脲醛树脂微胶囊的制备及其对烟碱类杀虫剂的缓释性能

选择脲醛树脂作为囊壁材料,采用原位聚合法对烟碱类杀虫剂噻虫嗪、呋虫胺进行包裹,制备了具有缓释功能的微胶囊。获得脲醛树脂微胶囊最佳工艺参数:甲醛的摩尔比为1.0∶1.8,乳化60 min,酸化0.5 h,固化2 h。使用智能溶出试验仪,考察了微胶囊的包裹率、载药量和溶出率。结果表明,脲醛树脂微胶囊在18 d内可以实现均匀释放。田间试验表明,采用噻虫嗪微胶囊和呋虫胺微胶囊,用量分别为90g.ai/hm~2和45 g.ai/hm~2具有较好的防治水稻飞虱的效果。     

Interaction of dinotefuran and its analogues with nicotinic acetylcholine receptors of cockroach nerve cords

To investigate the action of dinotefuran (MTI-446, 1-methyl-2-nitro-3-(tetrahydro-3-furylmethyl)guanidine), a recently developed insecticide, on insect nicotinic acetylcholine receptors (nAChRs), we determined the potencies of the compound and 15 analogues in inhibiting the specific binding of [3H]epibatidine (EPI), a nAChR agonist, and [3H]alpha-bungarotoxin (alpha-BGT), a competitive nAChR antagonist, to the nerve cord membranes of American cockroaches (Periplaneta americana). Racemic dinotefuran inhibited [3H]EPI binding with an IC50 of 890 nM and [3H]alpha-BGT binding with an IC50 of 36.1 microM. Scatchard analysis indicated that the dinotefuran inhibition of [3H]EPI binding was a competitive one. Slight structural modification caused a drastic reduction in potency; only four analogues were found to be equipotent to or more potent than dinotefuran. Chloropyridinyl and chlorothiazolyl neonicotinoid insecticides displayed two or three orders of magnitude higher potency than dinotefuran. There was a good correlation between the IC50 values of tested compounds obtained with [3H]EPI and those obtained with [3H]alpha-BGT. A better correlation was observed between 3-h knockdown activities (KD50) against German cockroaches (Blattella germanica) and IC50 values obtained from [3H]EPI assays than between 24-h lethal activities (LD50) and IC50 values. While the results indicate that dinotefuran and its analogues interact with the ACh-binding site in cockroach nAChRs, it remains to be elucidated why they displayed lower potencies than those expected based on their insecticidal activities.     

Structural effects of dinotefuran and analogues in insecticidal and neural activities

The insecticidal potencies of dinotefuran and analogues against the adult male American cockroach, Periplaneta americana (L) were measured by injection with or without metabolic inhibitors. The potency of dinotefuran was close to those of clothianidin and imidacloprid under the conditions used. The nerve-excitatory and nerve-blocking activities were measured with central nerve cords of P americana. The nerve-excitatory activity of dinotefuran was lower than that of imidacloprid, but was comparable with that of clothianidin. The nerve-blocking activity of dinotefuran was comparable with that of imidacloprid and slightly higher than that of clothianidin. Quantitative analyses showed that variations in the insecticidal activity were better correlated with variations in the nerve-blocking activity than with those in the nerve-excitatory activity when the contribution of the hydrophobic factor was allowed for.     

新一代烟碱类杀虫剂呋虫胺及中间体合成新工艺的研究

本文以丙二酸二乙酯为原料,在乙醇钠条件下与氯乙酸乙酯反应生成乙烷-1,2,2-三羧酸乙酯,再用硼氢化钠还原得2-羟基-1,4-丁二醇,在对甲苯磺酸的催化下脱水环合成3-羟甲基四氢呋喃,再与对甲苯磺酰氯、三乙胺反应生成3-四氢呋喃甲基对甲苯磺酸酯;甲醛水溶液、甲基硝基胍、甲胺水溶液在乙醇中反应生成1,5-二甲基-2-硝基亚胺六氢-1,3,5-三嗪;3-四氢呋喃甲基对甲苯磺酸酯与1,5-二甲基-2-硝基亚胺六氢-1,3,5-三嗪反应生成呋虫胺。     

呋虫胺在水稻生态系统中的残留消解及膳食风险评估

为评价呋虫胺在水稻生态系统中的残留消解行为和产生的膳食摄入风险,于2014年在海南、湖南和黑龙江进行了规范残留试验,建立了高效液相色谱法（HPLC）的分析方法检测呋虫胺在水稻糙米、稻壳、稻株、土壤、田水中的残留,并对我国不同人群的膳食暴露风险进行了评估。样品经乙腈提取,NH₂柱层析净化,高效液相色谱-紫外检测器（HPLC-UV）检测,外标法定量。结果表明,在0.02~0.5 mg/kg添加水平下,呋虫胺的平均回收率在75%~114%之间,相对标准偏差（RSD）在0.5%~19.0%之间;呋虫胺的最低检测浓度（LOQ）,稻株与稻壳中为0.1 mg/kg,糙米中为0.05 mg/kg,土壤与田水中为0.02 mg/kg;呋虫胺最小检出量（LOD）为0.08 ng。呋虫胺的消解基本符合一级动力学方程,半衰期在稻株中约0.5 d,田水中约1 d,土壤中约5 d。距末次施药后14 d糙米中呋虫胺的残留中值为0.058 mg/kg,最大残留值为0.13 mg/kg,低于我国规定的最大残留限量1 mg/kg。风险评估表明中国人群对稻米中呋虫胺长期膳食摄入的慢性风险较低。     

新烟碱类杀虫剂呋虫胺对褐飞虱的防效及安全性评价

为了明确新烟碱类杀虫剂呋虫胺对水稻褐飞虱的防治效果及其对水稻及其天敌拟水狼蛛的安全性。本研究通过室内作物安全性试验,测定了呋虫胺对水稻的安全性;采用浸渍法,测定了呋虫胺对褐飞虱和拟水狼蛛的毒力,并进行了田间药效试验。室内毒力测定表明,呋虫胺对水稻褐飞虱的LC50和LC帅分别为0.761 0和4.305 5mg/L,对天敌拟水狼蛛表现一定低风险,安全系数为5.443 3;安全性评估试验表明,20%呋虫胺悬浮剂喷施后水稻未出现药害,对水稻生长没有抑制作用;大田防效的试验表明,20%呋虫胺悬浮剂推荐剂量的防效高于350g/L吡虫啉悬浮剂推荐剂量的防效,施药后1d防效达到80%以上,施药后7d防效达到90%以上。综上所述,呋虫胺对水稻褐飞虱的防治效果好,对作物安全,对天敌拟水狼蛛低风险。     

呋虫胺在水稻中的残留消解及膳食风险评估

为评价呋虫胺在水稻中的残留消解行为和产生的膳食摄入风险,分别于2012和2013年在安徽、重庆和广西进行了规范残留试验,建立了高效液相色谱-紫外检测器(HPLC-UV)检测呋虫胺在水稻糙米、稻壳和植株中残留的分析方法,并对我国不同人群的膳食暴露风险进行了评估。样品经乙腈提取、Florisil柱层析净化,高效液相色谱-紫外检测器检测,外标法定量。结果表明:呋虫胺在糙米、稻壳和植株中的定量限(LOQ)均为0.05 mg/kg。在0.05~2 mg/kg添加水平下,呋虫胺的平均回收率在70%~100%之间,相对标准偏差(RSD)在0.5%~6.5%之间。呋虫胺在水稻植株中的消解符合一级动力学方程,半衰期为2.3~4.8 d,距末次施药后7 d糙米中的最大残留量为0.53 mg/kg,低于日本和国际食品法典委员会(CAC)规定的最大残留限量2和8 mg/kg。膳食摄入风险评价结果显示:我国各类人群的呋虫胺国家估计每日摄入量(NEDI)为0.438~1.087 μg/(kg bw·d),风险商值(RQ)为0.002~0.005,表明呋虫胺在糙米中的长期膳食摄入风险较低。     

Correlated responses to neonicotinoid insecticides in clones of the peach-potato aphid, Myzus persicae (Hemiptera: Aphididae)

BACKGROUND: Although there are still no confirmed reports of strong resistance to neonicotinoid insecticides in aphids, the peach-potato aphid (Myzus persicae Sulzer) shows variation in response, with some clones exhibiting up to tenfold resistance to imidacloprid. Five clones varying in response to imidacloprid were tested with four other neonicotinoid molecules to investigate the extent of cross-resistance.RESULTS: All four compounds-thiamethoxam, thiacloprid, clothianidin and dinotefuran-were cross-resisted, with ED(50) values ranked in the same order as for imidacloprid. Resistance factors ranged up to 11 for imidacloprid, 18 for thiamethoxam, 13 for thiacloprid, 100 for clothianidin and 6 for dinotefuran.CONCLUSION: This variation in response does not appear to be sufficient to compromise the field performance of neonicotinoids aimed at controlling aphids. However, it highlights the need for careful vigilance and stewardship in all M. persicae populations, and a need to consider neonicotinoids as a single cross-resisted group for management purposes.     

超高效液相色谱-串联质谱法检测棉花和土壤中呋虫胺残留

在QuEChERS方法基础上,建立了棉花和土壤中呋虫胺残留的超高效液相色谱-串联质谱(UPLC-MS/MS)快速检测分析方法。方法选用乙腈为提取剂,N-丙基乙二胺(PSA)和石墨化炭黑(GCB)为净化剂,外标法定量。添加回收试验结果表明,不同添加浓度的呋虫胺(0.01、0.05和0.5mg/kg)在棉花植株、棉籽和土壤中的平均回收率为80.9%~107.5%,变异系数为3.3%~10.3%,定量限(LOQ)分别为4.81、3.41和2.26μg/kg。呋虫胺在棉花植株上的消解动态表明,呋虫胺在河南省和山东省两地棉花植株中的降解半衰期分别为1.9d和1.2d。