Pymetrozine,a Fast-Acting and Selective Inhibitor of Aphid Feeding. In-situ Studies with Electronic Monitoring of Feeding Behaviour

Pymetrozine, a pyridine azomethine compound, represents a novel insecticide with a selective activity against homopteran insects. It acts in a unique way: aphids are not knocked down on contact but seem to die of starvation. This implies an effect of pymetrozine on feeding behaviour. The aim of the present work was to elucidate how and at which step pymetrozine interferes with the complex mechanisms underlying phloem feeding. The effect of pymetrozine, applied in various ways, on different phases of stylet penetration and feeding activity of individual aphids was studied using the Electrical Penetration Graph technique (EPG). Initial choice experiments indicated that pymetrozine does not have a deterrent or antifeedant action. Topical application (150 ng pymetrozine mg^-1 fresh weight) inhibited stylet insertion into the plant. When injected, less than 30 ng mg^-1 was sufficient to produce the same effect. When pymetrozine was systemically applied via plant spraying or root uptake, aphids started feeding normally. After some time, however, they withdrew their stylets from the phloem and walked around with unaffected locomotion. At low doses aphids eventually recovered and resumed feeding. High doses, however, irreversibly disrupted feeding and prevented stylet reinsertion. Aphid motility was not affected up to an estimated haemolymph concentration of 1 mM pymetrozine. Aphids which eventually stopped feeding on pymetrozine-treated plants showed EPGs with distorted salivation/ingestion patterns. It is concluded that pymetrozine does not have a general toxic effect on aphids but selectively interferes with the nervous regulation of feeding behaviour which consequently results in death due to starvation after a few days. © 1997 SCI.     

Electrical penetration graph evidence that pymetrozine toxicity to the rice brown planthopper is by inhibition of phloem feeding

BACKGROUND: Pymetrozine is a valuable novel insecticide for control of sucking insects, including the brown planthopper Nilaparvata lugens (Stål), one of the most serious pests on rice. This study was conducted to elucidate the action mechanisms of pymetrozine on the feeding behaviour of the planthopper. RESULTS: The activity test showed that pymetrozine primarily functioned as an antifeedant that caused starvation and death in N. lugens, rather than having neurotoxicity. Pymetrozine‐treated insects died at a significantly slower speed than insects treated with starvation. Electrical penetration graph (EPG) data indicated that pymetrozine significantly increased the duration of non‐probing periods and had a strong inhibition to phloem ingestion. The inhibition was strongly dose dependent, resulting in a complete suppression of the activity in the phloem region when the pymetrozine concentration was increased to 400 mg L^?1. Starvation caused by inhibition of phloem ingestion might be a major toxicity mechanism of pymetrozine. EPG data also showed that pymetrozine had no significant effect on stylet movement and duration of xylem sap ingestion. CONCLUSION: The study revealed that pymetrozine disturbed the feeding behaviour of N. lugens mainly by increasing the non‐probe period and inhibiting phloem ingestion. The inhibition resulted in a slow death similar to starvation. Copyright © 2011 Society of Chemical Industry     

吡蚜酮对禾谷缢管蚜的亚致死效应

本文研究了吡蚜酮对禾谷缢管蚜的亚致死效应。试验利用刺探电位图谱(EPG)技术测定了亚致死剂量的吡蚜酮对禾谷缢管蚜成虫取食行为的影响,结果表明:经吡蚜酮处理的蚜虫口针从开始刺探到持续吸食韧皮部和木质部汁液的时间明显延长,分别延长至(199.9±34.0)min和(236.4±29.5)min,对照分别为(155.5±18.1)min和(145.5±27.1)min。并且,经药剂处理的蚜虫口针在韧皮部和木质部中持续取食的时间明显缩短,分别为(44.7±9.4)min和(11.8±2.5)min,对照分别为(93.0±24.9)min和(19.0±3.6)min。通过生长和繁殖试验可知:亚致死剂量的吡蚜酮使禾谷缢管蚜的重量显著减轻,繁殖率明显降低。经药剂处理的蚜虫最大重量和最高繁殖率分别为(1.28±0.025)mg/10头和(2.9±0.2)头/成蚜,而对照分别为(1.56±0.099)mg/10头,(5.2±0.2)头/成蚜。     

Phloem translocation of strong acids—glyphosate,substituted phosphonic and sulfonic acids—in Ricinus communis L

The mobility in phloem of several substituted phosphonic acids and a sulfonic acid was studied in the castor bean plant, Ricinus communis L. For a series of¹⁴C-labelled phosphonate mono-esters applied to the petioles of mature leaves, phloem transport was modest, becoming poor over longer distances in the plant. Substituted phenylphosphonic acids were more efficiently moved in phloem; uptake from the petiole and subsequent redistribution were slow, but these dibasic compounds were very stable in plants and substantial amounts reached the roots after 72 to 120 h. Glyphosate was very efficiently transported to phloem sinks even within 24 h, with high concentrations in phloem sap. Toluene-4-sulfonic acid moved predominantly in the xylem to the mature leaves and its phloem transport was poor. Transport patterns are considered in relation to the physico-chemical properties of the compounds. Ion trapping appears to play little part in the phloem transport of these strong acids, though the good accumulation and transport in phloem of the complex molecule glyphosate cannot at present be explained.     

不同培养条件下甲霜灵在蓖麻幼苗韧皮部的输导性

甲霜灵是一种能通过植物叶片吸收后在韧皮部向下传导的杀菌剂,为了探明其在韧皮部的传导规律,以蓖麻幼苗为模式植物,通过改变试验过程培养液中甲霜灵含量、pH值以及培养的温度、时间及光照等因子,采用气相色谱-质谱联用 (GC-MS) 方法,检测了不同培养条件下蓖麻幼苗韧皮部渗出液中甲霜灵的含量。结果表明:光照对甲霜灵在蓖麻幼苗韧皮部中的输导性无显著影响;当培养液中甲霜灵质量浓度为400 mg/L时,其在蓖麻幼苗韧皮部中输导量最大;当培养液pH值为5.5时,甲霜灵在蓖麻幼苗韧皮部中输导量最大;当培养温度为28 ℃时培养效果最佳,温度过高或过低均会使甲霜灵在蓖麻幼苗韧皮部中的输导量减少;培养3 h以上,蓖麻幼苗韧皮部渗出液中甲霜灵的含量显著高于前2 h渗出液中甲霜灵的含量。该研究优化了蓖麻幼苗获得药剂最大吸收时的适宜培养条件,为检测其他未知化合物在植株韧皮部中的输导性提供了参考。     

Phloem mobility of xenobiotics VI. A phloem-mobile pro-nematicide based on oxamyl exhibiting root-specific activation in transgenic tobacco

Phloem mobility is a desirable attribute for pesticides in many applications, and the physicochemical properties necessary for phloem mobility are now well understood. However, attempts to derivatize pesticides to make them phloem mobile are often frustrated by a concomitant loss of activity. This study describes a phloem-mobile pro-nematicide, a hydroxymethyloxamyl glucuronide (JR522) coupled with an in-situ activation mechanism in transgenic tobacco expressing Escherichia coli β-glucuronidase in its root tips. When applied foliarly to the transgenic tobacco, JR522 and its methyl ester (JM775) showed greater nematicidal activity than oxamyl against root-knot nematodes. This example of combining pro-pesticide chemistry with crop genetic engineering for site-specific activation provides a model system for demonstrating how to circumvent the often mutual exclusivity of phloem mobility and pesticidal activity. Additional advantages of this scheme include the potential mammalian safety of the propesticide, as exhibited by JR522 in this study, and a high degree of site-specific release of xenobiotics in plants.     

Systemic properties of myclobutanil in soybean plants, affecting control of Asian soybean rust (Phakopsora pachyrhizi)

BACKGROUND: The demethylation inhibitor (DMI) fungicide myclobutanil can be an effective component of spray programmes designed to control the highly destructive plant pathogen Phakopsora pachyrhizi Syd. & P. Syd., causal agent of Asian soybean rust. Myclobutanil is known from previous studies in grapevines to be xylem mobile. This study investigates the mobility profile of myclobutanil in soybean as an important component of its effective field performance. RESULTS: Over a 12 day period under greenhouse conditions, a constant uptake of myclobutanil from leaflet surfaces into the leaflet tissue was observed. Once in the leaflet, myclobutanil was seen to redistribute throughout the tissue, although no movement out of leaflets occurred owing to a lack of phloem mobility. The ability of myclobutanil to redistribute over distance within the soybean plant was revealed when visualizing movement of the compound to foliage above the point of application on the plant stem. An efficacy bioassay demonstrated that the systemic properties of myclobutanil allow control of disease at a point remote from the initial site of compound application. CONCLUSION: It is suggested that the high degree of xylem systemicity displayed by myclobutanil in soybean foliage is a contributory factor towards its commercial effectiveness for control of Asian soybean rust. Copyright © 2008 Society of Chemical Industry     

两种施药器械对水稻中吡蚜酮残留量影响研究

本文建立了水稻样品中吡蚜酮的LC-MS/MS检测方法,同时2019年进行了背负式喷雾器和植保无人机施用吡蚜酮农药试验,对两种器械施药方式下吡蚜酮在水稻样品中的残留量进行了比较。结果表明,吡蚜酮在稻谷和植株空白样品添加的平均回收率在72%~104%之间,相对标准偏差在4%~11%之间,稻谷和植株中的定量限分别为0.01和0.02mg/kg。在同一用量下,在施药后2h和14d,稻谷和植株中吡蚜酮残留量表现为:植保无人机>人工背负式喷雾器。因此在采用植保无人机施药防治病虫害时,需关注农产品中残留量的变化。     

Effects of cycloxaprid,a novel cis‐nitromethylene neonicotinoid insecticide,on the feeding behaviour of Sitobion avenae

BACKGROUND: Cycloxaprid with cis‐configuration is a novel neonicotinoid insecticide, developed in China, that has good industrialisation prospects for its high activity against imidacloprid‐resistant pests. Studies were carried out to investigate the biological activity of cycloxaprid and its effect on the feeding behaviour of Sitobion avenae. RESULTS: The results demonstrated that cycloxaprid had good contact and root‐systemic activity. The electrical penetration graph (EPG) revealed that cycloxaprid significantly increased the total time of non‐probing periods and greatly inhibited phloem ingestion of treated aphids because it significantly reduced the total time and the frequency of phloem ingestion. Furthermore, cycloxaprid can increase the phloem salivation of treated aphids by comparison with aphids treated with imdacloprid and distilled water. Consequently, a sublethal dose of cycloxaprid impaired aphid ingestion of phloem sap and thereby reduced the weight of aphids. On the other hand, EPG data showed that a sublethal dose of cycloxaprid had no significant effect on xylem sap ingestion, in contrast to imidacloprid. CONCLUSION: All these tests indicated that cycloxaprid had both contact and root‐systemic activity, with sublethal effects resulting in reduction in Sitobion avenae phloem‐feeding behaviour and growth rate. Copyright © 2012 Society of Chemical Industry     

Vectorizing agrochemicals: enhancing bioavailability via carrier‐mediated transport

Systemicity of agrochemicals is an advantageous property for controlling phloem sucking insects, as well as pathogens and pests not accessible to contact products. After the penetration of the cuticle, the plasma membrane constitutes the main barrier to the entry of an agrochemical into the sap flow. The current strategy for developing systemic agrochemicals is to optimize the physicochemical properties of the molecules so that they can cross the plasma membrane by simple diffusion or ion trapping mechanisms. The main problem with current systemic compounds is that they move everywhere within the plant, and this non‐controlled mobility results in the contamination of the plant parts consumed by vertebrates and pollinators. To achieve the site‐targeted distribution of agrochemicals, a carrier‐mediated propesticide strategy is proposed in this review. After conjugating a non‐systemic agrochemical with a nutrient (α‐amino acids or sugars), the resulting conjugate may be actively transported across the plasma membrane by nutrient‐specific carriers. By applying this strategy, non‐systemic active ingredients are expected to be delivered into the target organs of young plants, thus avoiding or minimizing subsequent undesirable redistribution. The development of this innovative strategy presents many challenges, but opens up a wide range of exciting possibilities. © 2018 Society of Chemical Industry     

Association of ‘Candidatus Liberibacter asiaticus’ root infection,but not phloem plugging with root loss on huanglongbing‐affected trees prior to appearance of foliar symptoms

Huanglongbing (HLB) is a systemic disease of citrus caused by phloem‐limited bacteria ‘Candidatus Liberibacter’ spp. with ‘Ca. Liberibacter asiaticus’ (Las) the most widespread. Phloem‐limited bacteria such as liberibacters and phytoplasmas are emerging as major pathogens of woody and herbaceous plants. Little is known about their systemic movement within a plant and the disease process in these tissues. Las movement after initial infection was monitored in leaves and roots of greenhouse trees. Root density, storage starch content, and vascular system anatomy in relation to Las presence in field and greenhouse trees, both with and without symptoms, showed the importance of root infection in disease development. Las preferentially colonized roots before leaves, where it multiplied and quickly invaded leaves when new foliar flush became a sink tissue for phloem flow. This led to the discovery that roots were damaged by root infection prior to development of visible foliar symptoms and was not associated with carbohydrate starvation caused by phloem‐plugging as previously hypothesized. The role of root infection in systemic insect‐vectored bacterial pathogens has been underestimated. These findings demonstrate the significance of early root infection to tree health and suggest a model for phloem‐limited bacterial movement from the initial insect feeding site to the roots where it replicates, damages the host root system, and then spreads to the rest of the canopy during subsequent leaf flushes. This model provides a framework for testing movement of phloem‐limited bacteria to gain greater understanding of how these pathogens cause disease and spread.     

咯菌腈羧酸衍生物内吸传导性及对香蕉枯萎病的防效测定

为研发用于防治香蕉枯萎病的维管组织导向杀菌剂,基于植物韧皮部“离子井”效应对非内吸杀菌剂咯菌腈进行弱酸化结构修饰,在蓖麻模型上完成韧皮部输导性筛选和机制验证,通过盆栽试验研究咯菌腈羧酸衍生物在香蕉植株上的输导分布,并测定衍生物对香蕉枯萎病的防效。结果表明：羧酸基团引入使咯菌腈衍生物在蓖麻幼苗上表现出韧皮部输导性,证明存在pH依赖的“离子井”效应机制;盆栽试验结果显示,衍生物1a在被叶片吸收后能向下传递到香蕉植株球茎和根部,并能够降解释放出咯菌腈,对香蕉枯萎病的防效为54.5%,显著高于咯菌腈原药处理组的防效6.5%。表明基于韧皮部“离子井”效应的结构修饰是香蕉维管组织导向杀菌剂研发的有效途径。     

氟虫腈衍生物-糖基偶合物的合成及其在蓖麻韧皮部的输导性研究

为提高氟虫腈在植物体内的输导性,利用葡萄糖、半乳糖与木糖作为导向基团对其进行了糖基化修饰,设计合成了3个含乙酰保护基的糖基-氟虫腈偶合物(a,b,c)和3个脱保护基的偶合物(d,e,f)。采用液相色谱法测定了其在蓖麻幼苗韧皮部中的输导积累性。结果表明:化合物a、b、c无韧皮部输导性,而d、e、f 则具有良好的韧皮部输导性;培养2 h后,收集的第3 h内韧皮部液中 d、e、f 的浓度分别为21.45、14.14 和14.82 μ mol/L。饲料拌毒法测定结果表明,与母体化合物氟虫腈(LC50为4.49 μ mol/L)相比,6个偶合物对亚洲玉米螟Ostrinia furnacalis的杀虫活性均有所下降,LC50值在47.54~78.00 μ mol/L之间。     

QuEChERS-高效液相色谱-串联质谱法测定高粱中吡蚜酮残留和消解动态

建立了高粱Sorghum bicolor (L.) Moench籽粒及高梁植株中吡蚜酮残留的QuEChERS-高效液相色谱-串联质谱 (HPLC-MS/MS) 检测方法。样品经0.1%甲酸-乙腈提取,通过乙二胺-Ｎ-丙基硅烷 (PSA) 和十八烷基键合硅胶 (C₁₈) 分散萃取净化,采用电喷雾离子化正离子扫描 (ESI+) 和多反应监测模式 (MRM) 检测,外标法定量。结果表明:在0.001~0.2 mg/L范围内,吡蚜酮质量浓度与对应的峰面积间线性关系良好,R2 ≥ 0.9970。在0.002、0.02和0.2 mg/kg添加水平下,吡蚜酮在高粱和高粱植株中的日内平均回收率为71%~92%,日内相对标准偏差 (RSD)(n = 5) 为0.8%~5.6%;日间平均回收率为71%~96%,日间RSD(n = 15) 为1.2%~4.2%。吡蚜酮在高粱籽粒和高粱植株中的定量限 (LOQ) 均为0.002 mg/kg。消解动态试验结果表明,吡蚜酮在高粱植株中的消解动态符合一级反应动力学方程,在内蒙古和黑龙江2个试验点的高粱植株中的消解半衰期分别为9.7 d和9.0 d。该方法可用于高粱中痕量吡蚜酮残留的检测。这些数据有助于高粱中吡蚜酮最大残留限量的制定,并指导吡蚜酮在高粱上的合理使用。     

A new derivative of fipronil: Effect of adding a glycinyl group to the 5-amine of pyrazole on phloem mobility and insecticidal activity

Glycinyl fipronil, a new fipronil derivative with 5-amine acylated by glycine, was synthesized. The phloem mobility of the synthesized derivative was higher that of the parent compound in intact soybean seedling and its insecticidal activity against the 3rd instar larvae of Plutella xylostella was comparable with that of fipronil.     

A new derivative of fipronil: Effect of adding a glycinyl group to the 5-amine of pyrazole on phloem mobility and insecticidal activity

Glycinyl fipronil, a new fipronil derivative with 5-amine acylated by glycine, was synthesized. The phloem mobility of the synthesized derivative was higher that of the parent compound in intact soybean seedling and its insecticidal activity against the 3rd instar larvae of Plutella xylostella was comparable with that of fipronil.     

吩嗪-1-羧酸双酰肼衍生物的合成、杀菌活性及韧皮部的输导性研究

天然产物吩嗪-1-羧酸（PCA,申嗪霉素）及其衍生物吩嗪-1-甲酰肼具有独特的化学结构和优良的杀菌等生物活性,但均没有韧皮部输导性。本文以具有抑菌活性的吩嗪-1-羧酸和具有韧皮部输导性的马来酰肼为先导化合物,将马来酰肼中的双酰肼结构引入到吩嗪-1-羧酸中,设计、合成了17个新化合物,其结构均经过核磁共振氢谱、高分辨质谱及X-射线单晶衍射分析确证。初步生物活性测试表明:大部分目标化合物在50 mg/L下对水稻纹枯病菌Thanatephorus cucumeris表现出中等偏上的抑制活性,其中化合物6m的抑制率达92%。但输导性研究结果显示,目标化合物没有明显的韧皮部输导性。     

Intraspecific variation in Capsella bursa-pastoris in plant quality traits for insect herbivores

The arable plant Capsella bursa‐pastoris is phenotypically variable in many life history traits, particularly time from germination to flowering. The hypothesis was investigated that, associated with this variation, there are differences in traits that influence plant quality for insect herbivores. Significant within‐species variation was found in plant growth, leaf surface characteristics and tissue nutrient composition among 21 accessions of Capsella. Short flowering time plants exhibited slow vegetative growth, relatively large shoot nitrogen content, high leaf hair densities and differences in phloem composition, compared with long flowering time plants. Insect herbivore response to distinctive trait combinations was assessed on a subset of seven accessions using the phloem‐feeding aphids Aphis fabae and Myzus persicae. Variation in aphid performance was small but significant, with 15–25% fewer nymphs produced on plant variants that exhibited greater tissue water content and low tissue C:N ratio (A. fabae) or on variants with less phloem nitrogen (M. persicae). The differential responses exhibited by the two aphid species to the test accessions confirmed that quantifying intraspecific plant variation is a necessary first step in understanding plant functional diversity and its impact on consumers in arable systems.     

Systemic action of novel neonicotinoid insecticide IPP‐10 and its effect on the feeding behaviour of Rhopalosiphum padi on wheat

BACKGROUND: IPP‐10 is a novel neonicotinoid insecticide recently developed in China and has good activity against sucking insects. Studies were carried out to investigate the activity of IPP‐10 against Rhopalosiphum padi L. RESULTS: The results demonstrated that IPP‐10 had both contact and systemic activity, including acropetal and basipetal translocation in wheat vascular bundles. Starved R. padi were allowed to stay on wheat treated with a sublethal dose of IPP‐10. The results of studying their feeding behaviour from an electrical penetration graph (EPG) revealed a decrease in total time and bout duration of xylem and phloem ingestion, but the total time and bout duration of phloem salivation were significantly prolonged. The frequency (7.03 ± 0.49 Hz) of the xylem ingestion waveform produced by aphids on wheat treated with IPP‐10 was significantly lower than that of blank control aphids (8.20 ± 0.30 Hz). Consequently, aphids born on wheat treated with IPP‐10 were obviously lighter and less fecund than the control aphids. CONCLUSION: These tests indicated that IPP‐10 had both contact and systemic activity, with sublethal effects resulting in reduction in R. padi feeding behaviour, growth rate and fecundity. Copyright © 2010 Society of Chemical Industry     

Fungicidal activity of N-(2-cyano-2-methoximinoacetyl)amino acids and their derivatives

More than 20 N-(2-cyano-2-methoximinoacetyl)amino acids and derivatives were synthesised and tested for antifungal activity against grape downy mildew, caused by Plasmopara viticola (de Bary) Berl. & de Toni, and rape downy mildew, Peronospora parasitica Fr. Two of the compounds containing a free carboxylic acid group, a moiety which has been shown to confer phloem mobility on compounds, showed high activity, especially against P. parasitica, in protectant tests. These results indicate that there is no incompatibility between the acid function and fungicidal activity. A number of the esters showed activity comparable with that of cymoxanil in the protectant tests, and the tert-butyl esters of the methionine derivative and its sulfone were more than ten times as active as the commercial compound.