Phytogrowth- and photosynthesis-inhibiting properties of nostoclide analogues

Six nostoclide analogues were synthesised from 3-benzyl-2(5H)-furanone in one step, with yields ranging from 10 to 71%, and subjected to several biological assays. The two most active of these, 5d and 5e, were shown to be phytogrowth inhibitors of the radicle of Lolium multiflorum Lam, while enhancing the root growth of Physalis ixocarpa Brot. Both compounds inhibited electron flow (basal, phosphorylating and uncoupled) from water to methylviologen (MV); both acted as Hill reaction inhibitors, since the synthesis of ATP was prevented. The uncoupled electron transport from photosystem II (PSII) (water to 2,6-dichlorophenol-indophenol (DPIP)) and photosystem I (PSI) (2,6-dichlorophenol-indophenol reduced (DPIPred) to MV) was inhibited with 500 microM of 5d by 22 and 14% respectively. In addition, 400 microM of 5d inhibited PSI (from tetramethyl-p-benzohydroquinone (TMQH(2)) to MV) by 40%. Thus 5d inhibited electron transport at the b(6)f complex. Finally, 500 microM of 5e inhibited electron flow (basal and phosphorylating) by 25%, and 300 microM of 5e enhanced light-activated membrane-bound Mg(2+)-ATPase by 66%. Thus 5e behaved as a weak Hill reaction inhibitor and an uncoupler. In general, the phytotoxicity of the synthetic lactones was only weakly related to inhibition of photosynthesis.     

Synthesis and herbicidal activity of novel alpha,alpha,alpha-trifluoro-m-tolyl pyridazinone derivatives

A series of novel alpha,alpha,alpha-trifluoro-m-tolyl pyridazinone derivatives was synthesised. Herbicidal activities of the two intermediate compounds and 15 pyridazinone derivatives were evaluated through barnyardgrass and rape cup tests and Spirodela polyrrhiza (L.) Schleiden tests. Selected compounds were also evaluated under greenhouse conditions. Bleaching activities were observed at 10 microg ml(-1) and some compounds exhibited herbicidal activities at a rate of 300 g ha(-1). The relationship between crystal structures and herbicidal activities is discussed through a comparison of two compounds (5a and 5f).     

Synthesis, characterization, absolute structural determination and antifungal activity of a new chlorinated aromatic avenaciolide analogue

BACKGROUND: Avenaciolide, a natural product isolated from Aspergillus avenaceus H. Smith, possesses several interesting biological properties, such as antifungal and antibacterial activities and inhibition of glutamate transport in mitochondria. In a study aiming to discover new compounds with antifungal activity, a bis‐γ‐lactone analogous to avenaciolide was prepared and characterized by elemental analysis, mass spectrometry, and infrared and NMR spectroscopy. RESULTS: The absolute structures of this compound and of the synthetic precursor (also a bis‐γ‐lactone) were determined by X‐ray diffraction analysis. The bis‐γ‐lactones synthesized crystallize in the orthorhombic space group P2₁2₁2₁, and the crystal packings are supported by C? H···O hydrogen bonds. The compound showed antifungal activity against Colletotrichum gloeosporioides (Penz.) Penz. & Sacc., while the synthetic precursor was inactive under the in vitro test conditions employed. CONCLUSION: The results indicate that it is not only the bis‐γ‐lactone skeleton that is important to antifungal activity. The latter also depends on the presence of the exocyclic double bond possibly due to a Michael addition type reaction with the fungal enzymes. Copyright © 2008 Society of Chemical Industry     

Interaction of dinotefuran and its analogues with nicotinic acetylcholine receptors of cockroach nerve cords

To investigate the action of dinotefuran (MTI-446, 1-methyl-2-nitro-3-(tetrahydro-3-furylmethyl)guanidine), a recently developed insecticide, on insect nicotinic acetylcholine receptors (nAChRs), we determined the potencies of the compound and 15 analogues in inhibiting the specific binding of [3H]epibatidine (EPI), a nAChR agonist, and [3H]alpha-bungarotoxin (alpha-BGT), a competitive nAChR antagonist, to the nerve cord membranes of American cockroaches (Periplaneta americana). Racemic dinotefuran inhibited [3H]EPI binding with an IC50 of 890 nM and [3H]alpha-BGT binding with an IC50 of 36.1 microM. Scatchard analysis indicated that the dinotefuran inhibition of [3H]EPI binding was a competitive one. Slight structural modification caused a drastic reduction in potency; only four analogues were found to be equipotent to or more potent than dinotefuran. Chloropyridinyl and chlorothiazolyl neonicotinoid insecticides displayed two or three orders of magnitude higher potency than dinotefuran. There was a good correlation between the IC50 values of tested compounds obtained with [3H]EPI and those obtained with [3H]alpha-BGT. A better correlation was observed between 3-h knockdown activities (KD50) against German cockroaches (Blattella germanica) and IC50 values obtained from [3H]EPI assays than between 24-h lethal activities (LD50) and IC50 values. While the results indicate that dinotefuran and its analogues interact with the ACh-binding site in cockroach nAChRs, it remains to be elucidated why they displayed lower potencies than those expected based on their insecticidal activities.     

Insecticidal compounds from the essential oil of Chinese medicinal herb Atractylodes chinensis

BACKGROUND: In a screening programme for new agrochemicals from Chinese medicinal herbs, the essential oil of Atractylodes chinensis (DC.) Koidz was found to possess strong insecticidal activity against the common vinegar fly, Drosophila melanogaster L. The essential oil was extracted via hydrodistillation, and its constituents were determined by GC‐MS analysis. RESULTS: The main components of A. chinensis essential oil were β‐eudesmol (21.05%), β‐selinene (11.75%), γ‐elemene (7.16%) and isopetasam (5.36%). Bioactivity‐directed chromatographic separation on repeated silica gel columns led to the isolation of five compounds, namely atractylon, α‐elemol, β‐eudesmol, hinesol and β‐selinene. β‐Selinene, α‐elemol and hinesol showed pronounced contact toxicity against D. melanogaster adults, with LD₅₀ values of 0.55, 0.65 and 0.71 µg adult^?1 respectively. Atractylon and β‐eudesmol were also toxic to the fruit flies (LD₅₀ = 1.63 and 2.65 µg adult^?1 respectively), while the crude oil had an LD₅₀ value of 2.44 µg adult^?1. CONCLUSION: The findings suggested that the essential oil of Atractylodes chinensis and its active constituents may be explored as natural potential insecticides. Copyright © 2011 Society of Chemical Industry     

Comparative actions of clomazone on beta-carotene levels and growth in rice (Oryza sativa) and watergrasses (Echinochloa spp)

Seedlings of rice, early watergrass (thiobencarb-resistant and thiobencarb-susceptible biotypes, R and S, respectively), and late watergrass (thiobencarb-resistant and thiobencarb-susceptible biotypes, R and S, respectively) were hydroponically exposed to clomazone at concentrations ranging from 0.08 to 7.9 microM. Whole-plant growth (mg fresh wt) and beta-carotene concentrations (microg g(-1) fresh wt) were measured after a 7-day exposure period. For growth, the no observed effect concentrations (NOECs) were 7.9, 0.21, 0.21, 0.46 and 0.46 microM clomazone for rice, early watergrass (R), early watergrass (S), late watergrass (R) and late watergrass (S), respectively, while the concentrations causing 25% inhibition in response (IC25) were 5.6 (+/-1.6), 0.46 (+/-0.06), 0.42 (+/-0.08), 0.92 (+/-0.45) and 0.79 (+/-0.08) microM clomazone, respectively. Clomazone inhibits beta-carotene synthesis via inhibition of the non-mevalonate isoprenoid synthetic pathway. For assessment of clomazone effects, beta-carotene levels proved to be a more sensitive toxicological endpoint than growth. For rice, early watergrass (R), early watergrass (S), late watergrass (R) and late watergrass (S), the beta-carotene NOECs were 0.21, <0.08, <0.08, 0.08 and 0.46 microM clomazone respectively, while IC25 values were 0.42 (+/-0.26), 0.08 (+/-0.02), 0.08 (+/-0.02), 0.33 (+/-0.09) and 0.54 (+/-0.15) microM, respectively. No evidence was found that the thiobencarb-resistance mechanisms present in early and late watergrasses impart resistance to clomazone. Due to similar sensitivity between rice and late watergrass, use of clomazone in rice culture will require the use of a safening technique.     

Thermal decomposition and isomerization of cis-permethrin and beta-cypermethrin in the solid phase

The stability to heart of cis-permethrin and beta-cypermethrin in the solid phase was studied and the decomposition products identified. Samples heated at 210 degrees C in an oven in the dark showed that, in the absence of potassium chlorate (the salt present in smoke-generating formulations of these pyrethroids), cis-permethrin was not isomerized, although in the presence of that salt, decomposition was greater and thermal isomerization occurred. Other salts of the type KXO3 or NaXO3, with X being halogen or nitrogen, also led to a considerable thermal isomerization. Heating the insecticides in solution in the presence of potassium chlorate did not produce isomerization in any of the solvents assayed. Salt-catalysed thermal cis-trans isomerization was also found for other pyrethroids derived from permethrinic or deltamethrinic acid but not for those derived from chrysanthemic acid. The main thermal degradation processes of cis-permethrin and beta-cypermethrin decomposition when potassium chlorate was present were cyclopropane isomerization, ester cleavage and subsequent oxidation of the resulting products. Permethrinic acid, 3-phenoxybenzyle chloride, alcohol, aldehyde and acid were identified in both cases, as well as 3-phenoxybenzyl cyanide from beta-cypermethrin. A similar decomposition pattern occurred after combustion of pyrethroid fumigant formulations.     

Isolation and characterization of a novel simazine-degrading beta-proteobacterium and detection of genes encoding s-triazine-degrading enzymes

A moderately persistent herbicide, simazine, has been used globally and detected as a contaminant in soil and water. The authors have isolated a simazine-degrading bacterium from a simazine-degrading bacterial consortium that was enriched using charcoal as a microhabitat. The isolate, strain CDB21, was gram-negative, rod-shaped (0.5-0.6 microm x 1.0-1.2 microm) and motile by means of a single polar flagellum. Based on 16S rRNA sequence analysis, strain CDB21 was identified as a novel beta-proteobacterium exhibiting 100% sequence identity with the uncultured bacterium HOClCi25 (GenBank accession number AY328574). PCR using primers that were specific for the genes of the atrazine-degrading enzymes (atzABCDEF) of Pseudomonas sp. strain ADP showed that strain CDB21 also possessed the entire set of genes of these enzymes. Nucleotide sequences of the atzCDEF genes of strain CDB21 were 100% identical to those of Pseudomonas sp. strain ADP. Sequence identity of the atzA genes between these bacteria was 99.7%. The 398-nucleotide upstream fragment of the atzB gene of strain CDB21 was 100% identical to ORF30 of Pseudomonas sp. strain ADP, and the 1526-nucleotide downstream fragment showed 99.8% sequence similarity to the atzB gene of the pseudomonad.     

Dehydro-alpha-lapachone isolated from Catalpa ovata stems: activity against plant pathogenic fungi

The methanol extract of stems of Catalpa ovata G Don exhibits potent in vivo antifungal activity against Magnaporthe grisea (Hebert) Barr (rice blast) on rice plants, Botrytis cinerea Pers ex Fr (tomato grey mould) and Phytophthora infestans (Mont) de Bary (tomato late blight) on tomato plants, Puccinia recondita Rob ex Desm (wheat leaf rust) on wheat plants and Blumeria graminis (DC) Speer f. sp. hordei Marchal (barley powdery mildew) on barley plants. An antifungal substance was isolated and identified as dehydro-alpha-lapachone from mass and nuclear magnetic resonance spectral data. It completely inhibited the mycelial growth of B. cinerea, Colletotrichum acutatum Simmonds, Colletotrichum gloeosporioides Simmonds, M. grisea and Pythium ultimum Trow over a range of 0.4-33.3 mg litre(-1). It also controlled the development of rice blast, tomato late blight, wheat leaf rust, barley powdery mildew and red pepper anthracnose (Colletotrichum coccodes (Wallr) S Hughes). The chemical was particularly effective in suppressing red pepper anthracnose by 95% at a concentration of 125 mg litre(-1).     

Localisation of the benzimidazole fungicide binding site of Gibberella zeae β2-tubulin studied by site-directed mutagenesis

BACKGROUND: The efficacy of benzimidazole fungicides is often limited by resistance, and this is the case with the use of carbendazim for controlling Fusarium head blight caused by Gibberella zeae (Schwein.) Petch (anamorph Fusarium graminearum). Recent studies have shown that carbendazim resistance in field strains of G. zeae is associated with mutations in the β ₂‐tubulin gene. The aims of the present study were to validate this mechanism and research the binding sites of carbendazim on β ₂‐tubulin. RESULTS: This work used site‐directed mutagenesis followed by gene replacement to change the β ₂‐tubulin gene of a carbendazim‐sensitive field strain of G. zeae at residues 50, 167, 198 or 200. The transformants were confirmed and tested for their sensitivity to carbendazim. All the mutants were resistant to carbendazim, but the level of resistance differed depending on the mutation. Biological characteristics did not differ between the field strain and the site‐directed mutants. A three‐dimensional model of β ₂‐tubulin was constructed, and the possible carbendazim binding site was analysed. CONCLUSION: Mutations at codons 50, 167, 198 and 200 of G. zeae β ₂tub could cause resistance to carbendazim, and these codons may form a binding pocket. Copyright © 2010 Society of Chemical Industry     

新杀菌剂对番茄灰霉病菌的室内毒力及田间防效

室内采用菌丝生长速率法、孢子萌发法和黄瓜子叶法测定了咯菌腈、抑霉唑、福美双、吡唑醚菌酯和嘧霉胺对番茄灰霉病菌( Botrytis cinerea)的抑制作用。结果表明,菌丝生长速率法和孢子萌发法的测定均以咯菌腈毒力最高,EC 50分别为0.005 2 μg/mL和0.087 6 μg/mL;黄瓜子叶法测定以抑霉唑毒力最高,其EC 50为0.675 3 μg/mL。田间药效试验结果表明：50%咯菌腈可湿性粉剂90 g/ hm2对番茄灰霉病的田间防效达到90%以上,显著高于对照药剂50%啶酰菌胺水分散粒剂300 g/hm2和40%嘧霉胺悬浮剂 480 g/hm2的防效。     

Ambient air concentrations of pesticides used in potato cultivation in Prince Edward Island, Canada

Ambient air concentrations of nine selected pesticides used in potato cultivation were investigated on Prince Edward Island by collecting samples during the summer of 1998 at three potato farm sites and one non-agricultural site. In 1999, air samples were collected at a single potato farm site during local application of pesticides. The fungicide chlorothalonil was the only pesticide detected in every sample in both years, even in samples with a duration as little as 5 h. In 1998, maximum (45-458 ng m(-3)) and mean (22-193 ng m(-3)) concentrations of chlorothalonil from composite 42 h samples were one to two orders of magnitude greater at agricultural sites than at the non-agricultural site (3.9 and 2.5 ng m(-3), respectively). Maximum and mean concentrations of chlorothalonil from combined 24 h samples at the farm site in 1999 were higher than those measured in 1998 (636 and 284 ng m(-3), respectively). The ubiquitous presence in air of relatively high concentrations of chlorothalonil in agricultural areas on Prince Edward Island is likely related to its repeated use on potato farms where fungicides account for 80-90% of pesticides applied. Eight of nine pesticides were detected at farm sites in 1998 and they are ranked by mean concentration from highest to lowest as follows: chlorothalonil, methamidophos, azinphos-methyl, alpha-endosulfan, beta-endosulfan, pirimicarb, metobromuron, metribuzin, metalaxyl and fluazifop-P-butyl. Concentrations of metalaxyl, pirimicarb, metobromuron and fluazifop-P-butyl in air are among the first reported values for these pesticides. Five pesticides were detected at the Summerside farm in 1999, but only two fungicides (chlorothalonil and metalaxyl) were used locally, while the presence of metribuzin, alpha-endosulfan and methamidophos in air was not associated with local application. Evidence of pesticide drift was observed for chlorothalonil, alpha-endosulfan and methamidophos, and these pesticides were identified as being of high concern in terms of potential wildlife exposure on the Island.     

Synergistic and antagonistic interactions of terpenes against Meloidogyne incognita and the nematicidal activity of essential oils from seven plants indigenous to Greece

BACKGROUND: Biorational means for phytonematode control were studied within the context of an increasingly ecofriendly pest management global approach. The nematicidal activity and the chemical composition of essential oils (EOs) isolated from seven plants grown in Greece and ten selected compounds extracted from them against second‐stage juveniles (J2) of Meloidogyne incognita (Kof. & White) Chitwood were evaluated using juvenile paralysis experiments. Additionally, synergistic and antagonistic interactions between nematicidal terpenes were studied using an effect addition model, with the comparison made at one concentration level. RESULTS: The 96 h EC₅₀ values of Foeniculum vulgare Mill., Pimpinella anisum L., Eucalyptus meliodora A Cunn ex Schauer and Pistacia terebinthus L. were 231, 269, 807 and 1116 µg mL^?1, respectively, in an immersion bioassay. Benzaldehyde (9 µg mL^?1) was the most toxic compound, followed by γ‐eudesmol (50 µg mL^?1) and estragole (180 µg mL^?1), based on 96 h EC₅₀ values. The most potent terpene pairs between which synergistic actions were found, in decreasing order, were: trans‐anethole/geraniol, trans‐anethole/eugenol, carvacrol/eugenol and geraniol/carvacrol. CONCLUSION: This is the first report on the activity of F. vulgare, P. anisum, E. meliodora and P. terebinthus, and additionally on synergistic/antagonistic nematicidal terpene interactions, against M. incognita, providing alternative methods for nematode control. Copyright © 2010 Society of Chemical Industry     

Nicotinic acetylcholine receptor binding of imidacloprid-related diaza compounds with various ring sizes and their insecticidal activity against Musca domestica

Fifteen 5-substituted 1-(6-chloro-3-pyridylmethyl)-2-nitromethylene-1,3- diazacyclohexanes and three other related compounds having a five- or seven-membered ring were synthesized and their biological activities were measured in vivo and in vitro. The insecticidal (in vivo) activity was evaluated against houseflies Musca domestica L under synergistic conditions with propargyl propyl phenyl phosphonate and piperonyl butoxide. The binding activity of each compound to nicotinic acetylcholine receptor in vitro was measured using [125I] alpha-bungarotoxin. The insecticidal activities of the unsubstituted diazacyclohexane analogues were slightly higher than those of the imidazolidine analogues, but the enlargement of ring size to diazacycloheptane lowered the activity. Substitution of 1,3-diazacyclohexane or imidazolidine rings was not generally favourable for the activity, but the unsubstituted 1,3-diazacyclohexane analogue showed the highest binding activity. Ring substitutions and ring enlargement decreased the activity 100-30,000-fold.     

Mutations in the CYP51 gene correlated with changes in sensitivity to sterol 14 alpha-demethylation inhibitors in field isolates of Mycosphaerella graminicola

In France, as in many other European countries, Mycosphaerella graminicola (Fuckel) Schr?ter in Cohn (anamorph Septoria tritici), the causal agent of wheat leaf blotch, is controlled by foliar applications of fungicides. With the recent generalization of resistance to strobilurins (QoIs), reliable control is mainly dependent upon inhibitors of sterol 14 alpha-demethylation (DMIs). To date, strains with reduced sensitivity to DMIs are widespread, but disease control using members of this class of sterol biosynthesis inhibitors has not been compromised. In this study, sensitivity assays based on in vitro effects of fungicides towards germ-tube elongation allowed the characterization of seven DMI-resistant phenotypes. In four of them, cross-resistance was not observed between all tested DMIs; this characteristic concerned prochloraz, triflumizole, fluquinconazole and tebuconazole. Moreover, the highest resistant factors to most DMIs were found only in recent isolates; according to their response towards prochloraz, they were classified into two categories. Molecular studies showed that DMI resistance was associated with mutations in the CYP51 gene encoding the sterol 14 alpha-demethylase. Alterations at codons 459, 460 and 461 were related to low resistance levels, whereas, at position 381, a valine instead of an isoleucine, in combination with the previous changes, determined the highest resistance levels to all DMIs except prochloraz. Mutations in codons 316 and 317 were also found in some isolates exhibiting low resistance factors towards most DMIs.     

Insecticide resistance of the oriental fruit fly, Bactrocera dorsalis (Hendel) (Diptera: Tephritidae), in mainland China

BACKGROUND: In order to investigate the extent of resistance of oriental fruit fly, Bactrocera dorsalis (Hendel), which is a widespread pest throughout tropical, subtropical and temperate fruit crops, 25 populations of this insect were collected from 13 sites in mainland China in 2007 and 2008. In addition, resistant strains were established that showed increasing development of resistance. RESULTS: Compared with the susceptible strain, one population of B. dorsalis expressed high resistance (RR = 70.4‐fold), 16 populations expressed medium resistance (11.5‐fold < RR < 25.8‐fold) and eight populations had low resistance or remained susceptible (1.4‐fold < RR < 8.9‐fold) to trichlorphon. As regards β‐cypermethrin, one population showed high resistance (RR = 44.0‐fold), nine populations expressed medium resistance (12.2‐fold < RR < 28.4‐fold), 14 populations expressed low or minor resistance (3.0‐fold < RR < 9.7‐fold) and one population remained susceptible (RR = 1.1‐fold). As regards avermectin, five populations had developed high resistance (44.3‐fold < RR < 104‐fold), seven populations expressed medium resistance (11.4‐fold < RR < 38.6‐fold) and three populations expressed low or minor resistance (3.5‐fold < RR < 5.6‐fold). A continuous resistance selection in the laboratory strain showed that the resistance ratios to trichlorphon, β‐cypermethrin and avermectin were 71.6‐fold, 333‐fold and 70.4‐fold respectively. CONCLUSION: The data provided a comprehensive survey of insecticide resistance in Bactrocera dorsalis in mainland China. All results suggested that early resistance management programmes should be established for restoring the efficacy of pesticide‐based control measures. Copyright © 2010 Society of Chemical Industry     

β-Tubulins in Gibberella zeae: their characterization and contribution to carbendazim resistance

BACKGROUND: Fusarium head blight caused by Gibberella zeae is an important disease of wheat and barley because it reduces grain yield and quality and results in the contamination of grain with mycotoxins. Recent studies have shown that carbendazim resistance in field strains of G. zeae is not caused by mutation of the β‐tubulin gene (β₁tub), which is the case with other filamentous fungi, but that fungicide resistance is greatly increased by deletion of β₁tub. The aim of the present study was to clarify the function of β₁tub and its role in carbendazim resistance in G. zeae by artificial gene operation. RESULTS: Deletion of β₁tub reduced vegetative growth and pathogenicity but increased asexual reproduction in G. zeae. All the mutants were more resistant to carbendazim than parent strains. A three‐dimensional model of β₁tub was constructed, and the possible carbendazim binding site was analysed. CONCLUSION: β₁tub is not an essential gene in G. zeae, but it affects the sensitivity of the fungus to carbendazim. Copyright © 2012 Society of Chemical Industry