Spectroscopic studies of the interactions of the pyrethroid insecticide fenvalerate with gramicidin

Fenvalerate is a pyrethroid insecticide which interacts with ionic channels. Using circular dichroism technique we have studied the interaction of fenvalerate with gramicidin, a model channel peptide which transports ions. In most organic solvents, gramicidin exists as a double helix except in trifluoroethanol where it exists as a channel forming single stranded beta(6.3) helical monomer. In model lipid membranes, under certain experimental conditions, gramicidin exists as a channel forming single stranded beta(6.3) helical dimer. Our results show that fenvalerate interacts more with the single stranded beta(6.3) helical monomer or dimer than with the double helical form of gramicidin. This was further confirmed by an increase in the rate of gramicidin mediated proton transport in liposomes by fenvalerate, using the pH sensitive fluorophore, pyranine.

Identification and preliminary evaluation of viriditoxin, a metabolite of Paecilomyces varioti, as an insecticide for sheep blowfly, Lucilia cuprina (Wied.)

Solvent extracts of cultures of the fungus Paecilomyces varioti are toxic to sheep blowfly, Lucilia cuprina (Wiedemann) (Diptera: Calliphoridae). Different components of the culture extracts were isolated and bioassayed with L. cuprina. The component with most toxicity was purified and identified from its proton magnetic resonance spectrum as viriditoxin, a known antibiotic metabolite of the fungus. The insecticidal properties of viriditoxin were then evaluated. Mean LCso values for first instar larvae of organophosphate susceptible and resistant strains of L. cuprina were 7.5 and 8.4 ppm respectively. Pilot implant trials in sheep demonstrated that the compound provided protection for 9-17 weeks against both strains of L. cuprina. No adverse effects on the trial sheep were detected.

Management of white grubs (Coleoptera: Scarabaeidae) on groundnut in southern India

The chemical control of groundnut white grubs, Holotrichia serrata F. and H. reynaudi Blanchard (Coleoptera: Scarabaeidae), was studied in south--central India. Microplot trials demonstrated that chlorpyrifos and imidacloprid seed--dressings were effective against H. serrata at rates as low as 0.6 and 3.5 g a.i. kg-1, respectively, while microplot and on--farm trials showed that 1.2 and 3.5 g a.i. kg-1of chlorpyrifos and imidacloprid, respectively, were required for H. reynaudi. Chlorpyrifos residue analyses indicated that at 20 days after sowing (d.a.s.) rates up to 5.0 g a.i. kg-1 produced residues in soil and groundnut seedlings markedly below the relevant MRL, and no detectable residues at harvest under the southern Indian rainy--season environment. A farmer survey found that in Andhra Pradesh (AP), insecticides (chlorpyrifos and phorate) were applied for white grub control in 37.5% of farms sampled, while no insecticides were applied for this purpose in Karnataka and Tamil Nadu. The white grub density on farms in AP where insecticide had been applied averaged 0.07 larvae m-2, compared to 1.04 larvae m-2 in the remaining AP farms. In AP, Karnataka and Tamil Nadu, 70%, 42% and 39% of currently untreated groundnut fields, respectively, exceed the provisional economic threshold. A survey in the Anantapur district of AP found that farmer’s target and achieved rates for seed treatment averaged 0.44 and 0.52 g a.i. kg-1, both below optimal rates determined in microplot experiments. These data provide the foundation for an effective and sustainable program of management for groundnut white grubs in south--central India by providing key efficacy data and baseline data on farmer insecticide- use patterns.

The helical conformations of 14- and 16-residue fragments of suzukacillin, a membrane channel-forming polypeptide

The suzukacillin fragments, Boc-Ala-Aib-Aib-Gln-Aib-Leu-Aib-Gly-Leu-Aib-Pro-Val-Aib-Aib-OMe (14), Boc-Ala-Aib-Ala-Aib-Aib-Gln-Aib-Leu-Aib-Gly-Leu-Aib-Pro-Val-Aib-Aib-OMe (16G) and the completely apolar 16-residue peptide in which the glutamine residue has been replaced by alanine (16A) have been studied by 270 MHz 1H-HMR, in C2HCl3 and (C2H3)2SO solution. Intramolecularly hydrogen-bonded NH groups have been identified by temperature and solvent dependence of chemical shifts. Peptides 14 and 16A adopt folded 310 helical conformations stabilized by 11 and 13 hydrogen bonds, respectively. In peptide 16G there are 12 intramolecular hydrogen bonds, with the glycine NH being solvent-exposed, in contrast to 14 and 16A.

Long-term impacts of harvest residue management on nutrition, growth and productivity of an exotic pine plantation of sub-tropical Australia

Residue retention is an important issue in evaluating the sustainability of production forestry. However, its long-term impacts have not been studied extensively, especially in sub-tropical environments. This study investigated the long-term impact of harvest residue retention on tree nutrition, growth and productivity of a F1 hybrid (Pinus elliottii var. elliottii × Pinus caribaea var. hondurensis) exotic pine plantation in sub-tropical Australia, under three harvest residue management regimes: (1) residue removal, RR0; (2) single residue retention, RR1; and (3) double residue retention, RR2. The experiment, established in 1996, is a randomised complete block design with 4 replicates. Tree growth measurements in this study were carried out at ages 2, 4, 6, 8 and 10 years, while foliar nutrient analyses were carried out at ages 2, 4, 6 and 10 years. Litter production and litter nitrogen (N) and phosphorus (P) measurements were carried out quarterly over a 15-month period between ages 9 and 10 years. Results showed that total tree growth was still greater in residue-retained treatments compared to the RR0 treatment. However, mean annual increments of diameter at breast height (MAID) and basal area (MAIB) declined significantly after age 4 years to about 68-78% at age 10 years. Declining foliar N and P concentrations accounted for 62% (p < 0.05) of the variation of growth rates after age 4 years, and foliar N and P concentrations were either marginal or below critical concentrations. In addition, litter production, and litter N and P contents were not significantly different among the treatments. This study suggests that the impact of residue retention on tree nutrition and growth rates might be limited over a longer period, and that the integration of alternative forest management practices is necessary to sustain the benefits of harvest residues until the end of the rotation.

Insecticide resistance and implications for future aphid management in Australian grains and pastures: A review

Aphids can cause substantial damage to cereals, oilseeds and legumes through direct feeding and through the transmission of plant pathogenic viruses. Aphid-resistant varieties are only available for a limited number of crops. In Australia, growers often use prophylactic sprays to control aphids, but this strategy can lead to non-target effects and the development of insecticide resistance. Insecticide resistance is a problem in one aphid pest of Australian grains in Australia, the green peach aphid (Myzus persicae). Molecular analyses of field-collected samples demonstrate that amplified E4 esterase resistance to organophosphate insecticides is widespread in Australian grains across Australia. Knockdown resistance to pyrethroids is less abundant, but has an increased frequency in areas with known frequent use of these insecticides. Modified acetylcholinesterase resistance to dimethyl carbamates, such as pirimicarb, has not been found in Australia, nor has resistance to imidacloprid. Australian grain growers should consider control options that are less likely to promote insecticide resistance, and have reduced impacts on natural enemies. Research is ongoing in Australia and overseas to provide new strategies for aphid management in the future.

Selectivity of chlorantraniliprole to parasitoid wasps.

BACKGROUND: Chlorantraniliprole is a novel anthranilic diamide insecticide registered for use in vegetables, fruits, grains and turf against a variety of insect pests. The objective of this article is to summarize results of acute toxicity testing of chlorantraniliprole on seven species of parasitic wasps with wide geographic distribution and relevance to different crops and integrated pest management (IPM) programmes. RESULTS: Tier-1, worst-case laboratory studies evaluated wasp survival and reproduction following different exposure concentrations and scenarios to chlorantraniliprole (i.e. fresh-dried spray deposits on glass plates, direct contact, ingestion, egg card, dipped leaf residue bioassays, sprayed mummies). No statistically significant effects on adult survival, percentage parasitism or emergence were observed following exposures to chlorantraniliprole compared with controls. CONCLUSION: Chlorantraniliprole was harmless to the parasitoid wasp species tested according to IOBC classification criteria (<30% effects) and may be a useful tool in IPM programmes.

Rice husk biochar and crop residue amendment in subtropical cropping soils: Effect on biomass production, nitrogen use efficiency and greenhouse gas emissions

We investigated the effect of maize residues and rice husk biochar on biomass production, fertiliser nitrogen recovery (FNR) and nitrous oxide (N2O) emissions for three different subtropical cropping soils. Maize residues at two rates (0 and 10 t ha−1) combined with three rates (0, 15 and 30 t ha-1) of rice husk biochar were added to three soil types in a pot trial with maize plants. Soil N2O emissions were monitored with static chambers for 91 days. Isotopic 15N-labelled urea was applied to the treatments without added crop residues to measure the FNR. Crop residue incorporation significantly reduced N uptake in all treatments but did not affect overall FNR. Rice husk biochar amendment had no effect on plant growth and N uptake but significantly reduced N2O and carbon dioxide (CO2) emissions in two of the three soils. The incorporation of crop residues had a contrasting effect on soil N2O emissions depending on the mineral N status of the soil. The study shows that effects of crop residues depend on soil properties at the time of application. Adding crop residues with a high C/N ratio to soil can immobilise N in the soil profile and hence reduce N uptake and/or total biomass production. Crop residue incorporation can either stimulate or reduce N2O emissions depending on the mineral N content of the soil. Crop residues pyrolysed to biochar can potentially stabilise native soil C (negative priming) and reduce N2O emissions from cropping soils thus providing climate change mitigation potential beyond the biochar C storage in soils. Incorporation of crop residues as an approach to recycle organic materials and reduce synthetic N fertiliser use in agricultural production requires a thorough evaluation, both in terms of biomass production and greenhouse gas emissions.

Biochemical and structural characterization of residue 96 mutants of Plasmodium falciparum triosephosphate isomerase: active-site loop conformation, hydration and identification of a dimer-interface ligand-binding site

Plasmodium falciparum TIM (PfTIM) is unique in possessing a Phe residue at position 96 in place of the conserved Ser that is found in TIMs from the majority of other organisms. In order to probe the role of residue 96, three PfTIM mutants, F96S, F96H and F96W, have been biochemically and structurally characterized. The three mutants exhibited reduced catalytic efficiency and a decrease in substrate-binding affinity, with the most pronounced effects being observed for F96S and F96H. The k(cat) values and K-m values are (2.54 +/- 0.19) x 10(5) min(-1) and 0.39 +/- 0.049 mM, respectively, for the wild type; (3.72 +/- 0.28) x 10(3) min(-1) and 2.18 +/- 0.028 mM, respectively, for the F96S mutant;(1.11 +/- 0.03) x 10(4) min(-1) and 2.62 +/- 0.042 mM, respectively, for the F96H mutant; and (1.48 +/- 0.05) x 10(5) min(-1) and 1.20 +/- 0.056 mM, respectively, for the F96W mutant. Unliganded and 3-phosphoglycerate (3PG) complexed structures are reported for the wild-type enzyme and the mutants. The ligand binds to the active sites of the wild-type enzyme (wtPfTIM) and the F96W mutant, with a loop-open state in the former and both open and closed states in the latter. In contrast, no density for the ligand could be detected at the active sites of the F96S and F96H mutants under identical conditions. The decrease in ligand affinity could be a consequence of differences in the water network connecting residue 96 to Ser73 in the vicinity of the active site. Soaking of crystals of wtPfTIM and the F96S and F96H mutants resulted in the binding of 3PG at a dimer-interface site. In addition, loop closure at the liganded active site was observed for wtPfTIM. The dimer-interface site in PfTIM shows strong electrostatic anchoring of the phosphate group involving the Arg98 and Lys112 residues of PfTIM.

Residue Potential of Norsesquiterpene Glycosides in Tissues of Cattle Fed Austral Bracken (Pteridium esculentum).

Austral bracken, Pteridium esculentum, occurs widely in Australian grazing lands and contains both the known carcinogen ptaquiloside and its hydroxy analogue, ptesculentoside, with untested carcinogenic potential. Calves were fed a diet containing 19% P. esculentum that delivered 1.8 mg of ptaquiloside and 4.0 mg of ptesculentoside per kilogram of body weight (bw) per day to explore the carcass residue potential of these compounds. Concentrations of ptaquiloside and ptesculentoside in the liver, kidney, skeletal muscle, heart, and blood of these calves were determined as their respective elimination products, pterosin B and pterosin G, by HPLC-UV analysis. Plasma concentrations of up to 0.97 mu g/mL ptaquiloside and 1.30 mu g/mL ptesculentoside were found, but were shown to deplete to <10% of these values within 24 h of bracken consumption. Both glycosides were also detected in all tissues assayed, with ptesculentoside appearing to be more residual than ptaquiloside. Up to 0.42 and 0.32 mu g/g ptesculentoside was present in skeletal muscle and liver, respectively, 15 days after bracken consumption ended. This detection of residual glycosides in tissues of cattle feeding on Austral bracken raises health concerns for consumers and warrants further investigation.

An essential arginine residue at the substrate binding site of 4-hydroxyisophthalate hydroxylase.

4-Hydroxyisophthalate hydroxylase was inactivated by treatment with phenylglyoxal by a process obeying pseudo-first order kinetics indicating the presence of an essential arginine located presumably in the active site. Addition of saturating amounts of 4-hydroxyisophthalate during the treatment resulted in complete protection of the enzyme from the inactivation, but addition of NADPH was totally ineffective. Analysis of the effect of various substrate analogs on the protection of the enzyme showed that carboxyl and hydroxyl groups at para positions on the aromatic ring are essential for substrate binding to the active site. It was also observed that analogs which protect the enzyme against phenylglyoxal inactivation are themselves effective inhibitors of the enzyme activity.

Sugarcane productivity response to different fallow and soybean residue management practices in the Bundaberg district

GRAIN LEGUME ROTATIONS underpin the sustainability of the Australian sugarcane farming system, offering a number of soil health and environmental benefits. Recent studies have highlighted the potential for these breaks to exacerbate nitrous oxide (N2O) emissions. An experiment was implemented in 2012 to evaluate the impact of two fallow management options (bare fallow and soybean break crop) and different soybean residue management practices on N2O emissions and sugarcane productivity. The bare fallow plots were conventionally tilled, whereas the soybean treatments were either tilled, not tilled, residue sprayed with nitrification inhibitor (DMPP) prior to tillage or had a triticale ‘catch crop’ sown between the soybean and sugarcane crops. The fallow plots received either no nitrogen (N0) or fully fertilised (N145) whereas the soybean treatments received 25 kg N/ha at planting only. The Fallow N145 treatment yielded 8% more cane than the soybean tilled treatment. However there was no statistical difference in sugar productivity. Cane yield was correlated with stalk number that was correlated to soil mineral nitrogen status in January. There was only 30% more N/ha in the above-ground biomass between the Fallow N145 and the Fallow N0 treatment; highlighting poor fertiliser nitrogen use efficiency. Supplying adequate nitrogen to meet productivity requirements without causing environmental harm remains a challenge for the Australian sugar industry. The soybean direct drill treatment significantly reduced N2O emissions and produced similar yields and profitability to the soybean tilled treatment (outlined in a companion paper by Wang et.al. in these proceedings). Furthermore, this study has highlighted that the soybean direct drill technique provides an opportunity to enable grain legume cropping in the sugarcane farming system to capture all of the soil health/environmental benefits without exacerbating N2O emissions from Australian sugarcane soils.

Soybean rotation and crop residue management to reduce nitrous oxide emissions from sugarcane soils

NITROUS OXIDE (N2O) IS a potent greenhouse gas and the predominant ozone-depleting substance in the atmosphere. Agricultural nitrogenous fertiliser use is the major source of human-induced N2O emissions. A field experiment was conducted at Bundaberg from October 2012 to September 2014 to examine the impacts of legume crop (soybean) rotation as an alternative nitrogen (N) source on N2O emissions during the fallow period and to investigate low-emission soybean residue management practices. An automatic monitoring system and manual gas sampling chambers were used to measure greenhouse gas emissions from soil. Soybean cropping during the fallow period reduced N2O emissions compared to the bare fallow. Based on the N content in the soybean crop residues, the fertiliser N application rate was reduced by about 120 kg N/ha for the subsequent sugarcane crop. Consequently, emissions of N2O during the sugarcane cropping season were significantly lower from the soybean cropped soil than those from the conventionally fertilised (145 kg N/ha) soil following bare fallow. However, tillage that incorporated the soybean crop residues into soil promoted N2O emissions in the first two months. Spraying a nitrification inhibitor (DMPP) onto the soybean crop residues before tillage effectively prevented the N2O emission spikes. Compared to conventional tillage, practising no-till with or without growing a nitrogen catch crop during the time after soybean harvest and before cane planting also reduced N2O emissions substantially. These results demonstrated that soybean rotation during the fallow period followed with N conservation management practices could offer a promising N2O mitigation strategy in sugarcane farming. Further investigation is required to provide guidance on N and water management following soybean fallow to maintain sugar productivity.