Additive effects on the improvement of insecticidal activity: Design,synthesis, and insecticidal activity of novel pymetrozine derivatives

A series of new pymetrozine analogues containing both methyl on the imine carbon and phenoxy group at the pyridine ring were designed and synthesized. Their insecticidal activities against bean aphid (Aphis craccivora), mosquito larvae (Culex pipiens pallens), cotton bollworm (Helicoverpa armigera), corn borer (Ostrinia nubilalis) and oriental armyworm (Mythimna separata) were evaluated. The results of bioassays indicated that most of the target compounds showed good insecticidal activity against bean aphid; especially, IIIf (80%) and IIIl (80%) exhibited higher aphicidal activity than pymetrozine (30%) at 5 mg/kg, and the two compounds still showed 20% and 30% mortality at 2.5 mg/kg, respectively, whereas pymetrozine displayed no activity at the same concentration. These compounds exhibited a completely different structure–activity relationship to that of known pymetrozine derivatives, in which it is thought introducing alkyl group on the imine carbon could be detrimental to the activities. Our new result suggested that the methyl on the imine carbon and phenoxy group at the pyridine ring of phenoxy group may play additive effects on the improvement of aphicidal activity. Besides this, compound IIIs, containing an allyl at the para position of phenoxy group, exhibited excellent insecticidal activity against mosquito larvae, lepidoptera pests cotton bollworm, corn borer and oriental armyworm.     

Effect of spray dryer processing parameters on the insecticidal activity of two encapsulated formulations of baculovirus

The effect of spray dryer processing parameters on the product yield and insecticidal activity of baculovirus was evaluated. Spray-dried samples of a granulovirus (GV) from Pieris rapae (L.) and a multiple nucleopolyhedrovirus (MNPV) from Anagrapha falcifera (Kirby) were prepared using two dryer-atomiser configurations (rotary atomiser and two-fluid spray atomiser), four drying temperatures (50–100°C outlet temperatures) and two encapsulating formulations (lignin and methacrylic acid polymer). The samples were evaluated based on yield and insecticidal activity under laboratory conditions. The two atomising configurations produced similar outlet temperatures for dryer stock feed rates of 4.12 and 20 ml/min when processed using increasing inlet temperatures. The atomiser selection significantly affected the physical properties like the product yield; the microparticles produced with a two-fluid spray atomiser had lower product yields (57.8 ± 18.80% – 74.6 ± 4.26%) when compared with paired samples produced with a rotary-disc atomiser (58.1 ± 7.13% – 82.6 ± 3.12%). Spray drying reduced insecticidal activity of the GV but did not significantly reduce insecticidal activity of the MNPV when compared with samples that were not dried. Among dried samples, the spray dryer processing parameters (atomiser, drying temperatures and formulation) had minimal effect on the insecticidal activity of either baculovirus. The versatility of spray drying for processing baculoviruses was demonstrated by identifying parameters that improve process yield while having minimal impact on insecticidal activity.     

The insecticidal activity of beauvericin and the enniatin complex

The insecticidal activity of a complex mixture of enniatins, cyclohexadepsipeptides produced by Fusarium lateritium, a pathogen of the scale insect Hemiberlesia rapax, is compared with that of enniatin A and beauvericin in two bioassays against Calliphora erythrocephala and Aedes aegypti.     

The biology of insecticidal activity and resistance

Identifying insecticide resistance mechanisms is paramount for pest insect control, as the understandings that underpin insect control strategies must provide ways of detecting and managing resistance. Insecticide resistance studies rely heavily on detailed biochemical and genetic analyses. Although there have been many successes, there are also many examples of resistance that still challenge us. As a precursor to rational pest insect control, the biology of the insect, within the contexts of insecticide modes of action and insecticide metabolism, must be well understood. It makes sense to initiate this research in the best model insect system, Drosophila melanogaster, and translate these findings and methodologies to other insects. Here we explore the usefulness of the D. melanogaster model in studying metabolic-based insecticide resistances, target-site mediated resistances and identifying novel insecticide targets, whilst highlighting the importance of having a more complete understanding of insect biology for insecticide studies.     

蓖麻提取物的杀虫作用研究进展

随着食品安全和发展低碳农业的需要,植物源农药的研究受到了空前的关注。在众多植物源杀虫剂中,蓖麻(Ricinus communis L.)由于其价廉易得、杀虫谱广、杀虫效果好、使用简单方便等优点,逐渐引起人们的高度重视。本文主要从蓖麻毒素粗提物、蓖麻毒蛋白和蓖麻碱的生物效应进行综述,并对其应用发展前景、使用过程中存在的问题与相应的解决办法进行了讨论。     

Effect of optical brighteners on the insecticidal activity of a nucleopolyhedrovirus in three instars of Spodoptera frugiperda

Certain optical brighteners are effective UV protectants, and can improve the insecticidal activity of baculoviruses. We evaluated the effect of 10 optical brighteners, from four chemically different groups, on the insecticidal activity of a nucleopolyhedrovirus (SfMNPV) in third instar Spodoptera frugiperda (J.E. Smith) (Lepidoptera: Noctuidae). The most effective optical brighteners were Blankophor BBH and Calcofluor M2R, both of which are stilbenes. The distyryl‐biphenyl derivative, Tinopal CBS, had no effect, whereas the stilbenes, Blankophor CLE and Leucophor SAC and the styryl‐benzenic derivative, Blankophor ER, resulted in a decrease in virus induced mortality compared to larvae infected with SfMNPV alone. Mixtures of SfMNPV + 0.1% Calcofluor M2R had relative potencies of 2.7, 6.5, and 61.6 in the second, third, and fourth instars, respectively. The mean time to death differed with instar, but was not affected by the addition of 0.1% Calcofluor M2R. Analysis of published studies indicated that the concentration of Calcofluor M2R‐related stilbenes was positively correlated with the relative potency observed in mixtures with homologous NPVs. The average magnitude of optical brightener activity did not differ significantly between early instars of 10 species of Lepidoptera. We conclude that virus formulations containing optical brighteners may be valuable for control of late instar lepidopteran pests.     

杠柳毒素NW的杀虫活性

杠柳毒素NW是从杠柳(Periploca sepium Bunge)中分离的新化合物,是其主要的杀虫成分。对杠柳毒素NW的杀虫活性进行了测定,结果表明:杠柳毒素NW对小地老虎无明显的胃毒活性,对3龄的小菜蛾、粘虫和菜粉蝶幼虫均有较强的胃毒活性,处理后24h的致死中浓(LC50)分别是866.17,927.92和1107.08mg·L-1;对上述供试昆虫均无明显的触杀活性。此外,杠柳毒素NW对棉蚜、棉红蜘蛛及卫生害虫家蝇3龄幼虫和淡色库蚊3龄幼虫均有很好的毒杀活性,处理后24h的LC50分别为1743.17,2179.49,714.94和653.29mg·L-1。     

海洋微生物杀虫活性筛选方法比较

采用活体昆虫浸渍法和细胞毒性测定法对海洋微生物发酵液进行了杀虫活性比较,从294株供试菌株中,共筛选出7株活性较好的菌株;对Lv7-1、02AB8 a、T31和BBY-9四株菌株,在不同时间的生物量、发酵液pH值与细胞毒活性等方面的关系进行了研究。     

荧光发光杆菌TT01品系pirA2B2 基因的克隆表达与杀虫活性

【目的】Photorhabdus luminescens TT01基因组中的一对ORF plu4437-plu4436(简称pirA2B2)的预测氨基酸序列与另一对已证明编码产物有口服杀虫活性的ORF plu4093-plu4092(简称pirA1B1)有50%和45%的一致性,本文旨在研究pirA2B2基因座的表达产物是否也有杀虫活性。【方法】PCR扩增并克隆了pirA2,pirB2和pirA2B2基因,构建了重组表达载体pQE-pirA2,pQE-pirB2和pQE-pirA2B2并分别转入M15菌株表达,经SDS-PAGE和Western blot检测证明,3个重组菌株经IPTG诱导后,分别成功表达了可溶的PirA2,PirB2和PirA2B2蛋白。用亲和层析结合脱盐技术对3个重组菌株表达的外源蛋白分别进行纯化,并通过生物测定确定纯化蛋白的杀虫活性。【结果】生物测定结果显示联合表达的PirA2B2对大蜡螟和斜纹夜蛾五龄幼虫均有明显的血腔杀虫活性,LD50分别为每虫4.0和2.8μg,单独表达的PirA2或PirB2对上述2种害虫没有血腔杀虫活性,但两者的混合物具有与两者联合表达相似的杀虫活性;PirA2B2对大蜡螟和斜纹夜蛾初孵幼虫均无口服杀虫活性。【结论】pirA2B2是P.luminescens TT01菌株基因组中的另一个二元杀虫毒素基因。【意义】pirA2B2的成功克隆表达和杀虫功能的确定为进一步研究其与pirA1B1的关系以及该基因的表达调控等打下了基础。     

Secondary metabolites and insecticidal activity of Anemone pavonina

The insecticidal properties of the crude extracts of the leaves and flowers of Anemone pavonina were evaluated on Pheidole pallidula ants and showed significant levels of activity. Bioassay-guided fractionations led to the isolation of the butenolide ranunculin (1) as the active principle. Chemical investigations of the extracts showed them to contain as major components the sitosterol glycopyranoside lipids 2-5 and the glycerides 6-8. The structures of the metabolites were elucidated, following acetylation and hydrolysis of the natural products, by interpretation of their NMR and mass spectral data. The uncommon lipid metabolites 2-8 were isolated for the first time from the genus Anemone and this is the first report of insecticidal activity of the Anemone metabolite ranunculin against ants.     

嗜线虫致病杆菌HB310菌株杀虫蛋白的纯化及活性鉴定

嗜线虫致病杆菌Xenorhabdus nematophila HB310是从河北省土壤中筛选出的一株昆虫病原线虫体内分离纯化获得的共生菌,该菌的发酵液对多种昆虫有较高的杀虫活性。利用85％饱和度的硫酸铵盐析分别获得胞内蛋白提取物和上清液中胞外蛋白提取物,生测结果表明这两种蛋白提取物中都含有胃毒素和血腔毒素。通过制备型非变性凝胶电泳对蛋白提取物进行分离和纯化,得到了3种有杀虫活性的毒素蛋白（毒素Ⅰ、毒素Ⅱ和毒素Ⅲ）,胞内的毒素蛋白与分泌到胞外上清液中的毒素蛋白是同种蛋白。毒素Ⅰ和毒素Ⅱ对棉铃虫初孵幼虫有明显的胃毒活性,但没有血腔毒性;毒素Ⅲ对大蜡螟幼虫有很强的血腔毒性,LD₅₀为0.18 μg/头。SDS-PAGE图谱显示毒素Ⅰ和毒素Ⅱ是由多个多肽组成的复合蛋白,而毒素Ⅲ只分离出一条多肽。毒素Ⅱ在50℃处理10 min,其杀虫活性没有显著变化;70℃处理10 min对毒素Ⅲ杀虫活性没有显著影响。     

一株具有杀虫活性真菌的鉴定

通过对分离的一株海绵共附生真菌F28的形态特征、生理生化特性的测定及ITS1-5.8S-ITS2序列分析,最终将其确定为米曲霉(Aspergillus oryzae)。该菌株具有生长快,易培养的特点。将该菌株进行发酵和杀虫活性物质提取分离后,通过杀卤虫(Brine Shrimp)活性测试,发现该真菌的代谢产物粗提物具有很强的杀虫活性。     

The insecticidal activity of some norditerpene dilactones

The effects on housefly (Musca domestica) of six norditerpene lactones (nagilactones B, D, E, podolide, hallactone B and 14-epi-ponalactone A) in a defined diet were tested. Nagilactone D was the most active, with an LD₅₀ of 0.7 ppm. Nagilactones C and D were also toxic to light-brown apple moth (Epiphyas postvittana) and codling moth (Laspeyresia pomonella).The relationship between lactone structure and toxicity to housefly is discussed.

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Zusammenfassung Viele aus Podocarpus-Arten isolierte Norditerpenlactone sind für Stubenfliegen toxisch. Es wird über die Resultate der Fütterung von sechs Lactonen an die Stubenfliege in einem definierten Nährboden berichtet und die LD₅₀ von zwölf Verbindungen werden verglichen. Der aktivste Stoff ist Nagilacton mit einer LD₅₀ von 0,7 ppm. Nagilacton C und D sind auch toxisch für Epiphyas postvittana und für den Apfelwickler. Die wirksamsten Verbindungen haben eine kurze nichtpolare Seitenkette und eine elektronenreiche, funktionelle Gruppe bei C-8, ferner sind sie Epoxyalkohole in Ring-A. Diese in der Natur vorkommenden Lactone spielen wahrscheinlich eine Schutzrolle in der Pflanze.

     

The insecticidal activity of some fungal dihydroisocoumarins

The insecticidal activity of asperentin, a dihydroisocoumarin secondary metabolic product of an entomogenous strain of Aspergillus flavus, and some derivatives and analogues, is compared with that of fusarentin dimethyl ether, from Fusarium larvarum, and ochratoxin A in two bioassays against Calliphora erythrocephala and Aedes aegypti.     

Polyhydroxylated azetidine iminosugars: Synthesis,glycosidase inhibitory activity and molecular docking studies

An efficient and practical strategy for the synthesis of unknown azetidine iminosugars (2S,3R,4S)-2-((R)-1,2-dihydroxyethyl)-3-hydroxy-4-(hydroxymethyl)azetidine 2, (2S,3r,4R)-3-hydroxy-2,4-bis(hydroxymethyl)azetidine 3 and (2S,3R,4S)-3-hydroxy-4-(hydroxymethyl)-N-methylazetidine-2-carboxylic acid 4, starting from the d-glucose has been reported. The methodology involves preparation of the 3-amino-N-benzyloxycarbonyl-3-deoxy-6-O-tert-butyldimethylsillyl-1,2-O-isopropylidene-α-d-glucofuranose 9, which was converted to the C-5-OMs derivative 11. Intramolecular nucleophilic displacement of the C-5-OMs group with in situ generated 3-amino functionality provided the required key azetidine ring skeletons 10 with additional hydroxymethyl group. Removal of 1,2-acetonide protection, followed by reduction and hydrogenolysis afforded azetidine iminosugar 2. Alternatively, removal of 1,2-acetonide group and chopping of C1-anomeric carbon gave C2-aldehyde that on reduction or oxidation followed by hydrogenolysis gave 2,4-bis(hydroxymethyl) azetidine iminosugars 3 and N-methylazetidine-2-carboxylic acid 4 respectively. The glycosidase inhibitory activity of 2–4 iminosugars was screened against various glycosidase enzymes and compared with a standard miglitol. Amongst synthesized targets, the compound 2 was found to be more potent amyloglucosidase inhibitor than miglitol. These results were supported by molecular docking studies.     

Structure-function relationships affecting the insecticidal and miticidal activity of sugar esters

Synthetic sugar esters are a relatively new class of insecticidal compounds that are produced by reacting sugars with fatty acids. The objective of this research was to determine how systematic alterations in sugar or fatty acid components of sugar ester compounds influenced their insecticidal properties. Sucrose octanoate, sorbitol octanoate, sorbitol decanoate, sorbitol caproate, xylitol octanoate, xylitol decanoate and xylitol dodecanoate were synthesized and evaluated against a range of arthropod pests. Dosage-mortality studies were conducted on pear psylla (Cacopsylla pyricola Foerster) on pear, tobacco aphid (Myzus nicotianae) Blackman and tobacco hornworm (Manduca sexta [Johannson]) on tobacco, and twospotted spider mite (Tetranychus urticae Koch) on apple in laboratory bioassays. These sugar esters were compared with insecticidal soap (M-Pede, Dow AgroSciences L.L.C., San Diego, CA), to determine how toxicologically similar these materials were against the arthropod pests. Substitutions in either the sugar or fatty acid component led to significant changes in the physical properties and insecticidal activity of these compounds. The sugar esters varied in their solubility in water and in emulsion stability, yet, droplet spread upon pear leaves occurred at low concentrations of 80-160 ppm and was strongly correlated with psylla mortalities (R2 = 0.73). Sequentially altering the sugar or fatty acid components from lower to higher numbers of carbon chains, or whether the sugar was a monosaccharide or disaccharide did not follow a predictable relationship to insecticidal activity. Intuitively, changing the hydrophile from sorbitol (C6) to xylitol (C5) would require a decrease in lipophile chain length to maintain hydrophilic-lipophilic balance (HLB) relationships, yet an increase in lipophile chain length was unexpectedly needed for increasing insecticidal activity. Thus, the HLB of these materials did not correlate with pear psylla mortalities. Initial insect bioassays and dosage-mortality data found significant differences among sugar ester compounds' toxicity to the range of arthropod species. Sucrose octanoate high in monoester content had the highest activity against the range of arthropod pests at low concentrations of 1200-2400 ppm. No single chemical structure for the xylitol or sorbitol esters were optimally effective against the range of arthropods we tested and sorbitol octanoate and xylitol decanoate had the highest insecticidal activity of this group. All of the sugar ester materials produced high T. urticae mortalities on apple at very low concentrations of 400 ppm. Overall, most of the sugar esters that were examined had superior insecticidal activity compared with insecticidal soap. Sugar ester chemistry offers a unique opportunity to design an insecticide or miticide specific to certain arthropod pests which would be valuable in crop integrated pest management (IPM) programs. Sucrose esters are currently used as additives in the food industry which makes them especially attractive as safe and effective insecticides.     

鱼藤属植物内生真菌的分离及杀虫活性研究

本文是以毛鱼藤、白花鱼藤、蜜花鱼藤3种鱼藤属植物为试验材料,分离筛选代谢物具有生物活性的内生真菌菌株。通过组织分离法,从3种鱼藤属植物中分离得到4株代谢表现旺盛的内生真菌菌株。杀虫活性实验表明:4种内生真菌的代谢产物对松材线虫都具有一定的毒杀作用,其中青霉菌的代谢产物活性最高,48 h校正死亡率达90%以上。4种内生真菌中,只有青霉菌的代谢产物对家蚕4龄幼虫具有触杀活性,1.5 mg/头剂量处理时,24 h校正死亡率即达到100%。     

Chemical intra-Mediterranean variation and insecticidal activity of Crithmum maritimum

The chemical composition of the volatile metabolites of Crithmum maritimum harvested from several geographic localities along the Mediterranean coasts was studied by GC and GC-MSD. The major oil constituents were found to be dillapiole, gamma-terpinene, sabinene, limonene and beta-phellandrene. The Western populations were richer in dillapiole, whereas the Southern collections were characterized by increased amounts of thymol methyl ether and gamma-terpinene. The Italian chemical profiles differentiated by the significant contributions of carvacrol methyl ether and isoterpinolene. The essential oils were also investigated for their insecticidal activity and their repellency against Pheidole pallidula (Nylander) ants and found to possess significant activity.