能接近侵染的时间点时的侵染之前或之后。
施用时间、施用次数和在每种情况下使用的施用率必须与盛行的条件相适应且必须由本领域熟练技术人员对每一单独的情况确定。
活性化合物可以直接、以其配制剂形式或由其制备的使用形式借助喷雾、雾化、撒粉、撒播或浇灌来施用。使用形式完全取决于意欲的目的，尤其是禾谷类的属性和栽培品种以及要施用它们的禾谷类产品；在每种情况下应确保本发明所用活性化合物以及助剂的最佳可能分布。
环戊唑菌和氧唑菌以及包含这两种活性化合物的组合物通常以作物保护和材料保护领域常用的配制剂使用。
常规配制剂例如为溶液、乳液、悬浮液、分散体、糊、粉剂、撒播用材料、粉末和颗粒。
配制剂以已知方式制备，例如通过将活性化合物与溶剂和/或载体混合，需要的话使用乳化剂和分散剂而制备。适于该目的的溶剂/助剂主要为：
-水、芳族溶剂(如Solvesso产品、二甲苯)、石蜡(如矿物油馏分)、醇类(如甲醇、丁醇、戊醇、苄醇)、酮类(如环己酮、γ-丁内酯)、吡咯烷酮(NMP、NOP)、乙酸酯(乙二醇二乙酸酯)、二元醇、二甲基脂肪酰胺、脂肪酸及脂肪酸酯。原则上还可以使用溶剂混合物。
-载体如磨碎的天然矿物(如高岭土、粘土、滑石、白垩)和磨碎的合成矿物(如细碎硅石、硅酸盐)。
-表面活性剂，例如芳族磺酸如木素磺酸、苯酚磺酸、萘磺酸和二丁基萘磺酸的碱金属、碱土金属和铵盐，以及脂肪酸，烷基芳基磺酸盐，烷基硫酸盐，烷基磺酸盐，脂肪醇硫酸盐，脂肪酸和硫酸化脂肪醇二醇醚，此外还有磺化萘和萘衍生物与甲醛的缩合物，萘或萘磺酸与苯酚和甲醛的缩合物，聚氧乙烯辛基酚醚，乙氧基化异辛基酚、辛基酚或壬基酚，烷基酚聚乙二醇醚，三丁基苯基聚乙二醇醚，三硬脂基苯基聚乙二醇醚，烷基芳基聚醚醇，异十三烷醇，醇和脂肪醇/氧化乙烯缩合物，乙氧基化蓖麻油，聚氧乙烯烷基醚或聚氧丙烯烷基醚，乙氧基化聚氧丙烯，月桂醇聚乙二醇醚乙酸酯，山梨醇酯，木素亚硫酸盐废液，甲基纤维素或硅氧烷。合适的硅氧烷例如为聚醚/聚甲基硅氧烷共聚物，后者也称为“铺展剂”或“渗透剂”。
尤其适合制备可直接喷雾溶液、乳液、糊或油分散体的惰性配制助剂主要为中到高沸点的矿物油馏分，如煤油或柴油，此外还有煤焦油和植物或动物来源的油，脂族、环状和芳族烃类，例如甲苯、二甲苯，石蜡，四氢化萘，烷基化萘或其衍生物，醇类，如甲醇、乙醇、丙醇、丁醇和环己醇，酮类，如环己酮和异佛尔酮，强极性溶剂，如二甲亚砜、N-甲基吡咯烷酮或水。
粉末、撒播用材料和粉剂可以通过将活性物质与固体载体混合或同时研磨而制备。
颗粒如涂覆颗粒、浸渍颗粒和均质颗粒可以通过将活性化合物与固体载体粘附而制备。
固体载体例如为矿土如硅胶、硅酸盐、滑石、高岭土、活性粘土(attaclay)、石灰石、石灰、白垩、红玄武土、黄土、粘土、白云石、硅藻土、硫酸钙、硫酸镁、氧化镁；磨碎的合成材料；肥料如硫酸铵、磷酸铵、硝酸铵、脲类；以及植物产品如谷粉、树皮粉、木粉和坚果壳粉，纤维素粉和其它固体载体。
配制剂通常基于配制剂总重量以0.01-95重量％，优选0.1-90重量％的总量包含环戊唑菌、氧唑菌或其混合物。
用水稀释的产品(配制剂)例如为水溶性浓缩物(SL)、分散性浓缩物(DC)、可乳化浓缩物(EC)、乳液(EW，EO)、悬浮液(SC，OD)、水分散性和水溶性颗粒(WG，SG)以及水分散性和水溶性粉末(WP，SP)。直接施用的产品(配制剂)例如为粉剂(DP)、颗粒(GR，FG，GG，MG)和ULV溶液(UL)。
含水使用形式可以通过加入水由储存稳定的配制剂如浓缩溶液、乳液浓缩物、悬浮液、糊、可湿性粉末(喷雾粉末、油分散体)或水分散性颗粒制备并且它们可以例如通过喷雾施用。
为了制备乳液、糊或油分散体，可以使用润湿剂、粘合剂、分散剂或乳化剂将环戊唑菌和氧唑菌直接或在溶于油或溶剂中之后在水中均化。然而，还可以由活性物质和润湿剂、增粘剂、分散剂或乳化剂以及合适的话溶剂或油制备浓缩物，该浓缩物适于用水稀释。使用形式当然包含用于储存稳定的配制剂中的助剂。
活性化合物在用水稀释的制剂中的浓度可以在较宽范围内变化。它们通常为0.0001-10重量％，优选0.01-1重量％。
可以将各种类型的油、润湿剂、助剂、除草剂、其他杀真菌剂、杀虫剂、杀菌剂、生长调节剂或肥料加入活性化合物中，合适的话甚至在紧临施用之前(桶混物)。这些试剂可以1∶10-10∶1的重量比加入根据本发明使用的杀真菌剂中。
环戊唑菌和氧唑菌与一种或多种作物保护中常用的活性化合物，例如其他杀真菌剂的联合使用可以通过使用这些活性化合物(例如联合配制剂或桶混物)或通过依次施用各活性化合物而进行。
根据本发明，化合物(I)和(II)可以与其联合使用的下列杀真菌剂意欲说明可能的组合，但不限制它们：
·酰基丙氨酸类，例如苯霜灵(benalaxyl)、甲霜灵(metalaxyl)、甲呋酰胺(ofurace)、霜灵(oxadixyl)，
·胺衍生物，例如4-十二烷基-2，6-二甲基吗啉(aldimorph)、多果定(dodine)、吗菌灵(dodemorph)、丁苯吗啉(fenpropimorph)、苯锈啶(fenpropidin)、双胍盐(guazatine)、双胍辛醋酸盐(iminoctadine)、螺茂胺(spiroxamine)、克啉菌(tridemorph)，
·苯胺基嘧啶类，例如二甲嘧菌胺(pyrimethanil)、嘧菌胺(mepanipyrim)或环丙嘧啶(cyprodinil)，
·抗菌素，例如放线菌酮(cycloheximide)、灰黄霉素(griseofulvin)、春雷素(kasugamycin)、多马霉素(natamycin)、多氧霉素(polyoxin)或链霉素(streptomycin)，
·唑类，例如双苯三唑醇(bitertanol)、糠菌唑(bromoconazole)、环唑醇(cyproconazole)、醚唑(difenoconazole)、烯唑醇(dinitroconazole)、腈苯唑(fenbuconazole)、喹唑菌酮(fluquinconazole)、氟硅唑(flusilazole)、己唑醇(hexaconazole)、烯菌灵(imazalil)、腈菌唑(myclobutanil)、戊菌唑(penconazole)、丙环唑(propiconazole)、丙氯灵(prochloraz)、丙硫菌唑(prothioconazole)、戊唑醇(tebuconazole)、三唑酮(triadimefon)、唑菌醇(triadimenol)、氟菌唑(triflumizole)、戊叉唑菌(triticonazole)、5-氯-7-(4-甲基哌啶-1-基)-6-(2，4，6-三氟苯基)-[1，2，4]三唑并[1，5-a]嘧啶，
·二羧酰亚胺类，如异丙定(iprodione)、甲菌利(myclozolin)、杀菌利(procymidone)、烯菌酮(vinclozolin)，
·二硫代氨基甲酸盐类，如福美铁(ferbam)、代森钠(nabam)、代森锰(maneb)、代森锰锌(mancozeb)、威百亩(metam)、代森联(metiram)、甲基代森锌(propineb)、福代锌(polycarbamate)、福美双(thiram)、福美锌(ziram)、代森锌(zineb)，
·杂环化合物，如敌菌灵(anilazine)、苯菌灵(benomyl)、啶酰菌胺(boscalid)、多菌灵(carbendazim)、萎锈灵(carboxin)、氧化萎锈灵(oxycarboxin)、氰霜唑(cyazofamid)、棉隆(dazomet)、二噻农(dithianon)、唑酮菌(famoxadone)、咪唑菌酮(fenamidone)、异嘧菌醇(fenarimol)、麦穗宁(fuberidazole)、氟酰胺(flutolanil)、呋吡唑灵(furametpyr)、稻瘟灵(isoprothiolane)、丙氧灭绣胺(mepronil)、氟苯嘧啶醇(nuarimol)、噻菌灵(probenazole)、丙氧喹啉(proquinazid)、啶斑肟(pyrifenox)、咯喹酮(pyroquilon)、喹氧灵(quinoxyfen)、硅噻菌胺(silthiofam)、涕必灵(thiabendazole)、溴氟唑菌(thifluzamide)、甲基托布津(thiophanate-methyl)、噻酰菌胺(tiadinil)、三环唑(tricyclazole)、嗪氨灵(triforine)，
·铜杀真菌剂，如波尔多液(Bordeaux混合物)、醋酸铜、王铜(copperoxychloride)、碱式硫酸铜，
·硝基苯基衍生物，如乐杀螨(binapacryl)、敌螨普(dinocap)、敌螨通(dinobuton)、异丙消(nitrophthal-isopropyl)，
·苯基吡咯类，如拌种咯(fenpiclonil)或氟菌(fludioxonil)，
·硫，
·其它杀真菌剂，如噻二唑素(acibenzolar-S-methyl)、苯噻菌胺(benthiavalicarb)、氯环丙酰胺(carpropamid)、百菌清(chlorothalonil)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、哒菌清(diclomezine)、双氯氰菌胺(diclocymet)、乙霉威(diethofencarb)、克瘟散(edifenphos)、噻唑菌胺(ethaboxam)、环酰菌胺(fenhexamid)、薯瘟锡(fentin acetate)、氰菌胺(fenoxanil)、嘧菌腙(ferimzone)、氟啶胺(fluazinam)、藻菌磷(fosetyl)、乙膦铝(fosetyl-aluminum)、异丙菌胺(iprovalicarb)、六氯苯(hexachlorobenzene)、苯菌酮(metrafenone)、戊菌隆(pencycuron)、百维灵(propamocarb)、四氯苯酞(phthalide)、甲基立枯磷(tolclofos-methyl)、五氯硝基苯(quintozene)、苯酰菌胺(zoxamid)，
·嗜球果伞素类(strobilurins)，如腈嘧菌酯(azoxystrobin)、醚菌胺(dimoxystrobin)、氟嘧菌酯(fluoxastrobin)、亚胺菌(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、肟醚菌胺(orysastrobin)、啶氧菌酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)或肟菌酯(trifloxystrobin)，
·次磺酸衍生物，如敌菌丹(captafol)、克菌丹(captan)、抑菌灵(dichlofluanid)、灭菌丹(folpet)、对甲抑菌灵(tolylfluanid)，
·肉桂酰胺及类似化合物，如烯酰吗啉(dimethomorph)、氟联苯菌(flumetover)或氟吗啉(flumorph)。
其他杀真菌剂优选选自丙氯灵、戊叉唑菌、5-氯-7-(4-甲基哌啶-1-基)-6-(2，4，6-三氟苯基)-[1，2，4]三唑并[1，5-a]嘧啶、醚菌胺、唑菌胺酯、亚胺菌、丁苯吗啉和苯菌酮。
若环戊唑菌和氧唑菌与其他杀真菌剂组合使用，则优选将它们与一种或两种其他杀真菌剂联合使用。
在田间施用的优选实施方案中，即在对活植物或其植物部分施用时，环戊唑菌和氧唑菌以含水喷雾液形式使用。施用优选通过喷雾进行。这里将喷雾液喷雾于植物的整个地面上部分或仅喷雾于各植物部分。待施加喷雾液的各植物部分的选择取决于植物品种及其发育阶段。施用优选对植物的整个地面上部分进行或对要求对毒素污染提供特殊保护或优选被形成单端孢菌素的真菌侵染的部分进行。
在田间施用的情况下，每次施用时环戊唑菌和氧唑菌通常以10-1000g/ha，优选10-600g/ha，特别优选20-450g/ha的总量使用。
具体而言，优选在田间条件下每次施用使用下列量的活性物质：
·环戊唑菌(I)：优选5-500g/ha；特别优选5-300g/ha；尤其是10-200g/ha。
·氧唑菌(II)：优选5-600g/ha；特别优选5-400g/ha；尤其是10-300g/ha。
按照季节，环戊唑菌和氧唑菌优选施用1-5次，特别优选1-3次，尤其是1或2次。
本发明因此提供了一种降低或防止禾谷类被产生单端孢菌素的真菌形成的真菌毒素污染的方法，其中将禾谷类用环戊唑菌与氧唑菌组合处理。最后，本发明还提供了一种降低或防止禾谷类被产生单端孢菌素的真菌形成的真菌毒素污染的方法，其中用包含环戊唑菌和氧唑菌的组合物处理禾谷类。
对于环戊唑菌和氧唑菌的量以及其中使用环戊唑菌和氧唑菌的方式，以及对于真菌毒素和产生它们的真菌，参考上面所述那些。
环戊唑菌和氧唑菌的联合使用对禾谷类被来自产生单端孢菌素的有害真菌的单端孢菌素毒素和其他真菌毒素污染具有协同增效作用。“协同增效作用”是指以超加和方式增加对至少一种禾谷类品种被来自产生单端孢菌素的有害真菌的至少一种单端孢菌素毒素或至少一种其他真菌毒素污染的作用。以此方式，与基于单一活性化合物的活性所预期的相比，更有效地显著降低了这些真菌毒素的污染。活性化合物组合的预期效力例如可以使用Colby公式(S.R.Colby，计算除草剂组合的协同增效和拮抗响应，Weeds，15，第20-22页)确定。
下列实施例用于说明本发明，但不限制本发明。
实施例
1.在田间条件下在用环戊唑菌和氧唑菌处理之后降低小麦粒被脱氧瓜萎镰菌醇(DON)的污染
在生长阶段GS 25-29(分蘖)将栽培品种为“Ritmo”的室外冬小麦用被镰孢霉属真菌侵染的黑麦粒接种。活性化合物在生长阶段GS 63(开始开花)施用。环戊唑菌和氧唑菌均以成品配制剂使用(环戊唑菌：商品名“Caramba”；氧唑菌：商品名“Opus”；环戊唑菌呈SL＝可悬浮液体；氧唑菌呈SC＝可悬浮浓缩物)。将这些配制剂用水稀释至所需浓度并通过用这些稀释制剂喷雾而处理植物。活性化合物以桶混物联合施用。为了对比，还仅使用单一杀真菌剂。施用3周后肉眼确定镰孢霉属真菌对麦穗的侵染。收获小麦粒并在提取和通过HPLC/MS分析之后确定麦粒的DON含量。为了进行对比评价，将对未处理小麦测定的镰孢霉属真菌侵染和DON值定义为100％。侵染效果为0％对应于与未处理对照相同的侵染，效力为100％对应于0％侵染。DON含量的降低为0％对应于与未处理对照相同的DON含量，100％的降低对应于DON含量低于检测限。对已处理小麦测定的值以相对值示于表1中，即以基于100％的百分数表示。活性化合物组合的预期效力使用Colby公式(S.R.Colby，计算除草剂组合的协同增效和拮抗响应，Weeds，15，第20-22页，1967)确定并与观察到的效力比较。
表1
| 实施例 | 活性化合物 | 施用率[g/ha] | 对侵染的效果[％] | 预期效果[％]1 | DON含量的降低[％] | DON含量的预期降低[％]1 |
| 1 | - | - | 0 | 02 | ||
| 2 | 环戊唑菌 | 45 | 27 | 33 | ||
| 3 | 氧唑菌 | 75 | 5 | 0 | ||
| 4 | 环戊唑菌+氧唑菌 | 4575 | 56 | 31 | 41 | 33 |
1根据Colby
2未处理小麦粒的DON含量：33.7mg/kg
由结果可以看出联合使用环戊唑菌和氧唑菌导致对小麦的镰孢霉属真菌侵染和收获麦粒的DON含量均产生协同增效作用。
Claims (10)
1.环戊唑菌与氧唑菌联合在降低或防止禾谷类被产生单端孢菌素的真菌形成的毒素污染中的用途。
2.包含环戊唑菌和氧唑菌的组合物在降低或防止禾谷类被产生单端孢菌素的真菌形成的毒素污染中的用途。
3.根据前述权利要求中任一项的用途，其中所述产生单端孢菌素的真菌是选自镰孢霉属、木霉属或葡萄穗霉属的那些。
4.根据前述权利要求中任一项的用途，其中所述毒素是单端孢菌素或玉米赤霉毒素。
5.根据权利要求4的用途，其中所述单端孢菌素包含至少一种下列物质：脱氧瓜萎镰菌醇，瓜萎镰菌醇，3-和15-乙酰氧基瓜萎镰菌醇，T-2毒素，HT-2毒素，新茄病镰刀菌烯醇，单乙酰氧基镰草镰菌醇，草镰孢烯醇，15-乙酰氧基镰孢烯二醇，镰刀烯酮，T-2四醇或疣孢菌醇。
6.根据前述权利要求中任一项的用途，其中禾谷类选自小麦、大麦、黑麦、黑小麦、燕麦、稻和玉米。
7.根据前述权利要求中任一项的用途，其中环戊唑菌和氧唑菌以10∶1-1∶10的比例使用。
8.一种降低或防止禾谷类被产生单端孢菌素的真菌形成的真菌毒素污染的方法，其中用环戊唑菌与氧唑菌组合处理禾谷类。
9.一种降低或防止禾谷类被产生单端孢菌素的真菌形成的真菌毒素污染的方法，其中用包含环戊唑菌和氧唑菌的组合物处理禾谷类。
10.根据权利要求8或9的方法，其中环戊唑菌与氧唑菌以10∶1-1∶10的比例使用。
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| EP2036438A1 (en) * | 2007-09-12 | 2009-03-18 | Bayer CropScience AG | Post-harvest treatment |
| EP2064952A1 (en) | 2007-11-29 | 2009-06-03 | Bayer CropScience AG | Method for reducing mycotoxin contamination in maize |
| WO2009071419A1 (de) * | 2007-12-04 | 2009-06-11 | Basf Se | Fungizide mischungen |
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| CN102037980B (zh) * | 2010-12-31 | 2013-05-29 | 利尔化学股份有限公司 | 杀菌农药组合物 |
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