银锭夜蛾性信息素拮抗剂的合成及活性研究

银锭夜蛾Macdunnoughia crassisigna Warren是豆类作物和十字花科蔬菜上重要的食叶性害虫。因其具有暴食性，迁飞性等特点，逐渐成为东北、华北地区重要的农业害虫。由于缺乏有效的绿色防控技术，目前化学农药仍是防控银锭夜蛾有效的方法之一。为提高银锭夜蛾的防治效果，以银锭夜蛾性信息素主要成分顺-7-十二碳烯乙酸酯（Z7-12：Ac）、顺-9-十四碳烯乙酸酯（Z9-14：Ac）为母体结构，通过酯化反应得到结构新颖的类似物14个，结构经GC-MS、¹H NMR、¹³C NMR和HR-MS确证。触角电生理试验（EAG）表明，有11个类似物具有较好的EAG反应。EAG抑制试验发现，类似物4、13和14具有明显的抑制效果。在100 μg剂量下，类似物4对Z7-12：Ac的抑制率达50.2%。风洞试验表明，当添加1500 μg的类似物4时，对银锭夜蛾的干扰尤为显著，没有成虫到达诱芯。田间试验表明，类似物4具有潜在的抑制活性，当添加150、1500 μg的类似物4时，平均诱捕量与性信息素存在显著性差异，抑制率分别为56.90%、59.34%。研究结果有助于揭示性信息素拮抗剂对银锭夜蛾种内化学通讯调控方式，为银锭夜蛾绿色防控技术提供新的思路与手段。     

Inhibition of pheromone action in Sesamia nonagrioides by Haloacetate analogues

The electrophysiological activity of some halogenated analogues of the major component of the sex pheromone of the corn stalk borer Sesamia nonagrioides Lef. (1) is presented. The analogues comprise a series of fluoro-, chloro- and bromoacetate analogues 4 – 10 as well as trifluoromethyl ketone 11. The fluoro derivatives 4 – 6 displayed remarkable electro-antennogram (EAG) intrinsic activities in comparison with the parent acetate 1, while the remaining analogues elicited significantly lower response. The compounds have also been tested as inhibitors of the sex pheromone perception in EAG and in the field. In the laboratory. fluoro analogues 4 – 6 were better inhibitors than chloro derivatives 7 – 9 , which in turn behaved similarly to the bromoacetate 10 . Trifluoromethyl ketone 11, however, was a poor inhibitor of the pheromone action. In the field, baits of mixtures of compounds 5 – 11 with the corn stalk borer pheromone in 10 :1 ratio inhibited the concomitant attraction of the clover cutworm moth Scotogramma irifolii Rott., while the difluoro analogue 5, trichloroacetate 9 and trifluoromethyl ketone 11 also diminished the number of catches of the armyworm Mythimna unipuncta Haw. The monofluoroacetate 4. trifluoro analogue 6 and bromo derivative 10 significantly disrupted the pheromone action of the corn borer, whereas trifluoromethyl ketone 11 synergistically increased the number of males attracted to the pheromone trap alone. Addition of 11 to baits containing the corn borer pheromone caught S. nonagrioides selectively with regard to the other habitat-sharing species M. unipuncta and S. trifolii.     

Inhibition of pheromone response in Sesamia nonagrioides by the pheromone of the sympatric corn borer, Ostrinia nubilalis

Sesamia nonagrioides Lef. and Ostrinia nubilalis (Hübn.) are two corn borers present in the Mediterranean area that share a similar feeding habitat. The female sex pheromones of the two species consist of (Z)-11-hexadecenyl acetate, (Z)-11-hexadecen-1-ol, (Z)-11-hexadecenal and dodecyl acetate (77:8:10:5 w/w) and (Z)-11-tetradecenyl acetate and (E)-11-tetradecenyl acetate (97:3 w/w) respectively. Although the pheromones share no common components, previous work had shown the inhibition of the response by O. nubilalis males to their own pheromone owing to the presence of S. nonagrioides pheromone. In this study, the pheromone of O. nubilalis and its two components separately were shown to inhibit the attraction of S. nonagrioides males to the synthetic female pheromone in both laboratory wind-tunnel bioassay and field trapping studies. In the wind tunnel, the number of contacts of S. nonagrioides males with the source were significantly (P < 0.05) reduced by the single pheromone components of O. nubilalis. In the field, the addition of 1% of O. nubilalis pheromone significantly (P < 0.05) reduced the catches of S. nonagrioides males. The components of both pheromones also elicited electroantennographic responses from antennae of male S. nonagrioides moths. The ecological consequences and the possibilities of applying this cross-inhibition for mating disruption techniques are discussed.     

Disruption of responses to pheromone by (Z)-11-hexadecenyl trifluoromethyl ketone,an analogue of the pheromone,in the cabbage armyworm Mamestra brassicae

The effects of (Z)-11-hexadecenyl trifluoromethyl ketone (Z11-16:TFMK) a fluorinated pheromone analogue, on the responses to sex pheromone of the male cabbage armyworm, Mamestra brassicae, have been investigated in an actograph and by electroantennography (EAG). In spite of its structural proximity with the natural pheromone, Z11-16:TFMK was poorly active in EAG, and not active on male behaviour. When permeated in the air, Z11-16:TFMK reversibly inhibited the electroantennographic responses to (Z)-11-hexadecenyl acetate (Z11-16:Ac), the main component of the sex pheromone. In the actograph, the latency of the activation was increased and the intensity of the behavioural activity of males in response to Z11-16:Ac was significantly reduced in the presence of Z11-16:TFMK. These results, along with others previously reported by us, provide new pointers to the possible use of Z11-16:TFMK in pest-control strategies.     

大豆食心虫性信息素的化学结构触角电位及田间诱蛾效果

用气相色谱(GC)和气相色谱-质谱(GC-MS)分析,证明反-8,反-10-十二碳二烯醇醋酸(B)是大豆食心虫[Leguminivora glycinivorella (Mats.)]性信息素的组分。通过触角电位(EAG)测试,发现反-10-十二碳烯醇醋酸酯(A)、B和反-7,顺-9-十二碳二烯醇醋酸酯(C)对该虫雄蛾触角有强烈刺激作用。大量田间诱蛾试验表明,由A和B两化合物组成的性引诱剂,对该虫雄蛾有很高的引诱活性。其中A和B按5:2混合,剂量50μg/诱捕盆,单盆每日最多诱捕雄蛾达776头,诱捕雄蛾总数是1头活雌蛾的16.8倍。顺-10-十二碳烯醇醋酸酯(D)和反-10-十四碳烯醇醋酸酯(E)降低AB的引诱活性,甘油作为缓释剂,能延长诱芯的有效期,即诱蛾活性。上述结果表明,我国大豆食心虫性信息素不同于日本大豆食心虫性信息素。小面积防治应用试验效果明显。     

Responses of Rhynchophorus ferrugineus adults to selected synthetic palm esters: electroantennographic studies and trap catches in an urban environment

BACKGROUND: The red palm weevil (RPW), Rhynchophorus ferrugineus Olivier, accidentally introduced into the European countries facing the Mediterranean basin, is becoming the most serious pest for ornamental palms in the urban environment. In the present work, tests were conducted on the electroantennogram (EAG) and behavioural responses of RPW adults to five selected synthetic palm esters, ethyl propionate, ethyl butyrate, ethyl isobutyrate, ethyl lactate and ethyl acetate, to assess the application of a mass trapping technique in an urban environment. RESULTS: In the laboratory, EAG bioassays on RPW adults with the synthetic palm esters showed: (1) positive dose‐dependent responses; (2) differences among the treatments; (3) a greater response to ethyl propionate; (4) a higher sensitivity of female antennae compared with male antennae. In the urban environment, RPW behavioural responses, evaluated over six biweekly observations on pheromone‐ and molasses‐ baited traps, showed that more adults were caught by traps supplemented with ethyl propionate and ethyl acetate than by traps supplemented with only ethyl propionate. Similar catches were recorded in the traps supplemented with ethyl propionate or ethyl acetate. CONCLUSION: This study supports the application of the mass trapping implemented with synthetic palm esters as a potential tool for the management of RPW populations to protect ornamental palms in urban environments. Copyright © 2010 Society of Chemical Industry     

Optimisation of the pheromone blend of the swede midge,Contarinia nasturtii,for monitoring

BACKGROUND: The swede midge, Contarinia nasturtii Kieffer, is a serious pest in crucifers. Its pheromone is a blend of (2S,9S)‐diacetoxyundecane, (2S,10S)‐diacetoxyundecane and (2S)‐acetoxyundecane. The pheromone is used in monitoring traps, and this study examines possible ways to optimise the traps. RESULTS: Two dispenser types were compared: polyethylene dispensers and cotton dispensers. Polyethylene dispensers attracted male C. nasturtii for more than 6 weeks, whereas cotton dispensers were attractive for only 2 weeks. All three pheromone components were important for attraction of male midges in the field. The importance of the stereoisomeric compositions of the pheromone compounds was also tested—both in the wind tunnel and in the field. In the case of 2,9‐diacetoxyundecane and 2‐acetoxyundecane, the non‐natural stereoisomers did not inhibit male C. nasturtii attraction, whereas one or both of the stereoisomers of 2,10‐diacetoxyundecane did. CONCLUSION: Pheromone traps with the synthetic pheromone in a 1:2:0.02 ratio emitted from PE dispensers were highly effective and long lasting. As the mixture of stereoisomers of 2,10‐diacetoxyundecane strongly inhibited attraction of male C. nasturtii while those of 2,9‐diacetoxyundecane and 2‐acetoxyundecane did not have any inhibitory effect, it is possible to produce traps that are effective and long lasting but cheaper to produce and maintain. Copyright © 2009 Society of Chemical Industry     

Sublethal effects of larval treatment with deltamethrin on moth sex pheromone communication system of the Asian corn borer, Ostrinia furnacalis

The first, third, and fifth instar larvae of Asian corn borer, Ostrinia furnacalis (Guenée) (Lepidoptera: Pyralidae), were treated with a lethal dose 30% of deltamethrin to determine its sublethal effects on chemical communication of the adult survivors. The capability of all males surviving deltamethrin to contact the pheromone source in a wind tunnel was significantly reduced, but those treated as the first and third instars also exhibited lower percentages of `orientation,' `up-wind flight,' and `approaching' behaviors than the control males. Female moths from the deltamethrin treatment exhibited similar calling periodicity and percentages to the control moths during 10-h scotophase. However, approximately 20% of the females that survived the pyrethroid in the first and third instars contained significantly higher amounts of sex pheromone and wider coefficients of variation of the ratio of E12-tetradecenyl acetate to its Z isomer in those female survivors. There was no significant difference in the pheromone titers and coefficients of variation in control females and the females treated in the fifth instars. The present study indicates that the Asian corn borer may possess a compensation system by which the males that survived treatment at larval stage present a lower response to the pheromone, while the female survivors produce and release more pheromone.     

Effects of pheromone loading, dispenser age, and trap height on pheromone trap catches of the oriental fruit moth in apple orchards

The effects of field aging (0–28 days) and pheromone loading rate on the longevity of red rubber septa loaded with the sex pheromone blend of the oriental fruit mothGrapholita molesta (Busck), were evaluated in North Carolina apple orchards in 2002. Separate field tests examined the influence of trap height and pheromone loading rate of rubber septa on trap catches of adultG. molesta males in an abandoned orchard. The loss of the major pheromone component, (Z)-8-dodecenyl acetate (Z8–12:OAc), from red rubber septa over a 4-week period exhibited a relatively constant release rate with 30, 100 and 300 μg pheromone. Trap catch was significantly higher in pheromone traps placed in the upper canopy than in those in the lower canopy. Pheromone traps baited with 100μg lures caught more moths compared with those loaded with 300 μg. There was no apparent relationship between pheromone trap catch and septa age, with trap catch appearing to be primarily a function ofG. molesta population density. http://www.phytoparasitica.org posting May 14, 2006.     

Summation and gradient characteristics of local electroantennogram response of the European corn borer, Ostrinia nubilalis

Summation and gradient characteristics of the electroantennogram (EAG) responses of male moths of the European corn borer (Ostrinia nubilatis) to their pheromone, (Z)-11-tetradecenyl acetate, were studied. Direct evidence that the summation of the locally elicited EAGs contribute to the overall response amplitude is presented; if two simultaneously stimulated loci were separated by more than 1 mm, the observed response was the summation of the two independent local EAGs. Configuration of the local EAG response was obtained at various loci of the antenna. It was demonstrated that a gradient in the amplitude of the local EAG exists along the antennal axis and that this gradient has its origin in the epithelial layer of the antenna. Several possible morphological and physiological factors affecting the response characteristics were considered.     

Control of the codling moth (cydia pomonella) in apple and pear orchards in Israel by mating disruption

Control of the codling moth,Cydia pomonella (L.) (Lepidoptera: Tortricidae), by pheromone-mediated mating disruption, was studied in Israel using two types of dispensers: Shin-Etsu twist-tie (normal and long-life) and TNO matrix formulation (square wafers). Factors affecting mating disruption: initial pest population density, timing of the pheromone application, early season insecticide treatments and monitoring of the pest, were evaluated. Efficacy of mating disruption was assessed by comparing catch of males in pheromone traps located in pheromone-treated and chemically sprayed control plots. Fruit infestation during the season and at picking time was the major criterion to assess mating disruption. The preferred time for pheromone application was before the first flight of the moth. When pheromones were applied at a later stage, one or two early insecticide sprays had to be used to reduce the initial level of the codling moth population. In all tests, trap catch in pheromone-treated plots was drastically reduced as compared with respective control plots. In pheromone-treated plots where total seasonal trap catch (after pheromone application) was less than 12 males/trap, fruit infestation was less than 1.5%; zero trap catch resulted in 0.1-0.3% infestation. At high population levels, mating disruption was ineffective, with the rate of infestation at picking-time being similar in pheromone-treated and control plots. All the field tests indicated that mating disruption with either Shin-Etsu ropes or TNO squares can control codling moth infestations in apple and pear orchards, at relatively low densities of the pest, as efficiently as commercial insecticide sprays.     

Disruption of mating in codling moth (Lepidoptera: Tortricidae) by chlorantranilipole, an anthranilic diamide insecticide

The influence of the anthranilic diamide insecticide chlorantranilipole (DPX-E2Y45; Rynaxypyr against the adult stage of codling moth, Cydia pomonella L., was examined. Insecticide residues in plastic cups sprayed with 56 mg AI L(-1) (equivalent to the recommended field rate) had a minimal effect on adult survival or fecundity, but significantly fewer female moths were mated in treated than in untreated cups. Similar results were found in field studies with adults placed in screened cages on treated apple foliage for up to 3 weeks. Mating was disrupted when either sex was topically dosed with technical material (0.01-0.1 microg). Males were more sensitive to the disruptive effects of chlorantranilipole than females. A 2 h exposure significantly reduced male activity (walking and wing fanning), but not female calling. A 25 h exposure significantly reduced the activity of both sexes. The proportion of males landing near a sex pheromone source in a flight tunnel was significantly reduced following exposures of 2-4 h and completely eliminated following a 17 h exposure. Male moths partially recovered from either topical or residual exposure to chlorantranilipole, but the extent of their recovery was dose and time dependent. Male response to sex pheromone recovered within 2 h following a 4 h exposure, but following a 17 h exposure only a partial recovery occurred after 48 h. Mating by moth pairs exposed to chlorantranilipole residues for 24 h did not significantly increase during recovery periods of 24-96 h, except in cups treated with 10% of the standard concentration. The proportion of field-collected female codling moths caught in pear ester-baited traps that were mated was significantly lower in apple orchards treated season-long with chlorantranilipole compared with females caught in either untreated orchards or those treated with sex pheromones to cause mating disruption.     

高剂量性信息素环境对草地贪夜蛾求偶和交配行为的影响

本文在风洞中模拟形成高浓度性信息素Z7-12:Ac、Z9-14:Ac和 Z11-16:Ac 环境,研究草地贪夜蛾Spodoptera frugiperda (Smith)的求偶和交配行为,为进一步开发交配干扰技术提供技术参数和依据。研究结果表明,在高剂量性信息素环境下,草地贪夜蛾雄蛾的暗期活动时间延后,而雌蛾的活动节律则没有变化,雌雄蛾之间产生了活动节律的时间差。同时,雌雄交配率和交配持续时间显著下降,交配日龄则显著延迟2 d。由于交配日龄延迟,产卵量及其孵化率也相应降低。性信息素喷射时间间隔对草地贪夜蛾性信息素释放滴度有显著影响,当间隔时间为5、10、20 min时,雌蛾释放的性信息素滴度显著下降,以5 min为最低。因此,高剂量性信息素环境不仅影响雄蛾对性信息素的定向,对雌雄蛾间化学通讯和交配也有显著影响。     

Identification of the sex pheromone of the cotton bollworm,Heliothis armigera,in Israel

The composition of the female sex pheromone ofHeliothis armigera in Israel has been identified, with four main compounds detected: Z-9-hexadecenal (3%), Z-11-hexadecenal (87%), hexadecanal (4%), and hexadecanol (6%). The first two aldehydes are the essential components of the sex pheromone ofH. armigera.     

Efficacy of the pear ester as a monitoring tool for codling moth Cydia pomonella (Lepidoptera: Tortricidae) in New Zealand apple orchards

BACKGROUND: The behavioural response of both sexes of codling moth, Cydia pomonella to the pear-derived kairomone (ethyl (2E,4Z)-2,4-decadienoate), codling moth sex pheromone (E,E-8,10-dodecadien-1-ol), and sex pheromone combined with the pear derived kairomone loaded into red rubber septum were investigated in trapping experiments in New Zealand apple orchards. A range of 0.01-10.0 mg of pheromone loading in rubber septum dispensers was tested and the highest catch of males was in traps baited with 1.0 mg. No dose response in trap catch of males was seen in traps baited with different amounts of pear-derived kairomone (0.01-10.0 mg). RESULTS: The number of females caught was significantly affected by the amount of pear derived kairomone used to bait traps, with the highest catch obtained at 10 mg loading. The attractiveness of sex pheromone was not enhanced by the addition of the kairomone either when used in the same bait or in a separate bait. The mean number of males captured in traps was reduced by 44% when the pheromone and kairomone were combined at ratio of 1:1 (0.1 mg pheromone: 0.1 mg kairomone) in separate sources. CONCLUSION: Kairomone baited traps showed some potential for monitoring the flight activity of female C. pomonella in apple orchards in two locations (Canterbury and Hawke's Bay). However, the number of male moths caught was low as compared to the number of male moths caught in pheromone-baited traps, and therefore the sex pheromone should continue to be used for monitoring male activity.     

Comparison of wind tunnel and field experiments to measure potential deposition of fenpropimorph following volatilisation from treated crops

The potential for short-range transport via air, i.e. volatilisation from the area of application and subsequent deposition on adjacent non-target areas, was investigated for the fungicide fenpropimorph in a wind tunnel system and under outdoor conditions in a higher-tier field study. Fenpropimorph 750 g L(-1) EC was applied post-emergence to cereal along with a reference standard lindane EC. Stainless steel containers of water were placed at different distances downwind of the application area to trap volatile residues during a study period of 24 h following application. Meteorological conditions in the wind tunnel as well as on the field were constantly monitored during the study period. The wind tunnel system was a partly standardised system on a semi-field scale, i.e. wind direction and wind speed (2 m s(-1)) were constant, but temperature and humidity varied according to the conditions outside. In the field experiment, the average wind speed over the 24 h study period was 3 m s(-1) and no rainfall occurred. Three different measuring lines were installed on the non-target area beside the treated field to cover potential variations in the wind direction. However, no significant differences were observed since the wind direction was generally constant. Fenpropimorph was detected in minor amounts of 0.01-0.05% of the applied material in the wind tunnel experiment. Even at a distance of 1 m beside the treated field, no significant deposition occurred (0.04% of applied material after 24 h). In the field, less than 0.1% of the applied fenpropimorph was detected at 0 m directly beside the treated field. At 5 m distance the deposition values were below 0.04%, and at 20 m distance about 0.01%. In general, the amounts of deposited fenpropimorph detected in the partly standardised wind tunnel system and the higher-tier field study were in good agreement.     

Spread of local electroantennogram response of the European corn borer, Ostrinia nubilalis

The electroantennogram (EAG) responses of male moths of the European corn borer (Ostrinia nubilalis) to locally applied pheromone, (Z)-11-tetradecenyl acetate, were studied with multiple electrodes. The amplitude of the locally elicited EAG was different depending on the stimulated point and also on the recorded locus, and a gradient in the amplitude was observed along the antennal axis. The locally stimulated region responded as a local negative deflection relative to the resting region, and the response spread from the stimulated point in an asymmetric way, more effectively in the proximal direction than in the distal direction. A possible mechanism of the local EAG spread is discussed.     

甜菜夜蛾性信息素组分的鉴定及其田间试验

采用气相色谱仪(GC)及气质联用仪(GC-MS)等技术对我国甜菜夜蛾性信息素组分的鉴定结果表明,雌蛾性信息素腺体中含有4种组分,分别为Z9,E12-14:Ac(A)、Z9-14:OH(B)、Z9-14:Ac(C)和Z9,E12-14:OH(D);田间和室内种群各组分的比例(A:B:C:D)分别为47:18:18:17和43:18:23:16,比例及滴度在两种群间未有显著差异;雄蛾田间引诱测定表明,组分A、B显示性信息素活性。几种不同配比的硅橡胶塞诱芯在田间均显示极高的诱蛾活性,以9:1的AB二元诱芯(剂量100μg)最高,其诱蛾量与黑光灯相当,两者呈显著的正相关性,表明该诱芯可替代黑光灯用于甜菜夜蛾的种群测报。利用性诱捕器进行田间种群监测显示,1999年浙江省慈溪市的甜菜夜蛾共发生6代,以第4、5代发生量最高。     

绿盲蝽对七种锦葵科植物挥发物的EAG和趋向行为反应

研究绿盲蝽Apolygus lucorum(Meyer-Dür)对锦葵科植物挥发物的EAG和趋向行为反应,为研发绿盲蝽引诱剂或驱避剂策略提供科学依据。田间采用动态顶空采样方法收集了7种锦葵科植物的挥发物,通过室内气相-质谱联用系统(GC-MS)进行物质鉴定及定量分析,最终测定了雌、雄绿盲蝽成虫对11种候选特征挥发物的触角电位(EAG)反应和嗅觉趋向选择行为。结果表明,7种锦葵科植物的挥发物种类和含量有较大差异,而且4种棉花品种之间的挥发物差异也很显著。棉花石远321的挥发物总量最大,其中4,8-二甲基-1,3,7-壬三烯(DMNT)含量最高,壬醛和罗勒烯其次。蜀葵的挥发物种类和含量均最少。11种候选特征挥发物均能够引起绿盲蝽雌、雄成虫EAG反应,且雄性成虫的反应值大都高于雌性成虫。其中,绿盲蝽雌、雄成虫触角对反-2-己烯酸丁酯EAG反应值最大,芳樟醇、乙酸叶醇酯、甲基庚烯酮及DMNT也能够激发绿盲蝽较大的EAG反应。在趋向行为检测中发现,DMNT及柠檬烯等对雄性成虫具有吸引作用。对雌性成虫有吸引作用的物质有γ-萜品烯、DMNT、月桂烯、α-石竹烯、罗勒烯及乙酸叶醇酯等,其中γ-萜品烯和乙酸叶醇酯对雌性成虫具有极显著吸引效果。锦葵科候选植物挥发物对绿盲蝽雌、雄虫具有不同EAG和趋向行为反应影响,候选气味化合物可以作为设计绿盲蝽引诱剂组分进行害虫防控田间实践。     

Effect of kaolin particle film treatment on winterform oviposition of the pear psylla<Emphasis Type="Italic">Cacopsylla pyri</Emphasis>

Laboratory and field experiments were conducted to evaluate the efficacy of kaolin particle film on winterform oviposition of the pear psyllacacopsyllapyri (L.) (Hemiptera: Psyllidae). Kaolin particle film (kpf) treatment significantly reduced winterform oviposition rates in both choice and no-choice tests in the laboratory. In choice tests, overwintered females laid 11 times more eggs on water-treated dormant shoots than on shoots treated with particle film, within 21 days after treatment. In no-choice tests, kpf treatment also significantly reduced egg numbers compared with water-treated controls. The results of field trials carried out in southwestern Turkey (Antalya) during the late winter — early spring of 2004 and 2005 showed very good efficacy of kpf treatment in comparison with water-treated control. Kpf treatment (just before egg laying, during the dormant-postdormant period) delayed egg-laying activity in overwintered females for up to 3 weeks from the beginning of the experiment and continued to suppress oviposition significantly in comparison with watertreated control up to 4 weeks. Our overall results suggest that kpf treatment may be useful in pear psylla management programs by decreasing winterform oviposition, particularly in conjunction with other control tactics.