天然除虫菊酯检测方法的研究进展

天然除虫菊酯已成为当今无公害生物杀虫剂的研究热点之一,广泛应用于农业、林业、生物农药和食品卫生安全等多个领域。本文总结了目前相关研究的现状与成果,分析了目前应用于检测天然除虫菊酯的薄层色谱法、气相色谱法、液相色谱法及联用技术的优缺点。重点讨论了在天然除虫菊酯残留检测方法中,代表其发展趋势的免疫学方法及生物传感器技术,并在此基础上提出实现检测的设想。     

被动采样技术评价水生环境中拟除虫菊酯生物有效性的研究进展

拟除虫菊酯作为一类广谱杀虫剂，已大量应用于农林业及卫生领域，在各地区的水生环境中被频繁检出。同时，拟除虫菊酯易在水生生物体内富集且产生较高毒性。拟除虫菊酯属于强疏水性化合物，在使用常规化学分析方法分析其在环境介质中的总浓度时，往往会高估其环境风险。近20年来，生物有效性已被广泛用于疏水性有机污染物的环境风险评价。被动采样技术是待测物自发地由采样介质向采样器传输的一种采样技术，通过被动采样技术测定的拟除虫菊酯自由溶解态浓度比总浓度更能准确地反映其生物有效性。本文综述了利用被动采样技术评价水生环境中拟除虫菊酯生物有效性的最新研究进展。首先简单阐述了用于评价水生环境中拟除虫菊酯生物有效性的被动采样技术的基本原理，然后详细讨论了常用被动采样器的基本性能和应用特点，详细介绍了被动采样技术在水中拟除虫菊酯残留监测、水生生物毒性评价和积累量预测方面的应用，最后展望了这一技术在我国未来的发展方向。     

制剂中除虫菊酯和合成拟除虫菊酯的气相色谱分离法

导言以天然除虫菊、丙烯菊酯和一些新合成的拟除虫菊酯为主要原料的杀虫剂正被广泛地应用于农业和公共卫生方面。这些化合物有共性,但在化学结构、物理性质和生物活性方面也存在着明显的差异。随意地用一种菊酯代替另一种菊酯可能会造成危害。对这几种菊酯分别进行分析的方法已有报道。本文作者提出了一个能够同时对制剂中的天然除虫菊酯的六个主要活性组份和主要合成拟除虫菊酯进行定性、定量分析的方法。     

浓硫酸净化-气相色谱法检测茶叶中α-硫丹和拟除虫菊酯类农药残留

建立了一种茶叶中硫丹和5种拟除虫菊酯类农药(联苯菊酯、高效氯氟氰菊酯、氯氰菊酯、溴氰菊酯和氰戊菊酯)残留分析的新方法。样品以乙腈提取,浓硫酸-乙醇净化,毛细管柱气相色谱法(GC-ECD)测定。结果表明:在0.005～0.5 mg/kg添加水平内,4种茶叶样品中α-硫丹和5种拟除虫菊酯农药的添加回收率在81.6%～105.9%之间,相对标准偏差(RSD)为0.52%～13.0%(n=3)。α-硫丹和5种拟除虫菊酯农药在4种茶叶中的定量限(LOQ)均为0.005 mg/kg。本方法杂质干扰少,准确度及灵敏度满足农药残留检测要求,对检测硬件要求低,适用于茶叶中α-硫丹及拟除虫菊酯类农药残留的分析。     

拟除虫菊酯农药在茶园应用的安全性评价

采用田间模拟施药与气相色谱法研究了７种拟除虫菊酯在茶园生态环境中的降解动态,茶叶加工过程中的消解和泡茶过程中浸出率及其主要影响因子。根据实验结果推算出通过饮茶进入人体的农药量,结合农药的毒理特性,对拟除虫菊酯在茶园生态环境中应用的安全性进行了综合评价。结果表明,拟除虫菊酯类农药在茶园中应用的安全性显著高于有机磷农药,在拟除虫菊酯农药之间,其安全性也有较大差异。本研究不仅为茶园用农药的选择提供了依据     

十年来我国拟除虫菊酯类杀虫剂的发展及其展望

长期以来,天然除虫菊素是防治害虫的一种理想杀虫剂,具有高效、击倒快、低毒、低残留等优点。但是由于除虫菊花的生产受到土地、气候、栽培条件和劳动力的限制,供应量不大。 四十年代后期,第一个合成拟除虫菊酯丙烯菊酯问世,为拟除虫菊酯杀虫剂的发展开辟了广阔的前景。随着,有许多新的拟除虫菊酯品种不断试制成功,但它们对光的不稳定性限制了应用。 七十年代初,英国M.Elliott合成了二氯苯醚菊酯、氯氰菊酯和溴氰菊酯,以及日本N.ohno合成了戊酸氰醚酯,它们既保持了天然除虫菊素的特点,同时有更高的药效,对光稳定,适用于防治农业害虫,     

两种挥发性拟除虫菊酯杀虫剂对伊蚊的驱避作用研究

拟除虫菊酯杀虫剂广泛应用于蚊香及其他驱蚊产品,不仅对蚊子有杀虫作用,而且具有驱避效应,然而拟除虫菊酯杀虫剂对蚊子驱避作用的机理尚不清楚.本研究发现两种挥发性拟除虫菊酯杀虫剂四氟甲醚菊酯和氯氟醚菊酯对白纹伊蚊和埃及伊蚊具有非接触驱避作用.触角电位(EAG)试验表明除四氟甲醚菊酯有微弱EAG响应外,其他拟除虫菊酯杀虫剂均没...     

天然除虫菊素母药中主要成分质谱分析研究

除虫菊素是从除虫菊中提取出来的植物源农药，具有高效、广谱、低毒、对害虫有拒食和驱避作用、害虫不易产生抗性等功效，广泛应用于卫生杀虫领域。我国已有企业进行天然除虫菊素的开发和生产，由于除虫菊提取物成分复杂，各组分分析较难，国内除虫菊素的分析研究报道较少，国际上对除虫菊素的分析多采用气相色谱法和滴定法。本文采用气相色谱一质谱联用法对部分国内企业登记的除虫菊素母药进行分析，总结出除虫菊素各组分的质谱特征，为除虫菊素的质量、残留分析提供帮助。比较不同企业产品中各组分含量，为我国除虫菊素的登记管理提供有力支持。     

拟除虫菊酯类农药急性中毒的防治

拟除虫菊酯类农药急性中毒的防治鲁锡荣（中国预防医学科学院劳动卫生与职业病研究所１０００５０）拟除虫菊酯类杀虫剂是模拟天然植物除虫菊的有效杀虫成分除虫菊素，经人工合成的一类农药。自１９４９年合成第１个拟除虫菊酯化合物丙烯菊酯以来，已合成了近万种拟除虫菊...     

我国除虫菊酯原药产量占全球1／3

8月15日，从中国科学院昆明植物所获悉，该所在生物农药除虫菊产业化关键技术的研发方向取得一系列突破性成果，开发了从良种选育、推广种植，到除虫菊酯提取、精制技术等成套技术。在这一技术支持下，我国除虫菊产业已经形成规模，特别是由除虫菊干花制取的除虫菊酯农药原药产量已占到全球30%～40％。     

Effects of organic‐farming‐compatible insecticides on four aphid natural enemy species

BACKGROUND: The toxicities of pyrethrins + rapeseed oil, pyrethrins + piperonyl butoxide (PBO), potassium salts of fatty acids and linseed oil were assessed in the laboratory on the parasitic wasp Aphidius rhopalosiphi (Destefani‐Perez), the ladybird Adalia bipunctata (L.), the rove beetle Aleochara bilineata (Gyll.) and the carabid beetle Bembidion lampros (Herbst.). The methods selected were residual contact toxicity tests on inert and natural substrates. RESULTS: Both the pyrethrin products led to 100% mortality in the adult parasitic wasps and ladybird larvae on glass plates and plants. The pyrethrins + PBO formulation was toxic for B. lampros on sand and natural soil, but the pyrethrins + rapeseed oil formulation was harmless for this species. Insecticidal soaps were harmless for all these beneficial species. None of the tested products significantly affected the parasitism of the onion fly pupae by A. bilineata. CONCLUSION: The results indicated the potentially high toxicity of natural pyrethrins for beneficial arthropods. Although this toxicity needs to be confirmed in field conditions, the toxicity levels obtained in the laboratory were similar to or higher than those of several synthetic insecticides known to be toxic in the field. Insecticidal soaps could be considered as an alternative for aphid control in organic farming in terms of selectivity. Copyright © 2010 Society of Chemical Industry     

Changes in cross-resistance patterns of houseflies selected with natural pyrethrins or resmethrin (5-benzyl-3-furylmethyl (±)-cis-trans-chrysanthemate)

A pyrethrins-resistant strain of houseflies, 213ab, previously selected with a 1:10 (by wt.) mixture of natural pyrethrins and piperonyl butoxide, was further selected either with natural pyrethrins alone (strain NPR) or with resmethrin (strain 104). After 50 generations the two populations differed in their resistance to the natural and synthetic esters. Both were resistant to all pyrethroids. Part of strain NPR was immune and very much more resistant than strain 104 to the natural pyrethrins and allethrin, but it was only 2–3 times more resistant than strain 104 against the new synthetic esters resmethrin (5-benzyl-3-furylmethyl (±)-cis-trans-chrysanthemate), bio-resmethrin (5-benzyl-3-furylmethyl (+)-trans-chrysanthemate), pyresmethrin (5-benzyl-3-furylmethyl pyrethrate) and 5B2Me3FC (5-benzyl-2-methyl-3-furylmethyl (±)-cis-trans-chrysanthemate). Pretreatment of both strains with sesamex diminished but did not eliminate resistance. Synergism was greater in strain NPR, especially with natural pyrethrins and allethrin. Both strains had great resistance to DDT indicating that resistance to DDT and pyrethroids is linked. Differences in resistance to different compounds suggest that at least three factors can confer resistance, one of which, pen, delays penetration and two others involve detoxication, one py a on the acid side of the ester linkage and the other, py b, on the alcohol side. Natural pyrethrins and resmethrin select for different groupings of these factors. Treatment with resmethrin does not select for py b presumably because this mechanism cannot attack the resmethrin molecule. Similarly when piperonyl butoxide is added to the natural pyrethrins py b is inhibited and so removed from selection pressure. Under these conditions, the strain produced contains the same factors as one selected by resmethrin and so shows the same small resistance to natural pyrethrins alone.     

Responses of Corcyra cephalonica (Stainton) to pirimiphos-methyl, spinosad, and combinations of pirimiphos-methyl and synergized pyrethrins

Field control failures with pirimiphos-methyl against the rice moth, Corcyra cephalonica (Stainton), in Weslaco, Texas, USA, led us to investigate the susceptibility of this particular strain to pirimiphos-methyl, spinosad, pyrethrins synergized with piperonyl butoxide, and pirimiphos-methyl combined with synergized pyrethrins. In laboratory bioassays, 50 eggs of C cephalonica were exposed to untreated and insecticide-treated corn and sunflower seeds to determine larval survival after 21 days, egg-to-adult emergence after 49 days, and larval damage to seeds at both exposure periods. Pirimiphos-methyl at both 4 and 8 mg kg(-1) did not prevent larval survival or egg-to-adult emergence of C cephalonica on either corn or sunflower seeds, and seed damage was evident at both rates. The C cephalonica strain was highly susceptible to spinosad at 0.5 and 1 mg kg(-1). At both spinosad rates, reduction in larval survival, egg-to-adult emergence, and seed damage relative to the control treatment was > or = 93% on both corn and sunflower seeds. Pirimiphos-methyl and spinosad were generally more effective against C cephalonica on corn than sunflower seeds. The C cephalonica strain was completely controlled on corn treated with 1.5 mg kg(-1) of pyrethrins synergized with 15 mg kg(-1) of piperonyl butoxide. Many larvae survived and became adults on corn treated with synergized pyrethrins at < or = 0.75 mg kg(-1). Corn treated with pirimiphos-methyl at 4, 6 or 8 mg kg(-1) in combination with 0.38 to 1.5 mg kg(-1) of synergized pyrethrins reduced larval survival by > or = 95%, egg-to-adult emergence by > or = 97%, and seed damage by > or = 94%. Our results suggest that the C cephalonica strain can be controlled on corn by combining pirimiphos-methyl with synergized pyrethrins or with synergized pyrethrins at the labeled rate. Although spinosad is not currently labeled for use on stored corn and sunflower seeds, it appears to be effective against C cephalonica on both commodities at very low rates.     

Side effects of botanical insecticides on predatory mite Amblyseius andersoni (Chant)

The effects of the botanical insecticides Biopiren plus, Piresan plus and Neemazal T/S on the predatory mite Amblyseius andersoni (Chant) were tested under laboratory, semi-field, and field conditions. The tests carried out in the laboratory allowed detection of the direct toxicity on eggs and females as well as the effects on fecundity, whereas semi-field trials assessed their residual toxicity. In laboratory and semi-field tests, pyrethrins, particularly Piresan plus, proved to have the highest toxicity with E value, concerning both female mortality and fecundity, of 100% and 45%, respectively. The same product tested in the field only caused a significant reduction in the phytoseiid population shortly after the treatment. The relevant escape rate registered in semi-field tests could explain the lack of phytoseiid eradication in the field after treatment with pyrethrins.     

Side effects of botanical insecticides on predatory mite Amblyseius andersoni (Chant)

The effects of the botanical insecticides Biopiren plus, Piresan plus and Neemazal T/S on the predatory mite Amblyseius andersoni (Chant) were tested under laboratory, semi-field, and field conditions. The tests carried out in the laboratory allowed detection of the direct toxicity on eggs and females as well as the effects on fecundity, whereas semi-field trials assessed their residual toxicity. In laboratory and semi-field tests, pyrethrins, particularly Piresan plus, proved to have the highest toxicity with E value, concerning both female mortality and fecundity, of 100% and 45%, respectively. The same product tested in the field only caused a significant reduction in the phytoseiid population shortly after the treatment. The relevant escape rate registered in semi-field tests could explain the lack of phytoseiid eradication in the field after treatment with pyrethrins.     

植物源杀虫剂除虫菊素产品的纯化技术

用超临界CO2从除虫菊千花中萃取的除虫菊素，这种膏状物不能直接用来加工或深加工杀虫产品。用于家庭和大田的杀虫剂加工时，必须把里面大部分的杂质如蜡质、脂肪酸酯、色素等除去。纯化后的精菊油含有50％～70％除虫菊素，外观为淡黄色流动液体，符合FAO/WHO标准。     

Potential of piperonyl butoxide‐synergised pyrethrins against psocids (Psocoptera: Liposcelididae) for stored‐grain protection

BACKGROUND: Piperonyl butoxide (PB)‐synergised natural pyrethrins (pyrethrin:PB ratio 1:4) were evaluated both as a grain protectant and a disinfestant against four Liposcelidid psocids: Liposcelis bostrychophila Badonnel, L. entomophila (Enderlein), L. decolor (Pearman) and L. paeta Pearman. These are key storage pests in Australia that are difficult to control with the registered grain protectants and are increasingly being reported as pests of stored products in other countries. Firstly, mortality and reproduction of adults were determined in wheat freshly treated at 0.0, 0.75, 1.5, 3 and 6 mg kg^?1 of pyrethrins + PB (1:4) at 30 ± 1 °C and 70 ± 2% RH. Next, wheat treated at 0.0, 1.5, 3 and 6 mg kg^?1 of pyrethrins + PB (1:4) was stored at 30 ± 1 °C and 70 ± 2% RH and mortality and reproduction of psocids were assessed after 0, 1.5, 3 and 4.5 months of storage. Finally, the potential of synergised pyrethrins as a disinfestant was assessed by establishing time to endpoint mortality for adult psocids exposed to wheat treated at 3 and 6 mg kg^?1 of synergised pyrethrins after 0, 3, 6, 9 and 12 h of exposure. RESULTS: Synergised pyrethrins at 6 mg kg^?1 provided 3 months of protection against all four Liposcelis spp., and at this rate complete adult mortality of these psocids can be achieved within 6 h of exposure. CONCLUSION: Piperonyl butoxide‐synergised pyrethrins have excellent potential both as a grain protectant and as a disinfestant against Liposcelidid psocids. Copyright © State of Queensland, Department of Employment, Economic Development and Innovation, 2010. Published by John Wiley and Sons, Ltd.     

Genetics of resistance of pyrethroid-selected houseflies,Musca domestica L.

Four resistance factors were isolated genetically from the NPR strain of houseflies (Musca domestica L.), which resists natural pyrethrins, and were characterised toxicologically. The four factors were : pen, which reduces the rate of penetration of insecticides through the cuticle; kdr-NPR, a general pyrethroid resistance mechanism unaffected by the synergist sesamex; py-ses, a mechanism of resistance to natural pyrethrins that can be suppressed by sesamex; and py-ex, a factor that gives strong resistance to synergised natural pyrethrins and to the new synthetic esters, e.g. resmethrin, but little or none to natural pyrethrins alone.     

Measurements of temperature and degradation of pyrethroids in two thermal fogging machines,the swingfog and TIFA

The losses of natural pyrethrins, bioallethrin, bioresmethrin and tetramethrin have been measured during thermal fogging using the Swingfog Model SN6 and the Lightweight TIFA. Fogs produced from kerosene solutions of the insecticides containing an internal standard were analysed by gas chromatography. Losses of natural pyrethrins, bioresmethrin and tetramethrin were less than the experimental error showing that these compounds did not degrade in either machine. Losses of bioallethrin were 3.1 and 5.5% in the Swingfog and TIFA respectively but these figures were possibly exaggerated slightly by inefficiencies in the fog sampling technique and it is doubtful if losses of this magnitude would be detected under field conditions. Whilst operating with odourless kerosene, the maximum temperatures recorded within the fogging heads were 120°C in the Swingfog with a flow rate of 351/h and 265°C in the TIFA with a flow rate of 951/h.