Commercial products from bio-active extractives in cypress milling residues.

Extractive components obtained from milling residues of white cypress were studied for chemical identity and bioactivity with a view to developing a commercial use for these components, thus increasing the value of the residues and improving the economics of cypress sawn wood production. Extracts obtained by solvent or steam extraction techniques from cypress sawdust were each fractionated by a range of techniques into groups of similar compounds. Crude extracts and fractions were screened against a range of agricultural pests and diseases, including two fungi, subterranean termites, fruit spotting bugs, two-spotted mites, thrips, heliothis, banana scab moths, silverleaf whiteflies, cattle tick adults and larvae, and ruminant gastrointestinal nematodes. Additional screening was undertaken where encouraging results were achieved, for two-spotted mites, thrips, silverleaf whiteflies, cattle tick adults and ruminant gastrointestinal nematodes. After considering degrees of efficacy against, and economic importance of, the agricultural pests, and likely production costs of extracts and fractions, the crude extract (oil) produced by steam distillation was chosen for further study against silverleaf whitefly. A useful degree of control was achievable when this oil was applied to tomato or eggplant at 0.1%, with much less harmful effects on a beneficial insect. Activity of the oil against silverleaf whitefly was undiminished 3.5 years after it was generated. There was little benefit from supplementing the extract with co-formulated paraffinic oil. From the steam distilled oil, fifty-five compounds were characterised, thirty-five compounds representing 92.478 % of the oil, with guaiol (20.8%) and citronellic acid (15.9%) most abundant. These two compounds, and a group of oxygenated compounds containing bulnesol and a range of eudesmols, were found to account for most of the activity against silverleaf whitefly. This application was recommended for first progression to commercialisation.

Reducing the risk of herbicide runoff in sugarcane farming through controlled traffic and early-banded application

The off-site transport of agricultural chemicals, such as herbicides, into freshwater and marine ecosystems is a world-wide concern. The adoption of farm management practices that minimise herbicide transport in rainfall-runoff is a priority for the Australian sugarcane industry, particularly in the coastal catchments draining into the World Heritage listed Great Barrier Reef (GBR) lagoon. In this study, residual herbicide runoff and infiltration were measured using a rainfall simulator in a replicated trial on a brown Chromosol with 90–100% cane trash blanket cover in the Mackay Whitsunday region, Queensland. Management treatments included conventional 1.5 m spaced sugarcane beds with a single row of sugarcane (CONV) and 2 m spaced, controlled traffic sugarcane beds with dual sugarcane rows (0.8 m apart) (2mCT). The aim was to simulate the first rainfall event after the application of the photosynthesis inhibiting (PSII) herbicides ametryn, atrazine, diuron and hexazinone, by broadcast (100% coverage, on bed and furrow) and banding (50–60% coverage, on bed only) methods. These events included heavy rainfall 1 day after herbicide application, considered a worst case scenario, or rainfall 21 days after application. The 2mCT rows had significantly (P < 0.05) less runoff (38%) and lower peak runoff rates (43%) than CONV rows for a rainfall average of 93 mm at 100 mm h−1 (1:20 yr Average Return Interval). Additionally, final infiltration rates were higher in 2mCT rows than CONV rows, with 72 and 52 mm h−1 respectively. This resulted in load reductions of 60, 55, 47, and 48% for ametryn, atrazine, diuron and hexazinone from 2mCT rows, respectively. Herbicide losses in runoff were also reduced by 32–42% when applications were banded rather than broadcast. When rainfall was experienced 1 day after application, a large percentage of herbicides were washed off the cane trash. However, by day 21, concentrations of herbicide residues on cane trash were lower and more resistant to washoff, resulting in lower losses in runoff. Consequently, ametryn and atrazine event mean concentrations in runoff were approximately 8 fold lower at day 21 compared with day 1, whilst diuron and hexazinone were only 1.6–1.9 fold lower, suggesting longer persistence of these chemicals. Runoff collected at the end of the paddock in natural rainfall events indicated consistent though smaller treatment differences to the rainfall simulation study. Overall, it was the combination of early application, banding and controlled traffic that was most effective in reducing herbicide losses in runoff. Crown copyright © 2012

Peptide models for the bacteriorhodopsin chromophore. Retinylidene-lysine systems containing aspartic acid and serine residues

The retinylidene Schiff base derivative of seven lysine containing peptides have been prepared in order to investigate solvent and neighboring group effects, on the absorption maximum of the protonated Schiff base chromophore. The peptides studied are Boc-Aib-Lys-Aib-OMe (1), Boc-Ala-Aib-Lys-OMe (2), Boc-Ala-Aib-Lys-Aib-OMe (3), Boc-Aib-Asp-Aib-Aib-Lys-Aib-OMe (4), Boc-Aib-Asp-Aib-Ala-Aib-Lys-Aib-OMe (5), Boc-Lys-Val-Gly-Phe-OMe (6) and Boc-Ser-Ala-Lys-Val-Gly-Phe-OMe (7). In all cases protonation shifts the absorption maxima to the red by 3150–8450 cm-1. For peptides 1–3 the protonation shifts are significantly larger in nonhydrogen bonding solvents like CHCl3 or CH2Cl2 as compared to hydrogen bonding solvents like CH3OH. The presence of a proximal Asp residue in 4 and 5 results in pronounced blue shift of the absorption maximum of the protonated Schiff base in CHCl3, relative to peptides lacking this residue. Peptides 6 and 7 represent small segments of the bacteriorhodopsin sequence in the vicinity of Lys-216. The presence of Ser reduces the magnitude of the protonation shift.

Increased options for controlling mikania vine (Mikania micrantha) with foliar herbicides

Mikania micrantha Kunth (mikania vine) is a highly invasive tropical weed that was first discovered in Australia in 1997, and has been the target of a nationally cost-shared weed eradication program since 2003. Field crews have been effectively treating the weed with herbicide solutions containing 1 g a.i. L−1 of fluroxypyr. During the eradication program there have been limited opportunities to test alternative foliar herbicides or rates. A newly discovered infestation provided sufficient immature vines to compare the effectiveness of eight herbicide treatments.

Influence of tillage, cover cropping, and herbicides on weeds and productivity of dry direct-seeded rice

The adoption of dry direct seeding of rice in many Asian countries has resulted in increased interest among weed scientists to improve weed management strategies, because of the large and complex weed flora associated with dry-seeded rice (DSR). Tillage and cover cropping practices can be integrated into weed management strategies as these have been known to affect weed emergence for several ecological reasons. A study was conducted in the summer seasons of 2012 and 2013 at the Punjab Agricultural University, Ludhiana, India, to evaluate the effects of tillage, cover cropping, and herbicides on weed growth and grain yield of DSR. Most of the weed species (Echinochloa crus-galli, Echinochloa colona, Eleusine indica, and Euphorbia hirta) under study tended to populate the cover crop (CC) treatment more than the no-cover crop (no-CC) treatment. Zero tillage (ZT) resulted in higher weed densities of most of the weed species studied. The interaction effects of these treatments suggest that lesser herbicide efficacy in ZT and CC plots led to higher weed pressure and weed biomass. Grain yield was significantly higher in the conventional tillage system (2.40–3.32 t ha−1), because of lesser weed pressure, than in ZT (2.08–2.73 t ha−1). Almost all weed species increased in number and biomass production in the second year (2013) compared with the preceding year. Herbicide application (pendimethalin followed by bispyribac-sodium) alone, though significantly increased DSR grain yield over that of the unsprayed check, resulted in lesser grain yield compared with the weed-free check (5.07–5.12 t ha−1) by 14% and 27% in 2012 and 2013, respectively. This was mainly due to the buildup of biomass by weeds that escaped from herbicide application. The study reveals that conservation practices such as ZT can form an important component of integrated weed management in DSR, provided that herbicide efficacy be improved by adjusting rate and time of herbicide application in such systems.

Interference and management of parthenium: The world's most important invasive weed

Parthenium (Parthenium hysterophorus L.) is one of the most aggressive herbaceous weeds of the Asteraceae family. It is widely distributed, almost across the world and has become the most important invasive weed. Comprehensive information on interference and control of this devastating species is required to facilitate better management decisions. A broad review on the interference and management of this weed is presented here. Inspite of its non-tropical origin, parthenium grows quite successfully under a wide range of environmental conditions. It is spreading rapidly in Australia, Western Africa, Asia, and Caribbean countries, and has become a serious weed of pastures, wastelands, roadsides, railwaysides, water courses, and agricultural crops. The infestations of parthenium have been reported to reduce grain and forage yields by 40–90%. The spread of parthenium has been attributed to its allelopathic activity, strong competitiveness for soil moisture and nutrients, and its capability to exploit natural biodiversity. Allelochemicals released from parthenium has been reported to decrease germination and growth of agronomic crops, vegetables, trees, and many other weed species. Growth promoting effects of parthenium extracts at low concentrations have also been reported in certain crops. Many pre- and post-emergence herbicides have been evaluated for the control of parthenium in cropped and non-cropped areas. The most effective herbicides are clomazone, metribuzin, atrazine, glyphosate, metsulfuron methyl, butachlor, bentazone, dicamba, and metsulfuron methyl. Extracts, residues, and essential oils of many allelopathic herbs (Cassia, Amaranthus, and Xanthium species), grasses (Imperata and Desmostachya species), and trees (Eucalyptus, Azadirachta, Mangifera species, etc.) have demonstrated inhibitory activities on seed germination and seedling growth of parthenium. Metabolites of several fungi, e.g., Fusarium oxysporun and Fusarium monilifonne, exhibit bioherbicidal activity against seeds and seedlings of this weed. Intercropping, displacement by competitive plant species like Cassia species, bisset bluegrass, florgen blugress, buffelgrass, along with the use of biological control agents like Mexican beetle, seed-feeding and stem-boring weevils, stem-galling and leaf-mining moth, and sap-feeding plant hopper, have been reported as possible strategies for the management of parthenium. An appropriate integration of these approaches could help minimize spread of parthenium and provide sustainable weed management with reduced environmental concerns.

Agronomic indices, growth, yield-contributing traits, and yield of dry-seeded rice under varying herbicides

Dry-seeded rice (DSR) is an emerging resource-conserving technology in many Asian countries, but weeds remain the major threat to the production of DSR systems. A field study was conducted in 2012 and 2013 at the International Rice Research Institute (IRRI), Los Baños, Philippines, to evaluate the performance of sole and sequential applications of preemergence (oxadiazon and pendimethalin), early postemergence (butachlor + propanil and thiobencarb + 2,4-D), and late postemergence herbicides (bispyribac-sodium and fenoxaprop + ethoxysulfuron) with different modes of action in comparison to manual weeding in DSR. The sequential applications of all preemergence and postemergence herbicides reduced weed density and biomass by 80–100% compared to the nontreated plots. The sole application of postemergence herbicides reduced weed density by only 44–54% and weed biomass by 51–61%, whereas oxadiazon alone reduced weed density and biomass by 96–100%. All herbicide treatments and manual weeding significantly affected tiller number, biomass, crop growth rate, agronomic indices, yield-contributing parameters (panicle density and filled grains), and yield (biological and grain) of rice. The highest grain yield was obtained in the manually weeded plots (5.9–6.1 t ha−1) and the plots treated with oxadiazon alone (5.4–5.6 t ha−1) and oxadiazon followed by postemergence herbicides (5.2–5.8 t ha−1). The lowest paddy yield (0.22 t ha−1) was achieved in the nontreated plots followed by the plots treated with the sole application of bispyribac-sodium and fenoxaprop + ethoxysulfuron. The results suggest that oxadiazon is the best broad-spectrum and economically effective herbicide when applied alone or in combination with other effective postemergence herbicides with different modes of action, depending on the weed species present in the field.

Weed control in dry direct-seeded rice using tank mixtures of herbicides in South Asia

Dry direct-seeded rice (DSR) faces with complex weed problems particularly when farmers missed pre-emergence herbicide applications. Thus, an effective and strategic weed control in DSR is often required with available options of post-emergence herbicides. In such situations, tank mixtures of herbicides may provide broad spectrum weed control in DSR. Field experiments were conducted in the wet seasons of 2013 and 2014 to study weed control in response to tank mixtures of herbicides currently applied in DSR in South Asia. Results revealed that the tank mixtures of the currently available herbicides (azimsulfuron plus bispyribac or fenoxaprop, bispyribac plus fenoxaprop, and azimsulfuron plus bispyribac plus fenoxaprop; all applied as post-emergence) rarely resulted in antagonistic effects. Highest weed control efficiency (∼98%) was recorded with the tank mixture of azimsulfuron plus bispyribac plus fenoxaprop during both the years. This treatment also produced highest grain yield (7.2 t ha−1 in 2013 and 7.9 t ha−1in 2014), which was similar to the grain yield in the plots treated with the tank mix of azimsulfuron plus fenoxaprop, pendimethalin (applied as pre-emergence) followed by (fb) bispyribac, pendimethalin fb fenoxaprop, as well as pendimethalin fb azimsulfuron. Plots treated with the post-emergence application of single herbicide (i.e., azimsulfuron, bispyribac, or fenoxaprop) had lower grain yield (3.0–5.2 t ha−1 in 2013 to 3.5–6.1 t ha−1in 2014) than all the sequential herbicide treatments and tank mixtures (azimsulfuron plus fenoxaprop and azimsulfuron plus bispyribac), owing to a broad spectrum weed control. The study suggested that if farmers missed the pre-emergence application of herbicides (e.g., pendimethalin) due to erratic rains or due to other reasons, good weed control and high yield can still be obtained with tank mix applications of azimsulfuron plus fenoxaprop or azimsulfuron plus bispyribac plus fenoxaprop in DSR.

Studies on Aspergillus niger glutamine synthetase: Regulation of enzyme levels by nitrogen sources and identification of active site residues

The specific activity of glutamine synthetase (L-glutamate: ammonia ligase, EC 6.3.1.2) in surface grown Aspergillus niger was increased 3-5 fold when grown on L-glutamate or potassium nitrate, compared to the activity obtained on ammonium chloride. The levels of glutamine synthetase was regulated by the availability of nitrogen source like NH4 + , and further, the enzyme is repressed by increasing concentrations of NH4 +. In contrast to other micro-organisms, the Aspergillus niger enzyme was neither specifically inactivated by NH4+ or L-glutamine nor regulated by covalent modification.Glutamine synthetase from Aspergillus niger was purified to homogenity. The native enzyme is octameric with a molecular weight of 385,000±25,000. The enzyme also catalyses Mn2+ or Mg2+-dependent synthetase and Mn2+-dependent transferase activity.Aspergillus niger glutamine synthetase was completely inactivated by two mol of phenylglyoxal and one mol of N-ethylmaleimide with second order rate constants of 3·8 M–1 min–1 and 760 M–1 min–1 respectively. Ligands like Mg. ATP, Mg. ADP, Mg. AMP, L-glutamate NH4+, Mn2+ protected the enzyme against inactivation. The pattern of inactivation and protection afforded by different ligands against N-ethylamaleimide and phenylglyoxal was remarkably similar. These results suggest that metal ATP complex acts as a substrate and interacts with an arginine ressidue at the active site. Further, the metal ion and the free nucleotide probably interact at other sites on the enzyme affecting the catalytic activity.

Stabilization of the collagen structure by hydroxyproline residues

The molecular structure of collagen is now accepted to be based on a triple-stranded coiled-coil, in which the three strands are held together predominantly by hydrogen bonds. Recent experimental evidence has shown that the presence of hydroxyproline residues in the third position of the repeating tripeptide unit lends additional stability to the collagen structure. In this paper, we report a model structure, which is supported by these observations. In a model structure proposed earlier, there are two hydrogen bonds per tripeptide unit, one of which is a direct interchain hydrogen bond, while the second hydrogen bond can be formedvia a water molecule. It has now been shown that the same water molecule can also form a hydrogen bond with the oxygen of theγ-hydroxyl group of hydroxyproline in the third position in the sequence (Gly-R2-R3). This hydroxyl group can also take part in an inter-triple-helix hydrogen bond. Our studies thus show the role played by hydroxyproline residues in the structure and stability of collagen.

Chemical modification studies on Abrus agglutinin Involvement of tryptophan residues in sugar binding

The galactose-binding lectin from the seeds of the jequirity plant (Abrus precatorius) was subjected to various chemical modifications in order to detect the amino acid residues involved in its binding activity. Modification of lysine, tyrosine, arginine, histidine, glutamic acid and aspartic acid residues did not affect the carbohydratebinding activity of the agglutinin. However, modification of tryptophan residues carried out in native and denaturing conditions with N-bromosuccinimide and 2- hydroxy-5-nitrobenzyl bromide led to a complete loss of its carbohydrate-binding activity. Under denaturing conditions 30 tryptophan residues/molecule were modified by both reagents, whereas only 16 and 18 residues/molecule were available for modification by N-bromosuccinimide and 2-hydroxy-5-nitrobenzyl bromide respectively under native conditions. The relative loss in haemagglutinating activity after the modification of tryptophan residues indicates that two residues/molecule are required for the carbohydrate-binding activity of the agglutinin. A partial protection was observed in the presence of saturating concentrations of lactose (0.15 M). The decrease in fluorescence intensity of Abrus agglutinin on modification of tryptophan residues is linear in the absence of lactose and shows a biphasic pattern in the presence of lactose, indicating that tryptophan residues go from a similar to a different molecular environment on saccharide binding. The secondary structure of the protein remains practically unchanged upon modification of tryptophan residues, as indicated by c.d. and immunodiffusion studies, confirming that the loss in activity is due to modification only.

Conformation of polypeptide-chains containing both l-residues and D-residues .2. Double-helical structures of poly-ld-peptides

Polypeptides with alternating L- and D-amino acid residues can take up stereochemically satisfactory coaxial double-helical structures, both antiparallel and parallel, which are stabilized by systematic interchain NH O hydrogen bonds. Semiempirical energy calculations over allowed regions of conformational space have yielded the characteristics of these double-helices. There are four possible types of antiparallel double-helices - A3, A4, A5 and A6, with n, the number of LD peptide units per turn, around 2.8, 3.6, 4.5 and 5.5 respectively, while for the parallel double-helices there are two types, P3 and P4, having similar helical parameters as in A3 and A4. The hydrogen-bonding scheme restricts the pitch in all the models to the narrow range of 10.0 to 11.5 Å. All these helices have large central cores whose radii increase proportionately with n. In this respect, A3 and A4 are suitable models for the structure of gramicidin A. In terms of their relative energies, antiparallel double-helices are marginally more stable than those with parallel strands. Our results indicate that the energy differences amongst the members in the antiparallel family are not significant and thus provide an explanation for the polymorphism reported for poly(γ-benzyl-LD-glutamate).

Stereochemical restrictions on the occurrence of amino acid residues in the collagen structure

The primary structure of collagen is characterized by the repeating tripeptide sequence (Gly-R2-R3)n. The results of theoretical studies, carried out using contact criteria to compute the stereochemically allowed orientations for various side chains at locations 2 and 3, are reported here. It is found that side chains with only γ-atoms, as in valine, serine and threonine, or with only one δ-methyl group, as in isoleucine, can occur equally well at locations 2 and 3, as is actually the case in collagen. Side chains with two Cδ-atoms, as in leucine and phenyl-alanine, can also be accommodated at both positions. However, if they occur as R3 their freedom of orientation is severely restricted in the presence of a proline residue as R2 in a neighbouring chain. If water molecules bound to the chains of the triple helix are assumed to be present, then location 3 is virtually impossible for leucine and phenylalanine residues. Location 2 is, however, unaffected, and their presence as R2 can help to shield the water molecules from disturbance by the solvent medium. This may be the reason for the preferential occurrence of Leu and Phe residues in location 2 in the collagen triplets, although the polypeptides (Gly-Pro-Leu)n and (Gly-Pro-Phe)n form collagen-like structures.