Biological activity of terpenoid lactones as juvenile hormone analogues against the mustard aphid,Lipaphis erysimi

Several α,β-unsaturated γ-lactones were evaluated for their JHA activity. Some of the compounds were quite active in the mustard aphid,Lipaphiserysimi (Kaltenbach), resulting in the production of supernumerary instar nymphs, nymphal-adult intermediates and adultoids.     

New chlorinated juvenile hormone analogues and their biological activity

In the search for new juvenile hormone analogues (JHAs), a general approach was chosen based on the substitution of the isoprene unit, that carries the epoxy function in the natural hormone JHIII, by 3,3,3-trichloropropyl, 2,2-dichlorocyclopropyl- methyl, 3,3-dichloroallyl, or 3-chloroprop-2-ynyl groups. Accordingly, several terpenoid aromatic JHAs were prepared with, or without, oxygen atoms in the aliphatic chain. Structure-biological activity relationships of the most active compounds toward the yellow mealworm (Tenebrio molitor) and the large cabbage white butterfly (Pieris brassicae) are given. With a view to preparing synthetically accessible analogues, some alkyl phenyl ethers were also made, which were not branched in the aliphatic chain and were related terminally to the most active compounds. They were only moderately active against insects when tested for morphogenetic activity, but exhibited a good field persistence. The occurrence of a moderate acaricidal activity among these analogues prompted the examination of several 1,4-disubstituted-phenyl derivatives. The ovicidal effectiveness of these products against a susceptible strain of the two-spotted spider mite, Tetranychus urticae, was ten or 100 times higher than that of the well known and highly potent JHAs.     

Synthesis and juvenile hormone activity of benzimidazolylterpenes possessing a 2,7-dimethyloctane skeleton

Benzimidazolylterpenes, possessing a 2,7-dimethyloctane skeleton showed IGR-activity on pupae of Tenebrio molitor L in laboratory tests: N-(7-methoxy-2,7-dimethyl-2-octenyl)benzimidazole showed the greatest activity.     

Ovicidal activity of juvenile hormone mimics in the bean bug,Riptortus pedestris

Insect juvenile hormone (JH) mimics (JHMs) are known to have ovicidal effects if applied to adult females or eggs. Here, we examined the effects of exogenous JHMs on embryonic development of the bean bug, Riptortus pedestris. The expression profiles of JH early response genes and JH biosynthetic enzymes indicated that JH titer was low for the first 3 days of the egg stage and increased thereafter. Application of JH III skipped bisepoxide (JHSB₃) or JHM on Day 0 eggs when JH titer was low caused reduced hatchability, and the embryos mainly arrested in mid- or late embryonic stage. Application of JHMs on Day 5 eggs also resulted in an arrest, but this was less effective compared with Day 0 treatment. Interestingly, ovicidal activity of synthetic JHMs was much lower than that of JHSB₃. This study will contribute to developing novel insecticides that are selective among insect species.     

Stage-specific action of juvenile hormone analogs

The discovery of juvenile hormones (JH) and their synthetic analogs (JHA) generated excitement and hope that these compounds will replace first- and second-generation insecticides that have not so desirable environmental and human safety profiles. However, JHAs used commercially during the past four decades did not meet these expectations. The recent availability of advanced molecular and histological methods and the discovery of key players involved in JH action provided some insights into the functioning of JHA in a stage and species-specific manner. In this review, we will summarize recent findings and stage-specific action of JHA, focusing on three commercially used JHA, methoprene, hydroprene and pyriproxyfen and economically important pests, the red flour beetle, Tribolium castaneum, and the tobacco budworm, Heliothis virescens, and disease vector, the yellow fever mosquito, Aedes aegypti.     

13种萜类化合物对胶孢炭疽菌和链格孢的抑制活性

炭疽菌Colletotrichum和链格孢Alternaria是引起植物病害的重要真菌,给农业生产造成巨大的损失。本研究选取13种萜类化合物,采用菌丝生长速率法对胶孢炭疽菌、链格孢进行抑菌活性分析。研究结果表明:香芹酚、丁香酚、异丁香酚、枯茗醛、百里香酚对两种病原菌有较好的抑菌活性,其中香芹酚对胶孢炭疽菌和链格孢的抑菌活性最强,IC50分别为40.89μg/mL和18.19μg/mL。本试验为植物精油和天然杀菌剂的开发利用提供理论依据。     

Synthesis and precocious-metamorphosis-inducing activity of 3-pyridyl ethers

A new series of 5-(substituted phenoxy)pentyl 3-pyridyl ethers induced precocious metamorphosis in larvae of the silkworm, Bombyx mori. Both 2- and 4-pyridyl ethers were inactive, indicating that the 3-pyridine moiety was essential for the activity. Octyl, dodecyl and farnesyl 3-pyridyl ethers had no activity. Among the compounds tested so far, 5-(4-propylphenoxy)pentyl 3-pyridyl ether showed the highest activity. The activity fell off with increasing or decreasing length of the carbon chain between two oxygen atoms. Introduction of a methyl group at the 6 position of the pyridine ring completely eliminated the activity. Precocious metamorphosis induced by 3-pyridyl ethers was fully reversible by a simultaneous application of a small amount of tebufenozide, an ecdysteroid agonist, or methoprene, a JH agonist. © 1998 SCI.     

Fenoxycarb,an insect growth regulator with juvenile hormone activity: A candidate for Heliothis virescens (F.) control on cotton

Tobacco budworm eggs, deposited on cotton plants (Gossypium hirsutum L.) treated with fenoxycarb, do not produce viable larvae. The insects die either at the end of embryonic development or during 1st-2nd larval instars, even when the larvae hatching on the treated leaves are transferred to untreated plants. This ovo-larvicidal activity and indications of good foliar persistence make fenoxycarb a promising candidate for the control of tobacco budworm on cotton. This type of application could open new aspects for the control of lepidopterous pests with this novel compound.     

保幼激素类似物对白蚁的作用研究进展

本文介绍了保幼激素类似物对白蚁的影响,包括诱导前兵蚁、兵蚁和一些中间品级(形态畸形)的产生、抑制白蚁的取食、减少或消除白蚁的共生原生动物群、对白蚁产生不同水平的急性和慢性毒性、抑制工蚁蜕皮以及繁殖蚁建立新群体等方面的影响,其中最主要影响是诱导前兵、兵蚁和一些中间品级的产生破坏了白蚁群体品级比例的平衡性或完整性。因此,保幼激素类似物可用于白蚁的防治,并在田间防治散白蚁和乳白蚁均取得了较好的防治效果,并探讨了应用保幼激素类似物防治白蚁的潜力与前景。     

Lactones: Part 11. Feeding-deterrent activity of some bi- and tricyclic terpenoid lactones

The feeding-deterrent activities of thirteen synthetic terpenoid lactones, including isomeric bicyclic gamma-spirolactones with the limonene system and tricyclic gamma-lactones with the pinane system, were determined towards three storage pest insects: the adults of Sitophilus granarius, the adults and larvae of Tribolium confusum and the larvae of Trogoderma granarium. The configuration of chiral centres, as well as the presence of additional functional groups (double bond, iodine and hydroxy group) are important for antifeeding activity.     

Ecdysial failures in the cotton boll weevil: Synergism of diflubenzuron with juvenile hormone

The frequency and etiology of ecdysial failures occurring during the pupal-adult transformation of the cotton boll weevil, Anthonomus grandis, was studied after treatment with juvenile hormone (JH) and/or diflubenzuron (DFB). Failure at emergence was the result of inability of the adult insects to escape from their pupal exuviae. Teratogenic effects in the form of pupal-adult intermediates or adults with pupal characters were not obtained with JH or DFB treatment after the larval-pupal ecdysis. Combining JH with the DFB treatment yielded a synergistic response that increased the frequency of ecdysial failures about sevenfold when applied in the later pupal stages. The fine structure of the abdominal cuticle of adults experiencing ecdysial failure after treatment with JH as white-eyed pupae exhibited granular deposits within the lamellar region and interference with deposition of the nonlamellate endocuticle. DFB treatment of the earlier pupal stages interfered with deposition of the lamellate cuticle by eliminating or reducing the lamellar structure. It was concluded that the primary interaction of JH with DFB was that of extending or reinitiating DFB sensitivity in the later pharate adult. A secondary interaction may involve inhibition of cuticle hardening as both JH and DFB appear to inhibit the tanning process of adults treated as white-eyed pupae.     

Virtual screening identifies a novel piperazine-based insect juvenile hormone agonist

Juvenile hormone (JH) agonists constitute a subclass of insect growth regulators and play important roles in insect pest management. In this work, a multi-step virtual screening program was executed to find novel JH agonists. A database of 5 million purchasable compounds was sequentially processed with three computational filters: (i) shape and chemical similarity as compared to known JH-active compounds; (ii) molecular docking simulations against a Drosophila JH receptor, methoprene-tolerant; and (iii) free energy calculation of ligand–receptor binding using a modified MM/PBSA (molecular mechanics/Poisson–Boltzmann surface area) protocol. The 11 candidates that passed the three filters were evaluated in a luciferase reporter assay, leading to the identification of a hit compound that contains a piperazine ring system (EC₅₀=870 nM). This compound is structurally dissimilar to known JH agonists and synthetically easy to access; therefore, it is a promising starting point for further structure optimization.     

禾谷缢管蚜体内保幼激素的变化趋势

为明确禾谷缢管蚜Rjopalosiphum padi 不同发育阶段体内保幼激素(ju-venile hormone,JH)的变化趋势,借助高效液相色谱(HPLC),确定了蚜虫JH测试方法,并对其JH进行了测定.结果表明:在若蚜阶段存在三种JH即JHⅠ、JHⅡ和JHⅢ;在成蚜阶段只能检测到JHⅢ.在整个发育过程中,JH变化趋势为虫龄越高,JH滴度越低,无翅3、4龄若蚜体内三种JH均极显著高于同期有翅若蚜.母代翅型对子代不同龄期若蚜JH滴度有明显影响.无翅成蚜后代1龄JH滴度极显著高于同期有翅成蚜的后代;2龄时,有翅成蚜的后代JH滴度骤然上升;有翅成蚜后代在2、3龄时JH滴度极显著高于同期无翅成蚜的后代.2龄之前是两种翅型母代的后代滴度变化的转折点,表明1～2龄若蚜期是禾谷缢管蚜翅型分化的关键时期和JH影响翅型分化的敏感龄期.     

Substituted thiotrifluoropropanones as potent selective inhibitors of juvenile hormone esterase

A series of 27 substituted thio-1,1,1-trifluoropropanones was synthesized by reacting the corresponding thiol with 1,1,1-trifluoro-3-bromopropanone. The resulting sulfides were screened as inhibitors of hemolymph juvenile hormone esterase and α-naphthyl acetate esterase activity of the cabbage looper, Trichoplusia ni, electric eel acetylcholinesterase, bovine trypsin, and bovine α-chymotrypsin. The presence of the sulfide bond increased the inhibitory potency on all of the enzymes tested when compared with compounds lacking the sulfide. In general, the compounds proved to be poor inhibitors of chymotrypsin and moderate inhibitors of trypsin. By varying the substituent on the sulfide, good inhibitory activity was obtained on α-naphthyl acetate esterase, acetylcholinesterase, while some of the compounds proved to be extremely powerful inhibitors of juvenile hormone esterase. The most powerful inhibitor tested was 3-octylthio-1,1,1-trifluoro-2-propanone, with an I₅₀ of 2.3 × 10^?9M on JH esterase. This compound showed a molar refractivity similar to that of the JH II backbone, was not toxic to T. ni, and was moderately toxic to mice, with a 48-hr LD₅₀ of >750 mg/kg. It effectively delayed pupation when applied to prewandering larvae of T. ni, as expected for a JH esterase inhibitor. Thus, some members of this series are promising for evaluating the role of JH esterase in insect development. The series also indicates that, by varying the substituent on the sulfide moiety, potent “transition-state” inhibitors can be developed for a wide variety of esterases and proteases.     

Inhibition of juvenile hormone biosynthesis and methyl farnesoate epoxidase activity by 1,5-disubstituted imidazoles in the cockroach,Diploptera punctata

Seventeen substituted imidazoles were tested as inhibitors of juvenile hormone (JH) III synthesis by cockroach corpora allata in an in-vitro radio-chemical assay. Most of these 1,5-disubstituted imidazoles were highly potent, with IC₅₀ values of less than 100nM. The compounds differed in their ability to cause an accumulation of the precursor methyl farnesoate in the glands. Four of the imidazoles were tested by topical application to previtellogenic adult females, and all caused a significant inhibition of JH synthesis and an accumulation of intraglandular methyl farnesoate for at least three days after treatment. Methyl farnesoate epoxidase activity of homogenates of corpora allata was inhibited by the compounds TH -14 and TH -27. This P450-dependent epoxidase activity was inhibited at less than 10 nM. The results show that the 1,5-disubstituted imidazoles are powerful inhibitors of the last step of juvenile synthesis in this cockroach.     

Trifluoromethylketones as possible transition state analog inhibitors of juvenile hormone esterase

A series of compounds containing the trifluoromethylketone group have been synthesized utilizing either a modified Grignard procedure or by reacting selected aliphatic bromides or tosylates with the Collman reagent [Na₂Fe(CO)₄]. When tested in vitro as inhibitors of crude juvenile hormone esterase from the hemolymph of the cabbage looper, Trichoplusia ni (Noctuidae), the most active compounds were trifluoromethylketones possessing either a juvenoid-like structure or a straight aliphatic chain. The logarithm of the inhibitory potency of the aliphatic compounds was proportional to their chain length, up to 1,1,1-trifluorotetradecan-2-one (I₅₀ = 1 × 10^?7M). This powerful inhibition was found to be highly selective for JHE, reversible, competitive by Lineweaver-Burk analysis, and was characterized by high affinity of the inhibitor for the esterase (K_i = 3.2 × 10^?9M, K_m JH III = 2 × 10^?7M). Other trifluoromethylketones were shown to be inhibitors of T. ni α-naphthylacetate esterase and bovine trypsin. By analogy with the mechanism of trypsin action, trifluoromethylketones are probably potent inhibitors due to their resemblance to a tetrahedral transition state on the reaction coordinate to the acylated enzyme.     

Induction of prolonged larval feeding stage by juvenile hormone analogues inTribolium Castaneum

Dietary ZR-512 and ZR-619 at concentrations of 10 — 1000 ppm induced prolongation of the larval feeding period up to tenfold, increasing larval weight up to double that of untreated larvae. A comparison study of four juvenoids, using 200 ppm of ZR-512, ZR-515, ZR-619 or ZR-777, showed that ZR-515 elicits the highest larval weight (6.2 mg) and ZR-777 the lowest (3.6 mg). In all cases a pronounced enhancement of larval weight — of 50 — 250% relative to untreated larvae (2.4 mg) — was obtained.Tr. castaneum larvae reared up to their 3rd instars on a diet containing 100 ppm of ZR-512, ZR-515, ZR-619 or ZR-777 and then transferred to a juvenile hormone-free diet, were not affected. The period between 4th instar larva and pupation should therefore be considered as critical for juvenile hormone effect. The induced prolongation of the larval stage after juvenile hormone treatment was followed by a pronounced enhancement of cuticle phenoloxidase activity, indicating an alteration of the larval biochemical processes. Although juvenile hormone treatment inhibitsTr. castaneum pupation and emergence, it markedly prolongs larval feeding stage and weight and thus accelerates damage.