Structure-activity relationship observations for the bagworm moth pheromone

Structure-activity relationship (SAR) observations were made for the bagworm moth pheromone, (R)-2-pentyl decanoate, and a series of analogs with modifications in the alcohol portion of the molecule. Observed attractiveness of these analogs was related to molecular structure and their physical attributes using computational chemistry. Electrostatic potential and Van der Waals (VdW) electrostatic coded surface three-dimensional (3D) maps of the molecular mechanics (MM) minimized lowest energy conformation of the pheromone show that size, shape, charge distribution, and chirality of the molecule are related to attractiveness.     

Effect of green manure on the yield,N uptake and floodwater properties of a flooded rice,wheat rotation receiving15N urea on a highly permeable soil

Field studies were conducted for two years on a rapidly percolating loamy sand (Typic Ustochrept) to evaluate the effect of green manure (GM) on the yield,¹⁵N recovery from urea applied to flooded rice, the potential for ammonia loss and uptake of residual fertilizer N by succeeding crops. The GM crop ofSesbania aculeata was grownin situ and incorporated one day before transplanting rice. Urea was broadcast in 0.05 m deep floodwater, and incorporated with a harrow. Green manure significantly increased the yield and N uptake by rice and substituted for a minimum of 60 kg fertilizer N ha^–1. The recovery of fertilizer N as indicated by¹⁵N recovery was higher in the GM + urea treatments. The grain yield and N uptake by succeeding wheat in the rotation was slightly higher with GM. The recovery of residual fertilizer N as indicated by the¹⁵N recovery in the second, third and fourth crops of wheat, rice and wheat was only 3, 1 and 1 per cent of the urea fertilizer applied to the preceding rice crop. Floodwater chemistry parameters showed that the combined use of the GM and 40 kg N ha^–1 as urea applied at transplanting resulted in a comparatively higher potential for NH₃ loss immediately after fertilizer application. The actual ammonia loss as suggested by the¹⁵N recoveries in the rice crop, however, did not appear to be appreciably larger in the GM treatment. It appeared the ammonia loss was restricted by low ammoniacal-N concentration maintained in the floodwater after 2 to 3 days of fertilizer application.     

Nitrogen utilization by lowland rice as affected by fertilization with urea and green manure

Field studies were conducted during two consecutive wet seasons in flooded rice (Oryza sativa L.) to determine the effect of green manure on urea utilization in a rice-fallow-rice cropping sequence. Replicated plots were fertilized with 60 to 120 kg of urea N ha^–1 in three split applications (50, 25 and 25%) with or without incorporation of dhaincha (Sesbania aculeata L.) (100 kg N ha^–1). During the first crop only 31 to 44% of the urea added was used by the rice. Incorporatingin situ grown dhaincha (GM) into the soil at transplanting had little effect on urea utilization. Forty-four to 54% of the N added was not recovered in the soil, rice crop, or as nitrate leachate during the first cropping season. Incorporation of GM had no effect on fertilizer N recovery. Only about 2% of the urea N added to the first rice crop was taken up by the second rice crop and, as in the first crop, the GM had little effect on residual N, either in amount or utilization.     

Structure-activity relationships among aromatic analogs of trail-following pheromone of subterranean termites

A series of 12 substituted (Z)-4-phenyl-3-buten-l-ol (PBO) derivatives were synthesized and evaluated for trail-following activity in five species of subterranean termites in the generaCoptotermes, Prorhinotermes, Reticulitermes, andSchedorhinotermes (Isoptera: Rhinotermitidae). The unsubstituted parent PBO was the most active for all species, and electron-withdrawing and electron-donating groups both reduced potency. Sensitivity to substitution in the ortho position suggests steric inhibition of binding by the 2-substituted analogs. Different sensitivities to these pheromone analogs were found among the five species, withR.flavipes andS. lamanianus showing the highest level of trail-following activity for the PBO analogs.Fellow of the Alfred P. Sloan Foundation (1981–85) and Camille and Henry Dreyfus Teacher-Scholar (1981–86).     

Effect of urea and salt on micelle formation of zwitterionic surfactants

The effect of urea on micelle formation of zwitterionic surfactants was investigated by measuring conductivity, critical micelle concentration (CMC), relative viscosity, and the spectrophotometric shift in wavelength. We examined two zwitterionic surfactants, N,N-dimethyl dodecylamine N-oxide and N,N-dimethyl tetradecylamine N-oxide (DMTAO). The CMC values of the surfactants increased with the addition of urea. Also, the relative viscosity of the surfactant solutions decreased at higher concentrations of urea and increased with increasing KCl concentration. The absorbance maxima of the surfactants decreased with increasing urea concentration.     

Moth responses to selectively fluorinated sex pheromone analogs

Partially fluorinated analogs of the European corn borer (Ostrinia nubilalis) female sex pheromone, 11-tetradecenyl acetate (97:3Z:E), having mono- and trifluorsubstitutions at the terminal carbon of the pheromone chain, mimicked the biological activity of the pheromone, while analogs with fluorine at either side of the double bond and a pentafluoro analog were essentially inactive. Comparison of the pheromonal activity of these analogs with the previously reported activity of similarly fluorinated pheromones in five other species of moths revealed an unpredictable relationship between fluorine substitution pattern and pheromone-mimicking activity. Fluorine substitution patterns that rendered pheromonal analogs biologically inactive in the European corn borer had no detrimental influence upon pheromonal activity in other species and the converse was also true. This is evidence that the relative importance of electronic qualities of sites within a pheromone molecule differ from species to species. Furthermore, it indicates that the biochemical components (pheromone receptor proteins, binding proteins, and enzymes) that make up moth olfactory chemosensory systems must also vary structurally from species to species, despite the fact that they are involved in olfactory sensing of compounds having very similar chemical structure.     

Structure-activity correlations among analogs of the currant clearwing moth pheromone

Eleven analogs of (E,Z)-2,13-octadecadien-1-yl acetate1, a main pheromone component of the currant clearwing moth,Synanthedon tipuliformis Clerk (Lepidoptera: Sesiidae) were synthesized and tested for their biological activities by electroantennography (EAG). To correct the EAG data for differences in volatility of the analogs, their vapor pressures were estimated by a gas chromatographic method. All structural changes in the parent molecule were found to reduce the biological activity to various degrees. The most active analog tested was the carbamate12, whose activity was almost comparable to that of the pheromone component1. Structure-activity correlations showed that hydrophobic, steric, and electronic effects of chain terminal groups might be responsible for variations in biological activity of the conformationally unchanged (E,Z)-2,13-analogs     

Effect of prilled urea and modified urea materials on yield and quality of geranium (Pelargonium graveolens L. Her.)

Two field experiments were conducted to study the effect of prilled urea, neem cake coated urea, dicyandiamide treated urea and urea supergranules applied to a perennial aromatic herb, geranium (Pelargonium graveolens L. Her'.) grown on a sandy loam soil. Application of nitrogen increased the biomass and essential oil yields. Neem cake coated urea significantly increased the yields over prilled urea. There was no residual effect of N levels and N carriers. The concentration and quality of essential oil were not influenced either by levels or carriers of N.     

Incorporation of urea for transplanted rice as affected by floodwater and growing season

Incorporation of urea into puddled rice soils is known to reduce ammoniacal-N buildup in floodwater and the subsequent loss of N as ammonia. Little is known, however, about seasonal and temperature effects on the effectiveness of basal urea incorporation in puddled soils. A field experiment was conducted in northern Vietnam on an Aquic Ustifluvent in the spring season (February to June) and summer season (July to November) to determine the effect of the presence of floodwater and method of fertilizer incorporation on floodwater ammoniacal-N, floodwater urea-N, andpNH₃ following urea application. During the 4 d following basal urea application, floodwater temperature at 1400 h was 7 to 15°C higher in summer (July) than that in spring (February), and floodwater pH at 1400 h was 0.5 to 1.0 higher in summer than that in spring. ThepNH₃ was much higher in summer than that in spring, suggesting a high potential for ammonia volatilization in summer. The movement of transplanters through the field did not reducepNH₃, irrespective of floodwater depth (0 or 5 cm) and season. Harrowing and subsequent transplanter movement partially reducedpNH₃ in the summer;pNH₃ reduction, however, was greater when floodwater depth was 0 rather than 5 cm during harrowing and transplanting. This partial reduction ofpNH₃ in summer did not result in a corresponding increase in rice yield, presumably because N losses were only slightly reduced and because yield was constrained by additional factors, such as the adverse climate. In spring, the removal of floodwater before urea application and incorporation increased grain yield by 0.2 Mg ha^–1, even thoughpNH₃ was consistently low and was not reduced by urea incorporation. This result suggests that water management and tillage during basal urea application may influence rice growth and yield in ways other than reduced N loss.     

Synthesis and field bioassay of some analogs of sex pheromone of citrus mealybug,Planococcus citri (Risso)

A series of structural analogs of (s+)-cis-(1R)-3-isopropenyl-2,2-dimethylcyclobutanemethanol acetate, sex pheromone of the citrus mealybug,Planococcus citri (Risso), was synthesized. The analogs were tested in a field bioassay in order to determine the structure-activity relationships of the pheromone. All changes in structure reduced the activity of the test compounds, to various degrees. The most active analog tested was the homolog (+)-cis-(1R)-3-isopropenyl-2,2-dimethylcyclobutaneethanol acetate (IV), whose activity, at a higher dosage, was comparable to that of the pheromone. The alcohol (+)-cis-(1R)-3-isopropenyl-2,2-dimethylcyclobutanemethanol was tested in mixtures with the pheromone and found to be neither an inhibitor nor a Synergist. The results show that all functional groups of the pheromone molecule are essential for optimal biological activity.Homoptera: Coccoidea: Pseudococcidae.Contribution from the Agricultural Research Organization (ARO), The Volcani Center, Bet Dagan, Israel, No. 1667-E, 1986 series.Levi Eshkol Postdoctoral Fellow, 1984–1986.     

Alkyl ether and enol ether analogs of (Z)-5-decenyl acetate,a pheromone component of the turnip moth,Agrotis segetum: probing a proposed bioactive conformation for chain-elongated analogs

In order to test a previous conclusion that chain-elongated analogs of (Z)-5-decenyl acetate(1), a pheromone component of the turnip moth,Agrotis segetum, adopt a loop conformation of the terminal alkyl chain in the bioactive conformation, a series of alkyl ether and enol ether analogs of1 and (Z)-5-dodecenyl acetate(2) have been synthesized and tested using singlecell electrophysiology. In these analogs a methylene group in positions 7 and 9 of1 and in positions 7 and 11 in2 have been replaced by an oxygen atom in order to energetically facilitate the formation of a loop conformation in the chain-elongated analogs. The electrophysiological results in combination with molecular mechanics (MM2 and MM3) calculated conformational energies show that the activity decreases of the chain-elongated ether analogs are significantly smaller than that for2 and that these activity decreases parallel the conformational energies for a loop formation of the terminal chains in the analogs. The results support our previous conclusion that the terminal chain of chain-elongated analogs of1 adopts a loop conformation in their bioactive conformations.     

Relative susceptibility of conventional and experimental nitrogen sources to ammonia loss from flooded rice fields

Urea, the most common N source in Asia, is prone to high loss as ammonia when applied to tropical flooded rice (Oryza sativa L.). Chemical or physical modifications of urea could offer potential in reducing ammonia loss. Two field studies were conducted to identify conventional and experimental N-containing sources loss prone to ammonia less than prilled urea. Relative susceptibility to ammonia loss was inferred from equilibrium ammonia vapor pressure, pNH₃. For the sources studied, ammonia formation and presumably loss were least for guanylurea sulfate (GUS) and sulfur-coated urea (SCU). The slow mineralization and acidifying effect of GUS resulted in negligible ammonia concentration in the floodwater. Amendment of urea with either 5 or 10% paraformaldehyde (ureaform) reduced pNH₃, but never by more than 55%. Coating urea with phosphate rock tended to be less effective than amendment with paraformaldehyde in reducing pNH₃. There was no significant difference in the pNH₃, and presumably ammonia loss, for urea phosphate (17-44-0), urea-urea phosphate (34-17-0), and urea. About 3 days after fertilization, the floodwater pH tended to become higher with NP sources than with urea. This elevation in pH was apparently due to the stimulation of algal photosynthetic activity by added P, and it may explain the failure of a phosphoric acid amendment to urea (urea phosphate) in reducing pNH₃. Ammonia disappearance from broadcast diammonium phosphate (DAP) and ammonium phosphate sulfate (16-20-0) was complete within 3 days after N application, whereas ammonia remained in floodwater for up to 7 days following broadcast application of urea and ammonium sulfate.     

Selectively fluorinated analogs reveal differential olfactory reception and inactivation of green leaf volatiles in insects

The role of the alkyl terminus of green leaf volatile (GLV) molecules in olfactory reception and inactivation was examined in three diverse insect species: the beet armyworm,Spodoptera exigua (Lepidoptera); the Colorado potato beetle,Leptinotarsa decemlineata (Coleoptera); and the desert locust,Schistocerca gregaria (Orthoptera), using selectively fluorinated analogs of GLVs and electroantennograms (EAGs). When only the magnitude of the depolarization of the EAG is considered (a measure of reception), the order of effectiveness was 1-hexanol (6:OH)=(Z)-3-6:OH > 5,5,6,6,6-pentafluoro-(Z)-3-6:OH =5,5-difluoro-(Z)-3-6:OH 5,5,6,6,6-pentafluoro-6: OH. Percent recovery of the EAG (a measure of inactivation) was greater for the pentafluoro-(Z)-3-6: OH analog than for the difluoro-(Z)-3-6: OH analog. Our results show that the alkyl end of GLV molecules plays an important role not only in reception, but also inactivation processes in insect olfaction. Furthermore, specificities of these two processes may differ.Research conducted by J.C.D. while on an ARS Fellowship at IPO-DLO.     

Synthesis of the sex pheromone of the Japanese beetle

The stereospecific synthesis of the sex pheromone produced by the female Japanese beetle (Popillia japonica Newman), (R,Z)-5-1-decenyl)-dihydro-2(3H)-furanone, is described. The pure syntheticR,Z form is a powerful attractant for males of the species in field bioassays and was competitive in attractiveness with live females, whereas the racemicZ isomer and theS,Z enantiomer were strong inhibitors of male response. The saturated analogs of both enantiomers were also synthesized stereospecifically.Mention of a commercial or proprietary product in this paper does not constitute an endorsement of that product by the USDA.     

Structure-activity relationship observations for European corn borer moth pheromone and fluoro analogs via computer molecular modeling

Structure-activity relationship (SAR) observations were made for theZ-type European corn borer moth pheromone, (Z)-11-tetradecen-1-ol acetate, and a series of analogs with fluorination in the alcohol portion of the molecule. The attractiveness of these analogs and the pheromone was compared to the electrostatic potential map of the molecular mechanics (MM) minimized lowest energy conformation for each compound. A critical range of electrostatic potential on the protons of the double-bond appears to be essential for optimal acceptor fit and attractiveness.     

Effect of urea management on yield and N use efficiency of lowland rice on an acid sulfate soil

Field experiments were conducted during 1988–1989 at two adjacent sites on an acid sulfate soil (Sulfic Tropaquept) in Thailand to determine the influence of urea fertilization practices on lowland rice yield and N use efficiency. Almost all the unhydrolyzed urea completely disappeared from the floodwater within 8 to 10 d following urea application. A maximum partial pressure of ammonia (pNH₃) value of 0.14 Pa and an elevation in floodwater pH to about 7.5 following urea application suggest that appreciable loss of NH₃ could occur from this soil if wind speeds were favorable. Grain yields and N uptake were significantly increased with applied N over the control and affected by urea fertilization practices (4.7–5.7 Mg ha^–1 in dry season and 3.0–4.1 Mg ha^–1 in wet season). In terms of both grain yield and N uptake, incorporation treatments of urea as well as urea broadcasting onto drained soil followed by flooding 2 d later were more effective than the treatments in which the same fertilizer was broadcast directly into the floodwater either shortly or 10 d after transplanting (DT). The¹⁵N balance studies conducted in the wet season showed that N losses could be reduced to 31% of applied N by broadcasting of urea onto drained soil and flooding 2 d later compared with 52% loss by broadcasting of urea into floodwater at 10 DT. Gaseous N loss via NH₃ volatilization was probably responsible for the poor efficiency of broadcast urea in this study.     

Nitrogen leaching and plant uptake from controlled-release fertilizers

Controlled-release N fertilizers are commonly used in the production of container-grown ornamental crops, yet the relative effects of various nutrient sources on N leaching are not well known. A 27-week experiment was conducted to evaluate N leaching loss and plant growth following two applications of six controlled-release N fertilizers and one soluble N fertilizer to container-grownEuonymus patens Rehd. The controlled-release fertilizers evaluated were (noncoated) isobutylidene diurea, oxamide, urea formaldehyde, and (coated) Osmocote, Prokote Plus, and sulfur-coated urea. Of the fertilizers tested, the coated fertilizers generally out-performed the noncoated fertilizers in reducing N leaching losses, stimulating plant growth, and increasing tissue N concentrations. Low N concentrations in the leachate of some treatments indicated efficient nutrient use by the plant. In other treatments, low N concentrations in the leachate merely reflected incomplete N release from the fertilizer. A daily application of NH₄NO₃ resulted in a constant rate of N loss but was not the most effective in promoting growth. Plant growth, tissue N concentrations, and N leaching losses were all increased by doubling the fertilizer application rate from 1 kg N m^–3 to 2 kg N m^–3.     

Urea management for lowland transplanted rice as affected by application of farmyard manure

Farmyard manure (FYM) applied to rice-growing soils can substitute for industrial fertilizers, but little is known about the influence of FYM on the effectiveness and optimal management for industrial N fertilizers. A field experiment was conducted in northern Vietnam on a degraded soil in the spring season (February to June) and summer season (July to November) to determine the effect of FYM on optimal timing for the first application of urea. The experimental design was a randomized complete block with two rates of basal incorporated FYM (0 or 6 Mg ha^–1) in factorial combination with two timings of the first application of 30 kg urea-N ha^–1 (basal incorporated before transplanting or delayed until 14 to 16 d after transplanting). The FYM was formed by composting pig manure with rice straw for 3 months. Basal incorporation of FYM, containing 23 kg N ha^–1, increased rice grain yield in both seasons. The yield increase cannot be attributed to reduced ammonia loss of applied urea-N, because FYM did not reduce partial pressure of ammonia (pNH₃) following urea application in either season. Basal and delayed applications of urea were equally effective in the absence of FYM, but when FYM was applied rice yields in both seasons were higher for delayed (mean = 3.2 Mg ha^–1) than basal (mean = 2.9 Mg ha^–1) application of urea. Results suggest that recommendations for urea timing in irrigated lowland rice should consider whether farmers apply FYM.     

Eicosapentaenoic acid (20∶5n-3) from the marine microalgaPhaeodactylum tricornutum

Eicosapentaenoic acid (EPA, 20∶5n-3) was obtained from the marine microalgaePhaeodactylum tricornutum by a three-step process: fatty acid extraction by direct saponification of biomass, polyunsaturated fatty acid (PUFA) concentration by formation of urea inclusion compounds, and EPA isolation by semipreparative high-performance liquid chromatography (HPLC). Alternatively, EPA was obtained by a similar two-step process without the PUFA concentration step by the urea method. Direct saponification of biomass was carried out with two solvents that contained KOH for lipid saponification. An increase in yield was obtained because the problems associated with emulsion formation were avoided by separating the biomass from the soap solution before adding hexane for extraction of insaponifiables. The most efficient solvent, ethanol (96%) at 60°C for 1 h, extracted 98.3% of EPA. PUFA were concentrated by the urea method with a urea/fatty acid ratio of 4∶1 at a crystallization temperature of 28°C and by using methanol and ethanol as urea solvents. An EPA concentration ratio of 1.73 (55.2∶31.9) and a recover yield of 78.6% were obtained with methanol as the urea solvent. This PUFA concentrate was used to obtain 93.4% pure EPA by semipreparative HPLC with a reverse-phase, C₁₈, 10 mm i.d.×25-cm column and methanol/water (1% acetic acid), 80∶20 w/w, as the mobile phase. Eighty-five percent of EPA loaded was recovered, and 65.7% of EPA present inP. tricornutum biomass was recovered in highly pure form by this three-step downstream process. Alternatively, 93.6% pure EPA was isolated from the fatty acid extract (without the PUFA concentration step) with 100% EPA recovery yield. This two-step process increases the overall EPA yield to 98.3%, but it is only possible to obtain 20% as much EPA as that obtained by three-step downstream processing.     

The triglyceride composition,structure, and presence of estolides in the oils ofLesquerella and related species

Members of the genusLesquerella, native to North America, have oils containing large amounts of hydroxy fatty acids and are under investigation as potential new crops. The triglyceride structure of oils from twenty-fiveLesquerella species in the seed collection at our research center has been examined after being hydrolysis-catalyzed by reverse micellar-encapsulated lipase and alcoholysis-catalyzed by immobilized lipase. These reactions, when coupled with supercritical-fluid chromatographic analysis, provide a powerful, labor-saving method for oil triglyceride analysis. A comprehensive analysis of overall fatty acid composition of these oils has been conducted as well.Lesquerella oils (along with oils from two other Brassicaceae:Physaria floribunda andHeliophilia amplexicaulis) have been grouped into five categories: densipolic acid-rich (Class I); auricolic acid-rich (Class II); lesquerolic acid-rich (Class III); an oil containing a mixture of hydroxy acids (Class IV); and lesquerolic and erucic acid-rich (Class V). The majority of Class I and II triglycerides contain one or two monoestolides at the 1- and 3-glycerol positions and a C₁₈ polyunsaturated acyl group at the 2-position. Most Class III and IV oil triglycerides contain one or two hydroxy acids at the 1- and 3-positions and C₁₈ unsaturated acid at the 2-position. A few of the Class III oils have trace amounts of estolides. The Class V oil triglycerides are mostly pentaacyl triglycerides and contain monestolide and small amounts of diestolide. Our triglyceride structure assignments were supported by¹H nuclear magnetic resonance data and mass balances.