CN112841197A - 包含嘧啶羧酸苄酯类化合物和psii抑制剂的除草组合物及其应用 - Google Patents

包含嘧啶羧酸苄酯类化合物和psii抑制剂的除草组合物及其应用 Download PDF

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CN112841197A
CN112841197A CN201911317860.7A CN201911317860A CN112841197A CN 112841197 A CN112841197 A CN 112841197A CN 201911317860 A CN201911317860 A CN 201911317860A CN 112841197 A CN112841197 A CN 112841197A
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psii
active ingredient
herbicidal composition
compound
benzyl
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CN112841197B (zh
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彭学岗
金涛
赵德
张景远
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Jiangsu Qingyuan Nongguan Weed Control Co ltd
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Jiangsu Qingyuan Nongguan Weed Control Co ltd
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Abstract

本发明属于农药领域,具体涉及一种包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物及其应用。所述除草组合物包括除草有效量的活性成分A和活性成分B,其中,活性成分A为

Description

包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物及其 应用
本申请是申请日为2019年11月12日,申请号为201911099429.X,发明名称为“包含嘧啶羧酸苄酯类化合物的除草组合物及其应用”的中国发明专利申请的分案申请。
技术领域
本发明属于农药领域,具体涉及一种包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物及其应用。
背景技术
化学除草是农田杂草防除中最为经济、有效的手段,但长期连续高剂量地使用单一品种或单一作用方式的化学除草剂,容易造成杂草耐药和抗性演化等问题。除草剂化合物的合理复配或混配具有扩大杂草谱、提高防除效果、延缓杂草耐药性和抗药性的发生与发展等优点,是解决上述问题的最为有效的方法之一。如专利CN108774179A公开了一种取代的嘧啶-4-甲酸衍生物及其作为除草剂的用途,而生产上仍需开发安全性高、杀草谱广、能够产生增效作用并解决抗性杂草问题的除草组合物品种。
发明内容
为解决现有技术中存在的上述问题,本发明提供一种包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物及其应用。该组合物能有效防除作物田中的水莎草等莎草科杂草,马唐、稗草、牛筋草、绿狗尾等禾本科杂草,以及反枝苋、苘麻、马齿苋、粟米草等阔叶杂草问题,具有扩大杀草谱、减少施用量、能够产生增效作用并解决抗性杂草等特点。
一种包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物,包括除草有效量的活性成分A和活性成分B,其中,
活性成分A为
Figure BDA0002326329700000011
活性成分B选自以下化合物及其盐/酯中的一种或多种:
PSII抑制剂:嗪草酮(CAS:21087-64-9)、氨唑草酮(CAS:129909-90-6)、绿麦隆(CAS:15545-48-9)、异丙隆(CAS:34123-59-6)、莠去津(CAS:1912-24-9)、特丁津(CAS:5915-41-3)、敌稗(CAS:709-98-8)、灭草松(CAS:25057-89-0)、辛酰溴苯腈(CAS:1689-99-2)、扑草净(CAS:7287-19-6)、特丁净(CAS:886-50-0)、哒草特(CAS:55512-33-9)、敌草隆(CAS:330-54-1)、除草定(CAS:314-40-9)、环草定(CAS:2164-08-1)、特草定(CAS:5902-51-2)、甜菜安(CAS:13684-56-5)、甜菜宁(CAS:13684-63-4)、溴苯腈(CAS:1689-84-5)、碘苯腈(CAS:1689-83-4)。
在本说明书的上下文中,如果使用活性化合物的通用名称的缩写形式,则在每种情况下包括所有的常规衍生物,例如酯和盐,以及异构体,特别是光学异构体,特别是一种或多种市售形式。如果通用名称表示酯或盐,则在每种情况下还包括所有其他的常规衍生物,例如其他的酯和盐、游离酸和中性化合物,以及异构体,特别是光学异构体,特别是一种或多种市售形式。给出的化合物的化学名称表示至少一种被通用名称涵盖的化合物,通常是优选的化合物。在磺酰胺如磺酰脲的情况下,盐还包括通过阳离子与磺酰胺基团中的氢原子交换而形成的盐。例如,2甲4氯衍生物包含但不限于:2甲4氯钠盐、钾盐、二甲铵盐、异丙胺盐等,以及2甲4氯甲酯、乙酯、异辛酯、乙硫酯等;2,4-D衍生物包含但不限于:2,4-D盐如钠盐、钾盐、二甲铵盐、三乙醇铵盐、异丙胺盐、胆碱等,以及2,4-D酯如甲酯、乙酯、丁酯、异辛酯等。
其中,所述除草组合物中A、B的重量比为1:500~200:1和1:400~150:1;优选为1:300~100:1和1:200~80:1;更优选为1:150~50:1和1:120~30:1;进一步优选为1:100~20:1和1:80~15:1;更进一步优选为1:50~10:1、1:30~5:1、1:10~4:1和1:5~1:1。
所述除草组合物中A和B的质量百分含量占总量的1-95%,优选10-80%。
所述除草组合物中还包含常规助剂,所述常规助剂包括载体、表面活性剂。
本文中的术语“载体”表示一种有机或无机、天然或合成的物质。它们有助于活性成分的施用,该载体一般是惰性的且必须是农业上可接受的,特别是被处理的植物所接受。载体可以是固体的,如陶土、天然或合成的硅酸盐、二氧化硅、树脂、蜡、固体肥料等;或者液体的,如水、醇类、酮类、石油馏分、芳烃或蜡烃、氯代烃、液化气等。
表面活性剂可包括乳化剂、分散剂或润湿剂,它可以是离子型或非离子型的。可提及的实例是聚丙烯酸的盐、木质素磺酸盐、苯酚磺酸或萘磺酸的盐、环氧乙烷与脂肪族醇或与脂族酸或与脂肪族胺与取代苯酚(特别是烷基苯酚或芳基苯酚)的聚合物、磺基琥珀酸盐、牛磺酸衍生物(特别是牛磺酸烷脂)及醇的磷酸酯或多羟乙基化的苯酚的磷酸酯、烷基磺酸盐、烷基芳基磺酸盐、烷基硫酸盐、月桂基醚硫酸盐、脂肪醇硫酸盐,以及硫酸化十六-、十七-和十八烷醇以及硫酸化脂肪醇乙二醇醚,此外还有萘或萘磺酸与苯酚和甲醛的缩合物、聚氧乙烯辛基苯基醚、乙氧基化异辛基酚、辛基酚或壬基酚、烷基苯基聚乙二醇醚、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、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、乙氧基化聚氧丙烯、月桂醇聚乙二醇醚缩醛、山梨醇酯、木素亚硫酸盐废液,以及蛋白质、变性蛋白、多糖(例如甲基纤维素)、疏水改性淀粉、聚乙烯醇、聚羧酸盐、聚烷氧基化物、聚乙烯胺、聚乙烯吡咯烷酮及其共聚物。至少需要一种表面活性剂存在,以有利于活性成分在水中的分散并有利于使它们能正确地施用于植物。
上述组合物也可含有各种其他的组分,如保护胶体、粘合剂、增稠剂、触变剂、渗透剂、稳定剂、螯合剂、染料、着色剂和聚合物。
所述除草组合物进一步包括至少一种安全剂,优选双苯噁唑酸(CAS:163520-33-0)、cyprosulfamide(CAS:221667-31-8)、吡唑解草酯(CAS:135590-91-9)、解毒喹(CAS:99607-70-2)、赤霉酸(CAS:7-06-5)、furilazole(CAS:121776-33-8)、metcamifen(CAS:129531-12-0)中的一种或多种。
本发明的组合物可以由使用者在使用前经稀释或直接使用。其配制可由通常的加工方法制备,即将活性物质与液体溶剂或固体载体混合后,再加入表面活性剂如分散剂、稳定剂、湿润剂、粘合剂、消泡剂等中的一种或几种。
所述除草组合物的具体制剂为可分散油悬浮剂、水悬浮剂、悬乳剂、可湿性粉剂、乳油、水分散粒剂(干悬浮剂)、水乳剂、微乳剂。
简而言之,本发明的组合物可以和现有技术的配方中常规使用的固体和液体添加剂混合。随着外部条件的变化,有效成分的使用量也不同,外部条件为,例如温度、湿度、使用的除草剂的性质等等。它可以有大的变化幅度,例如在0.001到1.0kg/ha之间,或更多的活性物质,但优选在0.005到750g/ha之间,特别是在0.005到500g/ha之间。
本发明还提供一种所述除草组合物在防治杂草上的应用;以及提供一种防治不想要的植物生长的方法,其包括将所述除草组合物施用于植物、植物部位、植物种子或植物生长的区域。
另外,本发明的组合物可通过喷雾的方法被施用于待处理植物叶片上,即施用于杂草,特别是杂草侵扰或易侵扰影响的表面上。
当施用本发明的除草组合物时,获得了预料不到的增效效果,并且除草活性比使用单个除草剂的活性预期总和,以及单个除草剂的活性更为显著。增效效果表现为施用量减少、更宽的杂草控制谱、除草作用更快、更持久,这些特性是杂草控制实践过程中所需要的。就所描述的特性来说,这些新组合物明显地优越于现有的除草剂,达到减量使用,对环境更友好。
本发明的增效除草组合物还具有下述优点:
(1)本发明的组合物为环境友好型,在环境中均易于降解。
(2)本发明的除草组合物成本低、使用方便,其推广应用有巨大的经济效益和社会效益。
本文提到或引用的所有专利、专利申请和出版物整体引入本文作为参考,其引用程度如同单独地个别引用一样。
具体实施方式
下列实施例并非限制本发明,而只是用来说明本发明是如何实现的。对于某些杂草,这些实施例显示出特别显著的有效性。举例如下:
A)实施例
1.3.4%A·嗪草酮(0.4+3)乳油
0.4%A+3%嗪草酮+10%N-甲基吡咯烷酮+5%十二烷基苯磺酸钙+18%腰果酚聚氧乙烯醚+2%蓖麻油氧乙烯醚+100#溶剂油补足
2.15.4%A·氨唑草酮(0.4+15)可分散油悬浮剂
0.4%A+15%氨唑草酮+5%十二烷基苯磺酸钙+13%腰果酚聚氧乙烯醚+2%蓖麻油氧乙烯醚+2.0%有机膨润土+1.5%气相法白炭黑+8%100#溶剂油+油酸甲酯补足
3.50.4%A·绿麦隆(0.4+50)水悬浮剂
0.4%A+50%绿麦隆+2%聚羧酸盐分散剂+1%木质素磺酸钠+1%脂肪醇聚氧乙烯醚+0.05%黄原胶+2%乙二醇+0.1%消泡剂+去离子水补足
4.50.4%A·异丙隆(0.4+50)水悬浮剂
0.4%A+50%异丙隆+2%聚羧酸盐分散剂+1%脂肪醇聚氧乙烯醚+0.05%黄原胶+2%乙二醇+0.1%消泡剂+去离子水补足
5.50.4%A·莠去津(0.4+50)水悬浮剂
0.4%A+50%莠去津+2%聚羧酸盐分散剂+1%木质素磺酸钠+1%脂肪醇聚氧乙烯醚+0.05%黄原胶+2%乙二醇+0.1%消泡剂+去离子水补足
6.50.4%A·特丁津(0.4+50)水悬浮剂
0.4%A+50%特丁津+2%聚羧酸盐分散剂+1%脂肪醇聚氧乙烯醚+0.05%黄原胶+2%乙二醇+0.1%消泡剂+去离子水补足
7.25.2%A·敌稗(0.2+25)乳油
0.2%A+25%敌稗+10%N-甲基吡咯烷酮+10%异佛尔酮+2%十二烷基苯磺酸钙+24%苯乙基酚聚氧乙烯醚+100#溶剂油补足
8.20.2%A·灭草松(0.2+20)微乳剂
0.2%A+20%灭草松+3.4%氢氧化钠+5%环己酮+10%顺丁烯二仲辛酯磺酸钠+12%蓖麻油聚氧乙烯醚+去离子水补足
9.12.4%A·辛酰溴苯腈(0.4+12)乳油
0.4%A+12%辛酰溴苯腈+10%N-甲基吡咯烷酮+5%十二烷基苯磺酸钙+20%腰果酚聚氧乙烯醚+2%蓖麻油氧乙烯醚+100#溶剂油补足
10.50.4%A·扑草净(0.4+50)水悬浮剂
0.4%A+50%扑草净+2%聚羧酸盐分散剂+1%脂肪醇聚氧乙烯醚+0.05%黄原胶+2%乙二醇+0.1%消泡剂+去离子水补足
11.50.4%A·特丁净(0.4+50)水悬浮剂
0.4%A+50%特丁净+2.5%聚羧酸盐分散剂+1%脂肪醇聚氧乙烯醚+0.05%黄原胶+2%乙二醇+0.1%消泡剂+去离子水补足
12.50.4%A·哒草特(0.4+50)乳油
0.4%A+50%哒草特+10%N-甲基吡咯烷酮+5%十二烷基苯磺酸钙+20%腰果酚聚氧乙烯醚+2%蓖麻油氧乙烯醚+100#溶剂油补足
13.50.4%A·敌草隆(0.4+50)水悬浮剂
0.4%A+50%敌草隆+2.5%聚羧酸盐分散剂+1.5%丙二醇嵌段聚醚+1%脂肪醇聚氧乙烯醚+0.05%黄原胶+2%乙二醇+0.1%消泡剂+去离子水补足
上述乳油加工设备:混料釜、储罐等。
上述乳油加工过程:将所有物料投入混料釜中,搅拌混合至所有物料完全溶解,化验合格后,转移至储罐灌装。
上述微乳剂加工设备:混料釜、储罐等。
上述微乳剂加工过程:将原药、溶剂和乳化剂投入混料釜中,搅拌混合至所有物料完全溶解,之后缓慢抽进去离子水,边抽边搅拌,至最后均相液体,化验合格后,转移至储罐灌装。
上述水悬浮剂加工设备:混料釜、胶体磨、砂磨机、剪切机等。
上述水悬浮剂加工过程:将所有物料投入混料釜中,搅拌混合后过胶体磨,之后进入砂磨机三级砂磨,最后在剪切机中剪切均匀,化验合格后,转移至储罐灌装。
上述可分散油悬浮剂加工设备:混料釜、胶体磨、砂磨机、剪切机等。
上述可分散油悬浮剂加工过程:将所有物料投入混料釜中,搅拌混合后过胶体磨,之后进入砂磨机三级砂磨,最后在剪切机中剪切均匀,化验合格后,转移至储罐灌装。
B)药效试验
苗后茎叶喷雾处理:
1)试验条件
1.1)、供试靶标
苘麻采自黑龙江嫩江。上述杂草采用盆栽法培养,用180х140mm塑料营养钵,摆放于搪瓷盘中,内装从农田采回经风干过筛的表层土壤(4/5处),土壤湿度初期均控制在20%,挑选籽粒饱满均一的杂草种子,用25℃温水浸泡6小时,在28℃生化培养箱(黑暗)中催芽,将刚刚露白的杂草种子均匀摆放在土壤表面,根据种子粒径大小然后覆土0.5-1cm。
1.2)、培养条件
在可控日光温室内进行,温度20~30℃,自然光照,相对湿度57%~72%。土壤类型为壤土,有机质含量为1.63%,pH=7.1,碱解氮84.3mg/kg,速效磷38.5mg/kg,速效钾82.1mg/kg。
1.3)、仪器设备
3WP-2000型行走式喷雾塔,农业部南京农业机械研究所。GA0型万分之一电子天平(德国);ZDR2000智能数据记录仪(杭州泽大仪器有限公司);SPX型智能生化培养箱(宁波江南仪器厂)。
2)试验设计
2.1)、试剂
所需活性成分A来自于专利CN108774179A;所需活性成分B由试剂公司购买。原药均采用丙酮作溶剂,用含量0.1%乳化剂吐温-80水溶液稀释,现用现稀释。
2.2)、试验处理
2.2.1)、剂量设置
在确定A与活性成分B配比或含量时,应从两种药剂的作用特点及其毒力等衡量,还要考虑该配方的主要使用目的。本研究在前期预试的基础上,设A、B活性成分单用及混合用量分别见表格。以不含药剂、含相同溶剂及乳化剂的水作为空白对照。
2.2.2)、试验重复
每处理重复4次,每次处理3盆,每盆播种杂草种子20粒,每处理共60株。
2.3)、处理方式
2.3.1)、处理时间和次数
试验共用药1次。待杂草1.5-2叶期,间苗,保持每盆内杂草10株,每处理保留30株,然后继续培养至3-4叶进行处理。
2.3.2)、使用器械和用药方法
将培养好的试材均匀摆放在面积0.5m2的平台上,用3WP-2000型行走式喷雾塔茎叶喷雾,喷液量按450公斤/公顷计,喷雾压力0.3MPa。待全部药液喷完后,关闭气阀,30秒后,打开喷雾塔门,取出营养钵。然后打开气阀,喷清水50mL,清洗喷液管。
3)试验方法
采用盆栽法。杂草培养见1.1),参照《农药室内生物测定试验准则除草剂》进行。用药方法见2.3.2),采用茎叶处理法。处理后移入温室常规培养。
4)数据调查与统计分析
4.1)、调查方法
采用绝对数调查法,用刀片沿土壤表面切断存活杂草整株幼苗,用分析天平称量杂草鲜重。对于已经死亡的杂草,按鲜重为零计。
4.2)、调查时间和次数
处理后21天调查,共调查1次。
4.3)、数据统计分析
用Gowing法计算各处理混合组合的理论鲜重抑制率(E0=X+Y-X*Y/100),然后与实测抑制率(E)相比较,评价二者混用对杂草的联合作用类型,当E-E0值大于10%为增效作用、小于-10%为拮抗作用、在-10%~10%之间为加成作用。并根据实际防效和除草剂特点、配方的平衡性等因素确定最佳配比。式中X为活性成分A用量为P时的鲜重抑制率;Y为活性成分B用量为Q时的鲜重抑制率。
统计结果见下表1-13。
表1 A混配嗪草酮对苘麻的实际防效与联合作用评价
Figure BDA0002326329700000061
表2 A混配氨唑草酮对苘麻的实际防效与联合作用评价
Figure BDA0002326329700000062
表3 A混配绿麦隆对苘麻的实际防效与联合作用评价
Figure BDA0002326329700000063
表4 A混配异丙隆对苘麻的实际防效与联合作用评价
Figure BDA0002326329700000064
Figure BDA0002326329700000071
表5 A混配莠去津对苘麻的实际防效与联合作用评价
Figure BDA0002326329700000072
表6 A混配特丁津对苘麻的实际防效与联合作用评价
Figure BDA0002326329700000073
表7 A混配敌稗对苘麻的实际防效与联合作用评价
Figure BDA0002326329700000074
表8 A混配灭草松对苘麻的实际防效与联合作用评价
Figure BDA0002326329700000075
表9 A混配辛酰溴苯腈对苘麻的实际防效与联合作用评价
Figure BDA0002326329700000076
表10 A混配扑草净对苘麻的实际防效与联合作用评价
Figure BDA0002326329700000077
表11 A混配特丁净对苘麻的实际防效与联合作用评价
Figure BDA0002326329700000078
Figure BDA0002326329700000081
表12 A混配哒草特对苘麻的实际防效与联合作用评价
Figure BDA0002326329700000082
表13 A混配敌草隆对苘麻的实际防效与联合作用评价
Figure BDA0002326329700000083
C)大田示范
利用实施例1-13制得的除草组合物进行田间杂草效果试验。2017年在山东黄岛试验点进行示范性推广试验。田间发生的杂草主要有:稗草、马唐、绿色狗尾草、牛筋草、反枝苋、马齿苋、粟米草、水莎草,等等。
试验方法:
茎叶处理(F):待杂草处于2-3叶期,手动喷雾器,兑水量30公斤/667m2,采用茎叶喷雾均匀喷雾。
具体试验药剂及剂量详见表14,小区面积20平方米,每处理重复3次。施药后20天调查防除效果见表14。
Figure BDA0002326329700000084
表14 所述复配组合物的大田示范效果情况
Figure BDA0002326329700000085
经过大量试验和探索,本发明意外地发现,所述组合物用于防除主要禾本科杂草、阔叶杂草及莎草科杂草等,具有令人惊讶的、意想不到的增效作用,这种增效作用在低剂量下表现更为显著,可降低用药量,降低对环境的污染,且合理复配降低了农用成本,对ALS、ACCase抑制剂抗性杂草高效,具有很好的应用前景。同时经过测试在小麦田、玉米田、水稻田、花生、甘蔗、高粱、谷子、马铃薯、油菜、大豆、棉花、蔬菜、早熟禾、高羊茅、结缕草等植物显示良好的选择性和优异的增效作用,可以开发成具有广泛市场价值的除草剂混剂。

Claims (10)

1.一种包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物,其特征在于,包括除草有效量的活性成分A和活性成分B,其中,
活性成分A为
Figure FDA0002326329690000011
活性成分B选自以下化合物及其盐/酯中的一种或多种:
PSII抑制剂:嗪草酮、氨唑草酮、绿麦隆、异丙隆、莠去津、特丁津、敌稗、灭草松、辛酰溴苯腈、扑草净、特丁净、哒草特、敌草隆、除草定、环草定、特草定、甜菜安、甜菜宁、溴苯腈、碘苯腈。
2.根据权利要求1所述的一种包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物,其特征在于,所述除草组合物中A、B的重量比为1:500~200:1和1:400~150:1;优选为1:300~100:1和1:200~80:1;更优选为1:150~50:1和1:120~30:1;进一步优选为1:100~20:1和1:80~15:1;更进一步优选为1:50~10:1、1:30~5:1、1:10~4:1和1:5~1:1。
3.根据权利要求1或2所述的一种包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物,其特征在于,所述除草组合物中A和B的质量百分含量占总量的1-95%,优选10-80%。
4.根据权利要求1至3任意一项所述的一种包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物,其特征在于,所述除草组合物中还包括常规助剂。
5.根据权利要求4所述的一种包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物,其特征在于,所述常规助剂包括载体或表面活性剂。
6.根据权利要求1至5任意一项所述的一种包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物,其特征在于,所述除草组合物进一步包括至少一种安全剂。
7.根据权利要求6所述的一种包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物,其特征在于,所述安全剂选自双苯噁唑酸、cyprosulfamide、吡唑解草酯、解毒喹、赤霉酸、furilazole、metcamifen中的一种或多种。
8.根据权利要求1至7任意一项所述的一种包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物,其特征在于,所述除草组合物的具体制剂为可分散油悬浮剂、水悬浮剂、悬乳剂、可湿性粉剂、乳油、水分散粒剂、水乳剂或微乳剂。
9.如权利要求1至8任意一项所述包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物在防治杂草上的应用。
10.一种防治不想要的植物生长的方法,其包括将权利要求1至8任意一项所述包含嘧啶羧酸苄酯类化合物和PSII抑制剂的除草组合物施用于植物、植物部位、植物种子或植物生长的区域。
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