40%联苯肼酯.乙螨唑悬浮剂的配方研制

[目的] 制备40%联苯肼酯.乙螨唑悬浮剂,降低柑橘红蜘蛛防治的单剂用药量和生产成本,延长药剂使用寿命。[方法] 采用湿法研磨工艺,通过粒径、黏度、分散性、pH、冷贮和热贮稳定性等指标的测试,对配方中的润湿分散剂、增稠剂、防冻剂进行了筛选。[结果] 确定了40%联苯肼酯.乙螨唑悬浮剂优化配方：联苯肼酯原药25%,乙螨唑原药15%,AEO 2%,D1002 2%,木质素磺酸钠6%,乙二醇5%,黄原胶0.1%,去离子水补足100%。该悬浮剂施用30 d后对柑橘红蜘蛛的防效仍达到90.1%。[结论] 该配方复配比例合理,性能指标均符合相关标准,对柑橘红蜘蛛的田间防治效果优异。试验结果可以为联苯肼酯和乙螨唑开发提供依据。     

联肼·乙螨唑对蔬菜优势叶螨产卵发育的影响及其田间防效

为明确新型复配杀螨剂联肼·乙螨唑对目前蔬菜田常发生的2种优势叶螨二斑叶螨Tetranychus urticae和截形叶螨T. truncatus的杀螨活性,于室内采用离体叶碟法测定其对这2种叶螨产卵及发育的影响,于室外采用活体植株评价该药剂对2种叶螨的田间防效。结果表明,经复配杀螨剂联肼·乙螨唑及其单剂处理2种叶螨雌成螨24 h后,死亡率为20.50%～54.98%,均显著高于清水对照;联肼·乙螨唑处理较清水对照显著降低了2种叶螨卵发育至若螨期的比率,联肼·乙螨唑处理后二斑叶螨和截形叶螨的若螨率分别为4.91%和1.63%。田间试验中联肼·乙螨唑对2种叶螨具有一定的速效性,药后3 d对二斑叶螨和截形叶螨的防效分别达95.74%和89.83%,药后7 d防效分别为98.03%和99.44%,显示了优良的防控效果及持效性。表明复配杀螨剂联肼·乙螨唑可用于田间蔬菜优势叶螨种群的高效防控。     

乙螨唑110克/升悬浮剂高效液相色谱分析方法研究

本文采用高效液相色谱法,以乙腈＋水为流动相,使用以ZORBAX SB—C18、5μm为填料的不锈钢柱和二极管阵列检测器．在225nm波长下对乙螨唑110g／L悬浮剂进行分离和定量分析。结果表明,该分析方法的线性相关系数为0．9999;标准偏差为0．026;变异系数为0．26％;平均回收率为99．86％。     

超高效液相色谱-串联质谱法分析乙螨唑在柑桔和土壤中的残留消解动态

应用超高效液相色谱-串联质谱(UPLC-MS/MS)建立了乙螨唑在柑桔和土壤中残留的分析方法,并研究了田间试验条件下乙螨唑在柑桔和土壤中的消解动态。样品采用乙腈提取,硅胶柱净化,UPLC-MS/MS检测,外标法(ESTD)定量。在0.002 ~1 mg/L质量浓度范围内,乙螨唑的仪器响应值与质量浓度呈良好线性关系,相关系数为0.998 9。该方法的最小检出量为6.0×10-6 μg,乙螨唑在柑桔和土壤中的最低检测浓度均为0.002 mg/kg。当乙螨唑在柑桔和土壤中的添加水平为0.002 ~1 mg/kg时,平均回收率为87.3% ~98.4%,相对标准偏差在5.5% ~8.6%之间。消解动态试验表明,乙螨唑的消解动态曲线符合一级动力学方程,在柑桔和土壤中的半衰期分别为5.6 ~7.6 d 和 5.3 ~8.6 d。     

气相色谱-串联质谱法检测乙氧氟草醚、唑草酮和乙螨唑在4种香辛料中的残留

建立了气相色谱-三重四极杆串联质谱 (GC-MS/MS)检测留兰香、桂皮、薄荷和月桂叶中乙氧氟草醚、唑草酮、乙螨唑残留的分析方法。4种香辛料用超纯水饱和，乙腈提取，无水硫酸镁及氯化钠盐析，氨基/石墨化碳黑 (NH₂-Carb) 固相萃取柱净化，多反应监测模式，气相色谱-串联质谱测定。结果表明:乙氧氟草醚在0.002 5~2 mg/L范围内，唑草酮和乙螨唑在0.01~2 mg/L范围内，3种农药的进样质量浓度与对应的峰面积间呈良好的线性关系，r > 0.99；乙氧氟草醚在0.025、0.5和2 mg/kg 3个添加水平下，在4种香辛料中的平均回收率在86%~112%之间，相对标准偏差 (RSD)在2.4%~9.6%之间；唑草酮在0.2、0.5和2 mg/kg 3个添加水平下的平均回收率在87%~114%之间，RSD在2.4%~11%之间；乙螨唑在0.5、2和5 mg/kg 3个添加水平下的平均回收率在86%~116%之间，RSD在3.2%~11%之间。乙氧氟草醚、唑草酮和乙螨唑在4种香辛料中的定量限 (LOQ) 分别为0.025、0.2和0.5 mg/kg。     

Mode of action of etoxazole

The mode of action of the 2,4-diphenyl-1,3-oxazoline acaricide/insecticide etoxazole has been argued to be moulting inhibition, but experimental results supporting this hypothesis are lacking. This study investigated the effect of etoxazole on chitin biosynthesis in the fall armyworm, Spodoptera frugiperda (Smith) (Lepidoptera: Noctuidae). Etoxazole induced moulting defects in fall armyworm larvae similar, if not identical, to those caused by benzoylphenylureas, a well-known class of insecticidal chitin biosynthesis inhibitors. Furthermore, in contrast to untreated larvae, the chitin content in the integuments of larvae several days after treatment did not differ from that in freshly ecdysed individuals, thus suggesting strong chitin biosynthesis inhibition in vivo. A more detailed investigation of the inhibitory potential by incubating cultured integument pieces from larvae of S. frugiperda with [14C]N-acetyl-D-glucosamine, a radiolabelled chitin precursor, revealed I50 values of 2.95 and 0.071 microM for etoxazole and triflumuron respectively. The incorporation of radiolabel into potassium hydroxide-resistant material was inhibited by etoxazole in a dose-dependent manner. Based on these results, it is concluded that the acaricidal and insecticidal mode of action of etoxazole is chitin biosynthesis inhibition.     

HPLC-MS/MS法测定枇杷中乙螨唑残留量及安全评价

为评价乙螨唑在枇杷上使用的安全性,通过田间试验研究乙螨唑在枇杷上残留消解动态与最终残留量,并进行膳食风险评估。样品经乙腈提取,N-丙基乙二胺(PSA)与十八烷基键合硅胶(C₁₈)组合吸附剂净化,高效液相色谱-三重四级杆串联质谱仪(HPLC-MS/MS)检测,外标法定量。结果表明,在0.01~1.0 mg/kg 3个添加水平下,乙螨唑在枇杷上的平均回收率为89.2%~97.1%,相对标准偏差(RSD)为3.4%~5.3%,定量限(LOQ)为0.01 mg/kg。乙螨唑在枇杷上半衰期为6.9~8.9天,20%乙螨唑悬浮剂(SC)以33.3 mg/kg和50 mg/kg分别施用2、3次,当采收间隔期为14、21与28天时,枇杷中乙螨唑残留量均值依次是0.055~0.37、0.032~0.19、0.014~0.12 mg/kg,可见,随着采收间隔期的延长,枇杷上乙螨唑残留量呈减少趋势。膳食风险评估结果显示,乙螨唑的国家估算每日摄入量(NEDI)是0.0126 mg,风险商(RQ)是0.4%,对一般人群健康不会产生不可接受的风险。     

三种杀螨剂对山楂叶螨的毒力评价

为筛选出高效防治山楂叶螨Amphitetranychus viennensis Zacher的杀螨剂,利用玻片浸渍法和叶片残毒法测定了3种杀螨剂对其3种螨态的室内毒力,并对不同浓度杀螨剂的田间防效进行了测定。结果表明:240 g/L螺螨酯、110 g/L乙螨唑和43%联苯肼酯中仅联苯肼酯对山楂叶螨雌成螨有毒力,其LC50为37.65 mg/L;3种杀螨剂均能毒杀卵及幼螨,毒力大小依次为乙螨唑联苯肼酯螺螨酯;同一杀螨剂对幼螨的毒力均高于对卵的毒力。240 g/L螺螨酯和110 g/L乙螨唑对山楂叶螨的总体防效较好,除螺螨酯4 000倍液处理的防效在药后30 d达到最大97.11%外,其余各处理均在药后15 d达到最大,防效为88.76%~96.14%;但二者速效性较差,药后1~7 d防效均低于对照;而螺螨酯4 000、5 000倍液处理及乙螨唑5 000倍液处理的持效性较好,药后30 d防效仍有97.11%、90.90%和93.06%,均显著高于对照。43%联苯肼酯对山楂叶螨的总体防效在3种杀螨剂中最高,其1 800、2 500倍液处理分别在药后7 d和3 d时防效达到最大99.79%和98.64%;1~7 d防效为97.45%~99.79%,显著高于其余杀螨剂和对照;30 d时防效分别达98.14%和96.19%,速效性和持效性均较好。表明螺螨酯和乙螨唑对山楂叶螨的持效性较好,联苯肼酯则有良好的速效性和持效性,可以按照其不同特点推广应用。     

DL-α-生育酚聚乙二醇琥珀酸酯类非离子表面活性剂的合成及其在农药制剂中的应用

使用DL-α-生育酚作为表面活性剂的亲油端,聚乙二醇(polyoxyethylene ether,EO)链作为亲水端,合成了非离子表面活性剂DL-α-生育酚甲氧基聚乙二醇琥珀酸酯(DL-α-tocopherol methoxypolyethylene glycol succinates),简称TPGS-X-M(X=750,1000,1500,1900,表示所使用聚乙二醇单甲醚的相对分子质量),测定了该表面活性剂的临界胶束浓度(cmc)、静态和动态表面张力,进一步将该表面活性剂用作20%乙螨唑悬浮剂中的分散剂并测试了其理化参数,与商品化分散剂FS3000进行了对比。静态表面张力测试结果表明,聚乙二醇链的长度对cmc值的影响不大;动态表面张力测试结果显示,TPGS-1000-M、TPGS-1500-M和TPGS-1900-M在1249.3 ms时的动态表面张力下降的趋势较FS3000更大,具有一定优势。性能测试结果表明,以TPGS-1500-M和TPGS-1900-M制备的20%乙螨唑悬浮剂的粒径、悬浮率、有效成分含量、分散性、热贮稳定性以及低温稳定性与以FS3000制备的悬浮剂相当。新合成的表面活性剂TPGS-1500-M和TPGS-1900-M有望作为悬浮制剂的分散剂使用。     

Transovarial biotransference of etoxazole through a terrestrial trophic web

BACKGROUND: Transovarial transport is defined as the passage of chemicals from the maternal body to eggs within the ovaries. Little is known about the effects of transovarial transport on non‐target species. This study evaluates etoxazole (a transovarial acaricidal compound) on a terrestrial trophic web consisting of a ubiquitous phytophagous mite, Tetranychus urticae Koch, and three species of predatory mites. RESULTS: Predatory mite females that consumed eggs laid by etoxazole‐treated T. urticae also produced infertile eggs. There was a negative relationship between the proportion of etoxazole‐treated T. urticae females and the instantaneous rate of predatory mite increase at the population level (r² = 0.86). Reduced fertility of etoxazole‐treated T. urticae females continued for 18 days following application. Eggs laid by etoxazole‐treated T. urticae females remained toxic to predatory mite females for 42 days after treatment. CONCLUSIONS: Transovarial transport could lead to magnification in the ecosystem by enhancing both bioavailability and movement of an active ingredient. The potential for enhancement of residual activity by terrestrial organisms and its significance once reaching the food web should be taken into account for new classes of acaricides and insecticides. Copyright © 2012 Society of Chemical Industry